Cu-Catalyzed, Mn-Mediated Propargylation and Allenylation of Aldehydes with Propargyl Bromides

Cu-Catalyzed, Mn-Mediated Propargylation and Allenylation of Aldehydes with Propargyl Bromides | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Cu-Catalyzed, Mn-Mediated Propargylation and Allenylation of Aldehydes with Propargyl Bromides Rongli Zhang, Yanping Xia, Yuchen Yan, Lu Ouyang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1080113/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 18 Mar, 2022 Read the published version in BMC Chemistry → Version 1 posted 10 You are reading this latest preprint version Abstract A simple, practical, and high chemo-selective method for the synthesis of propargyl alcohol and allenyl alcohols via Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides has been established. When 3-bromo-1-propyne was conducted under the standard condition, the aldehydes were transformed to the corresponding propargylation products completely, while when 1-bromo-2-pentyne was used, allenic alcohol was the only product. Variety of homopropargyl alcohols and allenyl alcohols were obtained in high yields and the reaction is compatible with broad substrate scopes. In addition, the large-scale reaction could also be proceeded smoothly indicating the potential synthetic applications of this transformation. Inorganic Chemistry Propargylation Allenylation Mn powder Cu-catalyzed Gram scale Figures Figure 1 Figure 2 Introduction Propargyl and allenyl groups are not only valuable building blocks for further manipulations and organic transformations in organic synthesis, 1 but also sever as active structural moieties in plentiful functional molecules which are important in bioactive molecules, pharmaceuticals agents and natural products. 2 Thus, this interesting and promising synthetic method has been attracting a great deal of attentions. 3 Numerous methods have been established by using propargyl halides and metals to produce the nucleophilic character of the propargyl metal species. 4 When the nucleophilic receptor is an aldehyde, the homopropargyl alcohol can be obtained by the nucleophilic addition of propargyl metal species and aldehyde. 5 Variety of metals, including In, 6 Sb, 7 Pb, 8 Ti, 9 Cr, 10 Ga, 11 Sn, 12 Zn 13 Mn, 14 and Sc 15 , have been used for this coupling reaction which could afford the corresponding homopropargyl alcohols. While, the by-product allenyl alcohol is inevitable, which can be owned to the rearrangement of the crucial intermediate progargyl metal species to allenyl metal species. 16 Therefore, a mixture of homopropargyl alcohol and allenyl alcohol were generally obtained. Despite the encouraging progress has been made, long reaction time-cost, moderate yields and low chemo-selectivity has limited the applications. Therefore, there is still demands for the improved method with respect to selectivities for homopropargyl alcohol and allenyl alcohols. As we known, Cu catalyst, is not only abundant, easy to utilize, and relatively insensitive to water and air, but also has advantageous for the controllable access to Cu(0), Cu(I), Cu(II), and Cu(III) oxidation states; 17 possibly because of its single-electron transfer (SET) and two-electron processes (TEPs) pathway, 18 which make the catalytic system with high catalytic activities and rate. Moreover, Manganese has been widely used in organic reactions by virtue of its environmentally benign and sustainable nature, low cost and versatile reactivity 19 However, Mn-mediated proparylation reaction was discovered with only few examples. The combination of Cu-catalyst and Mn powder may increase the catalytic efficiency. In this paper, we developed the first example of Cu-catalyzed and Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides under a novel catalytic system, which is covered with advantages of high efficiency, good chemo-selectivity, and wide substrates scopes under mild reaction conditions (Figure 1). We initiated our investigation using benzaldehyde ( 1a ) and propargyl bromide ( 2a ) as model substrates which catalyzed by copper salts and Mn powder (Table 1). Without Mn, only trace amount of desired product was observed which indicated that Mn powder is indispensable (Table 1, entry 1). While in the absence of CuBr 2 , 16% of 3a was produced which demonstrated the great importance of Cu catalyst (entry 2). Screening of different solvents illustrated that MeCN is the best reaction medium, giving the desired product 3a in 47% yield (entries 3). While, only trace amount of product was observed in THF or DCM and 24% in EtOH (entries 4-6). The yield of products dropped sharply when the reaction was carried out in the open system (entry 7). Meanwhile, without the addition of CF 3 COOH, only 13% yield of 3a was achieved (entry 8). Subsequently, extensive experiments were conducted to investigate the effects of different copper salts on the reaction. Series of Cu catalysts, including CuSO 4 , CuCl, CuCl 2 , CuBr and CuI were tested and CuCl gave the best result (entries 9-13). Adding 5 equiv. Mn powder, a remarkable increase has been presented (entry 14). Simultaneously, a light increase of yield was observed by increasing the amount of catalyst (entry 15). Further studies indicated that extending the reaction time to 24 h, 1a can be transformed to 3a completely under the standard conditions (entry 16). With the optimized setup in hand, we next explored the substrates scope of aldehydes with different functional groups as shown in Table 2. It is pleasing that substrates bearing both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) can proceed smoothly. For example, substrates 3c , 3e , 3f , 3g , 3h , 3i and 3k with alkyl and alkoxy groups can be transformed to the corresponding products in excellent yield. Substrates containing the halogen ( 3b , 3d , 3i , 3j ) can also deliver the corresponding products with excellent yields. In addition, disubstituted benzaldehydes, such as 2,4-dimethyl ( 3l ), 2,3-dimethyl ( 3o ), 2,5-difluoro ( 3m ), 2,3-difluoro ( 3n ), 2-methoxy-4-methyl ( 3p ) 3-chloro-5-fluoro ( 3q ), 3-methoxy-4-fluoro ( 3r ) and 3-methyl-4-fluor ( 3s ) benzaldehydes were found to be compatible with the reaction in 85%- 95% yields. To further expand the scopes of the present catalytic system, reactions of heteroaromatic aldehydes including thiophenecarboxaldehyde ( 3u ), pyridylaldehydes ( 3v and 3w ) and quinolinecarboxaldehyde ( 3x ) which contain aromatic heterocycle in the molecules were also explored. Interesting, all of these substrates were compatible with the reaction conditions and produced the homopropargyl alcohols in excellent yield. Naphthyl compounds is also effective for the transformation converted to 3y and 3z in the yield of 94% and 96% respectively. When 1-bromo-2-pentyne ( 4a ) was used instead of propargyl bromide, the rearrangement product allenyl alcohol was achieved with good yield under the same reaction conditions (Table 3). Importantly, the direct propargylation product was not detected in this catalytic system, which indicated that the chemo-selectivity for this reaction is quite good. For example, substrates which substituted by isopropyl-( 5a ), methyl-( 5b ) and fluoro-( 5c ) groups on the aromatic ring, reacted well and provided the corresponding products in moderate yields. In addition, heteroaromatic aldehyde is also worked for the transformation and an allenyl substituted alcohol ( 5e ) was obtained with 85% yield. To demonstrate the synthetic applications of our protocols, we tried to scale up the reaction of benzaldehyde ( 1a) with 3-bromo-1-propyne ( 2a ) or 1-bromo-2-pentyne ( 4a ) independently under standard conditions (Figure 2). The corresponding products 3a or 5a was obtained in a gram-scale, which highlightened the potential applicability of this transformation in organic synthesis. Experimental Procedure for the synthesis of homopropargyl alcohol In a 10 mL Schlenk tube, a mixture of aldehyde (0.5 mmol), was added to a stirred solution of 3-bromo-1-propyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), CF 3 COOH (25 mol%) and MeCN (2 mL) at room temperature under N 2 atmosphere. After 24 hours, the mixture was extracted with EtOAc (3 × 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph. Procedure for the synthesis of allenyl alchols In a 10 mL Schlenk tube, a mixture of aldehyde (0.5 mmol), was added to a stirred solution of 1-bromo-2-pentyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), CF 3 COOH (25 mol%) and MeCN (2 mL) at room temperature under N 2 atmosphere. After 24 hours, the mixture was extracted with EtOAc (3 × 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph. 1-phenylbut-3-yn-1-ol (3a) 20 ： 98% yield (71.6 mg), colourless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.46-7.34 (m, 4H), 7.30 (ddd, J = 8.5, 3.6, 1.6 Hz, 1H), 4.88 (t, J = 5.4 Hz, 1H), 2.71-2.56 (m, 2H), 2.45 (s, 1H), 2.19-1.96 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 142.4, 128.5, 128.0, 125.8, 80.7, 72.3, 71.0, 29.5. 1-(4-chlorophenyl)but-3-yn-1-ol (3b) 20 ： 96% yield (86.7 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.33-7.25 (m, 4H), 4.80 (t, J = 5.1 Hz, 1H), 2.81 (s, 1H), 2.58 (dd, J = 6.4, 2.5 Hz, 2H), 2.06 (dd, J = 3.4, 1.7 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.9, 133.7, 128.6, 127.2, 80.3, 71.6, 71.4, 29.4. 1-(p-tolyl)but-3-yn-1-ol (3c) 20 ： 91% yield (72.8 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.25 (d, J = 7.7 Hz, 2H), 7.14 (d, J = 7.7 Hz, 2H), 4.79 (s, 1H), 2.58 (dd, J = 11.1, 8.7 Hz, 3H), 2.33 (s, 3H), 2.03 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.6, 137.7, 129.2, 125.8, 80.9, 72.2, 70.9, 29.3, 21.2. 1-(4-fluorophenyl)but-3-yn-1-ol (3d) 20 ： 97% yield (79.6 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.46-7.32 (m, 2H), 7.05 (t, J = 8.7 Hz, 2H), 4.86 (t, J = 5.5 Hz, 1H), 2.62 (dd, J = 6.3, 2.6 Hz, 2H), 2.49 (d, J = 2.5 Hz, 1H), 2.08 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.4 (d, J = 245 Hz), 138.2 (d, J = 3 Hz), 127.5 d, J = 8 Hz), 115.4 (d, J = 21 Hz), 80.4, 71.7, 71.2, 29.6. 1-(4-methoxyphenyl)but-3-yn-1-ol (3e) 20 ： 89% yield (78.4 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.29 (d, J = 8.6 Hz, 2H), 6.95-6.80 (m, 2H), 4.80 (t, J = 6.4 Hz, 1H), 3.79 (s, 3H), 2.64-2.58 (m, 2H), 2.05 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 159.3, 134.8, 127.1, 113.9, 80.9, 72.0, 70.9, 55.3, 29.3. 1-(4-isopropylphenyl)but-3-yn-1-ol (3f) 20 ： 89% yield (83.7 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.30 (d, J = 8.1 Hz, 2H), 7.21 (d, J = 8.2 Hz, 2H), 4.82 (s, 1H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.06 (t, J = 2.6 Hz, 1H), 1.24 (d, J = 6.9 Hz, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 148.7, 139.9, 126.6, 125.8, 81.0, 72.3, 70.9, 33.9, 29.3, 24.0. 1-(3-methoxyphenyl)but-3-yn-1-ol (3g) 20 ： 95% yield (83.6 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.27 (dd, J = 10.3, 5.9 Hz, 1H), 6.99-6.93 (m, 2H), 6.84 (ddd, J = 8.2, 2.5, 1.0 Hz, 1H), 4.85 (t, J = 6.3 Hz, 1H), 3.81 (s, 3H), 2.69-2.59 (m, 2H), 2.51 (s, 1H), 2.08 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 159.7, 144.2, 129.6, 118.1, 113.5, 111.3, 80.7, 72.3, 71.0, 55.3, 29.4. 1-(m-tolyl)but-3-yn-1-ol (3h) 20 ： 83% yield (66.5 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.24 (t, J = 7.5 Hz, 1H), 7.21-7.14 (m, 2H), 7.10 (d, J = 7.4 Hz, 1H), 4.82 (t, J = 6.4 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.35 (s, 3H), 2.06 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 142.5, 138.2, 128.8, 128.4, 126.4, 122.9, 80.9, 72.4, 70.9, 29.4, 21.5. 1-(2-chlorophenyl)but-3-yn-1-ol (3i) 20 ： 96% yield (86.4 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.62 (dd, J = 7.7, 1.4 Hz, 1H), 7.36-7.26 (m, 2H), 7.26-7.20 (m, 1H), 5.28 (dd, J = 7.8, 4.0 Hz, 1H), 2.80 (ddd, J = 16.9, 3.9, 2.7 Hz, 1H), 2.69 (s, 1H), 2.54 (ddd, J = 16.9, 7.8, 2.6 Hz, 1H), 2.10 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.7, 131.7, 129.4, 129.0, 127.1, 127.1, 80.3, 71.2, 68.7, 27.7. 1-(2-fluorophenyl)but-3-yn-1-ol (3j) 20 ： 95% yield (79.9 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.52 (td, J = 7.5, 1.5 Hz, 1H), 7.26 (ddd, J = 7.1, 4.6, 1.9 Hz, 1H), 7.16 (td, J = 7.5, 0.8 Hz, 1H), 7.02 (ddd, J = 10.4, 8.2, 0.9 Hz, 1H), 5.18 (dd, J = 7.2, 4.9 Hz, 1H), 2.74 (ddd, J = 16.8, 4.7, 2.6 Hz, 1H), 2.62 (ddd, J = 16.8, 7.6, 2.6 Hz, 2H), 2.07 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.0 (d, J = 244 Hz), 129.5, 129.3 (d, J = 8 Hz), 127.2 (d, J = 4 Hz), 124.3 (d, J = 3 Hz), 115.3 (d, J = 22 Hz), 80.3, 71.1, 66.4 (d, J = 2 Hz), 28.2. 1-(4-propoxyphenyl)but-3-yn-1-ol (3k) 20 ： 85% yield (86.8 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.30 (d, J = 8.5 Hz, 2H), 6.88 (d, J = 8.5 Hz, 2H), 4.83 (t, J = 6.2 Hz, 1H), 3.91 (t, J = 6.6 Hz, 2H), 2.68-2.58 (m, 2H), 2.36 (s, 1H), 2.07 (d, J = 2.3 Hz, 1H), 1.80 (dd, J = 14.1, 7.0 Hz, 2H), 1.03 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.9, 134.4, 127.0, 114.4, 80.9, 72.1, 70.8, 69.5, 29.4, 22.6, 10.5. 1-(2,4-dimethylphenyl)but-3-yn-1-ol (3l) 20 ： 85% yield (74.0 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.36 (d, J = 7.9 Hz, 1H), 7.03 (d, J = 7.7 Hz, 1H), 6.95 (s, 1H), 5.04 (t, J = 6.4 Hz, 1H), 2.62-2.54 (m, 2H), 2.45 (d, J = 4.8 Hz, 1H), 2.30 (s, 3H), 2.29 (s, 3H), 2.05 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 137.6, 137.4, 134.6, 131.3, 127.0, 125.1, 81.1, 70.7, 68.8, 28.3, 21.0, 19.0. 1-(2,5-difluorophenyl)but-3-yn-1-ol (3m) 20 ： 94% yield (85.6 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.26 (ddd, J = 8.8, 5.8, 3.0 Hz, 1H), 7.10-6.79 (m, 2H), 5.24-5.07 (m, 1H), 2.83-2.48 (m, 3H), 2.10 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.9 (dd, J = 241, 2 Hz), 155.3 (dd, J = 238, 3 Hz), 131.2 (dd, J = 16, 7 Hz), 116.3 (dd, J = 24, 8 Hz), 115.5 (dd, J = 24, 9 Hz), 113.9 (dd, J = 25, 4 Hz), 79.7, 71.6, 65.9, 28.2 (d, J = 1 Hz). 1-(2,3-difluorophenyl)but-3-yn-1-ol (3n) 20 ： 87% yield (79.2 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.33-7.23 (m, 1H), 7.18-7.01 (m, 2H), 5.19 (dd, J = 6.9, 5.2 Hz, 1H), 2.82 (s, 1H), 2.74 (ddd, J = 16.8, 4.8, 2.6 Hz, 1H), 2.63 (ddd, J = 16.8, 7.4, 2.5 Hz, 1H), 2.08 (t, J = 2.5 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 150.2 (dd, J = 246, 12 Hz), 147.6 (dd, J = 246, 13), 131.9 (d, J = 10 Hz), 124.2 (dd, J = 7, 5 Hz), 121.8 (t, J = 3 Hz), 116.5 (d, J = 2 Hz), 79.8, 71.4, 66. 0 (t, J = 2 Hz), 28.2. 1-(2,3-dimethylphenyl)but-3-yn-1-ol (3o) 20 ： 87% yield (75.7 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.36 (d, J = 7.4 Hz, 1H), 7.17-7.04 (m, 2H), 5.15 (dd, J = 7.6, 5.0 Hz, 1H), 2.61-2.51 (m, 2H), 2.28 (s, 3H), 2.22 (s, 3H), 2.07 (d, J = 2.4 Hz, 1H), 1.97 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.4, 137.0, 133.2, 129.4, 125.8, 122.9, 81.2, 70.7, 69.3, 28.3, 20.7, 14.7. 1-(2-methoxy-4-methylphenyl)but-3-yn-1-ol (3p) 20 ： 85% yield (80.8 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.25 (d, J = 7.6 Hz, 1H), 6.77 (d, J = 7.6 Hz, 1H), 6.68 (s, 1H), 5.09- 4.96 (m, 1H), 3.83 (d, J = 6.7 Hz, 3H), 2.98 (s, 1H), 2.67 (dddd, J = 24.2, 10.1, 6.3, 2.6 Hz, 2H), 2.34 (s, 3H), 2.03 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.2, 138.9, 127.4, 126.8, 121.2, 111.4, 81.5, 70.4, 68.9, 55.2, 27.5, 21.6. 1-(3-chloro-5-fluorophenyl)but-3-yn-1-ol (3q) 20 ： 95% yield (94.1 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.19 (s, 1H), 7.07-6.99 (m, 2H), 4.84 (t, J = 4.6 Hz, 1H), 2.65-2.61 (m, 1H), 2.59 (dd, J = 6.5, 3.0 Hz, 1H), 2.11 (t, J = 2.6 Hz, 1H), 1.68 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 163.7 (d, J = 248 Hz), 146.2 (d, J = 7 Hz), 135.1 (d, J = 10 Hz), 121.9 (d, J = 4 Hz), 115.6 (d, J = 25 Hz), 111.4 (d, J = 22 Hz), 79.6, 71.8, 71.2 (d, J = 2 Hz), 29.4. 1-(4-fluoro-3-methoxyphenyl)but-3-yn-1-ol (3r) 20 ： 88% yield (85.4 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.09-7.01 (m, 2H), 6.88 (ddd, J = 8.3, 4.3, 2.1 Hz, 1H), 4.83 (t, J = 6.3 Hz, 1H), 3.89 (d, J = 5.9 Hz, 3H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.55 (s, 1H), 2.09 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 151.914.7 (d, J = 244 Hz), 147.6 (d, J = 11 Hz), 138.8 (d, J = 3 Hz), 118.1 (d, J = 7 Hz), 115.8 (d, J = 19 Hz), 110.9 (d, J = 2 Hz), 80.4, 71.9, 71.3, 56.2, 29.6. 1-(4-fluoro-3-methylphenyl)but-3-yn-1-ol (3s) 20 ： 88% yield (78.4 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.24-7.08 (m, 2H), 6.97 (t, J = 8.9 Hz, 1H), 4.81 (t, J = 6.3 Hz, 1H), 2.61 (dd, J = 6.3, 2.4 Hz, 2H), 2.45 (s, 1H), 2.27 (s, 3H), 2.08 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.9 (d, J = 243 Hz), 137.87, 128.9 (d, J = 2 Hz), 125.0, 124.7(d, J = 8 Hz), 114.9 (d, J = 22 Hz), 80.6, 71.8, 71.1, 29.5, 14.7(d, J = 4 Hz) 2-(benzo[d][1,3]dioxol-4-yl)but-3-yn-1-ol (3t) 20 ： 85% yield (80.8 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 6.95-6.89 (m, 1H), 6.84 (t, J = 7.8 Hz, 1H), 6.78 (dd, J = 7.6, 1.0 Hz, 1H), 5.96 (dd, J = 9.2, 1.1 Hz, 2H), 4.98 (dd, J = 10.2, 6.3 Hz, 1H), 2.84-2.58 (m, 3H), 2.06 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.4, 144.1, 124.1, 121.8, 119.3, 108.2, 101.0, 80.5, 70.9, 68.3, 27.6. 1-(thiophen-2-yl)but-3-yn-1-ol (3u) 20 ： 88% yield (66.9 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.32-7.22 (m, 1H), 6.99 (ddd, J = 11.1, 6.1, 2.5 Hz, 2H), 5.11 (d, J = 3.7 Hz, 1H), 2.79-2.68 (m, 3H), 2.11 (dd, J = 5.2, 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.2, 126.7, 125.0, 124.2, 80.1, 71.5, 68.5, 29.5. 1-(4-chloropyridin-2-yl)but-3-yn-1-ol (3v) 20 ： 93% yield (84.1 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 8.46 (d, J = 5.3 Hz, 1H), 7.49 (d, J = 1.7 Hz, 1H), 7.26 (dd, J = 5.4, 2.0 Hz, 1H), 4.88 (t, J = 6.0 Hz, 1H), 2.78-2.65 (m, 2H), 2.06 (t, J = 2.6 Hz, 1H), 1.25 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.0, 149.4, 144.9, 123.3, 121.2, 80.0, 71.3, 71.1, 28.2. 1-(pyridin-3-yl)but-3-yn-1-ol (3w) 20 ： 95% yield (69.9 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 8.54 (d, J = 2.0 Hz, 1H), 8.47 (dd, J = 4.8, 1.5 Hz, 1H), 7.79 (dt, J = 7.9, 1.8 Hz, 1H), 7.33-7.26 (m, 1H), 4.92 (t, J = 6.4 Hz, 1H), 2.70-2.65 (m, 2H), 2.08 (t, J = 2.6 Hz, 1H), 1.35 – 1.23 (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 148.9, 147.6, 138.3, 133.9, 123.5, 79.9, 71.5, 70.0, 29.3. 1-(quinolin-2-yl)but-3-yn-1-ol (3x) 20 ： 93% yield (92.0 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (d, J = 8.5 Hz, 1H), 8.09 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 8.4, 1.4 Hz, 1H), 7.59-7.49 (m, 2H), 5.07 (t, J = 5.9 Hz, 1H), 2.80 (ddd, J = 5.9, 2.5, 1.7 Hz, 2H), 2.02 (t, J = 2.7 Hz, 1H), 1.25 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.0, 146.5, 137.0, 129.9, 128.9, 127.8, 127.7, 126.7, 118.5, 80.5, 71.0, 71.0, 28.3. 1-(naphthalen-2-yl)but-3-yn-1-ol (3y) 20 ： 94% yield (92.5 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.87-7.70 (m, 4H), 7.56-7.36 (m, 3H), 4.98 (t, J = 6.3 Hz, 1H), 2.75 (s, 1H), 2.69 (dd, J = 6.4, 2.6 Hz, 2H), 2.05 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.9, 133.2, 133.2, 128.4, 128.1, 127.8, 126.3, 126.1, 124.8, 123.8, 80.8, 72.5, 71.2, 29.4. 1-(naphthalen-1-yl)but-3-yn-1-ol (3z) 20 ： 96% yield (94.1 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 8.04 (d, J = 8.2 Hz, 1H), 7.89-7.83 (m, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.69 (d, J = 7.2 Hz, 1H), 7.54-7.44 (m, 3H), 5.63 (dd, J = 8.2, 4.2 Hz, 1H), 2.87 (ddd, J = 17.0, 4.2, 2.7 Hz, 1H), 2.73 (ddd, J = 17.0, 8.2, 2.6 Hz, 2H), 2.12 (t, J = 2.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 137.8, 133.8, 130.2, 129.1, 128.5, 126.3, 125.7, 125.4, 123.0, 122.8, 81.0, 71.3, 69.3, 28.7. 1-(4-isopropylphenyl)-2-methyl-3 λ 5-buta-2,3-dien-1-ol (5a) 20 ： 76% yield (76.8 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.30 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 5.07 (s, 1H), 4.96-4.85 (m, 2H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.18 (s, 1H), 1.58 (t, J = 3.0 Hz, 3H), 1.24 (d, J = 7.0 Hz, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 204.6, 148.6, 139.2, 126.6, 126.5, 102.7, 77. 9, 74.5, 33.9, 24.0, 14.7. 2-methyl-1-(p-tolyl)-3 λ 5-buta-2,3-dien-1-ol (5b) 20 ： 83% yield (54.9 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.25 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 7.9 Hz, 2H), 5.05 (s, 1H), 4.96-4.82 (m, 2H), 2.34 (s, 3H), 2.30 (s, 1H), 1.56 (t, J = 3.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 204.7, 138.9, 137.5, 129.1, 126. 6, 102.7, 77.8, 74.5, 21.2, 14.7. 1-(4-fluorophenyl)-2-methyl-3 λ 5-buta-2,3-dien-1-ol (5c) 20 ： 73% yield (73 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.34 (dd, J = 8.4, 5.6 Hz, 2H), 7.03 (t, J = 8.7 Hz, 2H), 5.08 (s, 1H), 4.93-4.86 (m, 2H), 2.39 (s, 1H), 1.55 (t, J = 3.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.3(d, J = 244 Hz), 137.5 (d, J = 3 Hz), 128.3 (d, J = 8 Hz), 115.2 (d, J = 21 Hz), 102.6, 78.1, 77.4, 74.0, 14.5. 2-methyl-1-(thiophen-2-yl)-3 λ 5-buta-2,3-dien-1-ol (5d) 20 ： 76% yield (63.1 mg), colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ 7.29-7.25 (m, 1H), 7.02 (d, J = 3.1 Hz, 1H), 6.99-6.95 (m, 1H), 5.35 (s, 1H), 4.99-4.86 (m, 2H), 2.34 (d, J = 4.4 Hz, 1H), 1.69 (t, J = 3.0 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 204.4, 146.1, 126.6, 125.2, 125.0, 102.6, 78.6, 70.7, 14.7. Conclusions In conclusion, we have established the first Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides. The unique combination of the Cu catalyst and Mn powder present a novel and effective catalyst system in the preparation of homopropargylation alcohols and allenyl alcohols. The overall transformation is highly efficient with mild conditions, large substrate scope, and excellent chem-selectivity. Declarations Ethics approval and consent to participate Not applicable. Consent for publication NA. Competing interests The authors declare no competing interests. Availability of data and materials All data generated or analyzed during this study are included in this published and its supplementary information files. Funding The authors thank the National Natural Science Foundation of China (22161003) and the Project of Science and Technology of Xuzhou Government (No. KC16SG250) Acknowledgement NA Author details 1 Xuzhou Medical University, Tongshan Road 209, Xuzhou, 221004, China. 2 School of Pharmaceutical Sciences, Gannan Medical University, Ganzhou 341000, China Authors’ contributions ZRL contributed to the conception of the study. XY and OL performed the experiment. ZRL and YYC contributed to analysis and manuscript preparation. All authors read and approved the final manuscript. References (a) Alami, M.; Hamze, A.; Provot, O.; ACS Catal. 2019 , 9, 3437. (b) Parker, K. D. J.; Fryzuk, M. D. Organometallics 2015 , 34, 2037. (c) Corpas, J.; Mauleón, P.; Gómez Arrayá, M.; Carretero, J. C. ACS Catal. 2021 , 11, 7513. (d) Gilmore, K.; Alabugin, I. V. Chem. Rev. 2011 , 111, 6513. (e) Liu, L.; Ward, R. M.; Schomaker, J. M. Chem. Rev. 2019 , 119, 12422. 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Tables Tables 1-3 are available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files BMC20211015SI.doc Table1.docx Table2.docx Table3.docx Cite Share Download PDF Status: Published Journal Publication published 18 Mar, 2022 Read the published version in BMC Chemistry → Version 1 posted Editorial decision: Major revision 16 Dec, 2021 Reviews received at journal 12 Dec, 2021 Reviewers agreed at journal 07 Dec, 2021 Reviewers agreed at journal 03 Dec, 2021 Reviewers agreed at journal 01 Dec, 2021 Reviewers invited by journal 29 Nov, 2021 Editor assigned by journal 24 Nov, 2021 Editor invited by journal 24 Nov, 2021 Submission checks completed at journal 24 Nov, 2021 First submitted to journal 14 Nov, 2021 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Zhang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA1ElEQVRIiWNgGAWjYBACNvkDyQ8SeGzq2/ibDxCnhU+C4ZnBB5k0xn6JYwnEaZGTYHwgOcPmEOPMhhwDIh0m3ZxgzJNzgNngwJmPN94w2MnpNhDSInMs4THPmTtsBod7N1vOYUg2NjtASAtDToIxb88zHoMDZ7dJ8zAcSNxGWEv+B2nef4clDA7kPCNSi0RCguQMnsMGkg05bERq4TmQZvCBJy2BX+KYseUcAyL8It/eAI7KBDb+5oc33lTYyRHUggIkeIiMGmQtpOoYBaNgFIyCEQEATXxEziyBiQcAAAAASUVORK5CYII=","orcid":"","institution":"Xuzhou Medical University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Rongli","middleName":"","lastName":"Zhang","suffix":""},{"id":65247549,"identity":"0304b729-8674-4985-bb74-ca8138b28207","order_by":1,"name":"Yanping Xia","email":"","orcid":"","institution":"Gannan Medical University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yanping","middleName":"","lastName":"Xia","suffix":""},{"id":65247550,"identity":"4206a05f-c9ed-4664-a77d-553d32ee9d95","order_by":2,"name":"Yuchen Yan","email":"","orcid":"","institution":"Xuzhou Medical University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yuchen","middleName":"","lastName":"Yan","suffix":""},{"id":65247551,"identity":"55d4a0eb-3d75-4d10-b1f1-d63f798cca1c","order_by":3,"name":"Lu Ouyang","email":"","orcid":"","institution":"Gannan Medical University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Lu","middleName":"","lastName":"Ouyang","suffix":""}],"badges":[],"createdAt":"2021-11-15 01:14:03","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1080113/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1080113/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1186/s13065-022-00803-3","type":"published","date":"2022-03-18T16:48:47+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":15867113,"identity":"8e2038dd-f3c9-4563-88de-3ee8291cbf2b","added_by":"auto","created_at":"2021-11-24 14:50:40","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":109362,"visible":true,"origin":"","legend":"Previous studies and our concept.","description":"","filename":"ScreenShot20211122at4.47.58PM.png","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/c102e21523aa1a4a2df6daa5.png"},{"id":15867114,"identity":"1d60a895-af5f-45a1-9dda-baedacce8770","added_by":"auto","created_at":"2021-11-24 14:50:40","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":33085,"visible":true,"origin":"","legend":"Gram-scale synthesis of 3a and 5a","description":"","filename":"ScreenShot20211122at4.48.19PM.png","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/3add2b5eaebba6d2d105dd71.png"},{"id":19374713,"identity":"0d5138c4-db1f-4978-a84c-70ab930b5d3a","added_by":"auto","created_at":"2022-03-18 16:48:55","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":650310,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/203d9bf5-1af1-4f5d-ab8e-f697e802b1e1.pdf"},{"id":15867116,"identity":"d69da7a3-3a21-4300-9f1d-6101ec22cb0e","added_by":"auto","created_at":"2021-11-24 14:50:40","extension":"doc","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3773952,"visible":true,"origin":"","legend":"","description":"","filename":"BMC20211015SI.doc","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/dd0f267cd96fc6deb0b9da78.doc"},{"id":15867115,"identity":"ad3d31ab-e553-4a9a-b456-dccc0c302603","added_by":"auto","created_at":"2021-11-24 14:50:40","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":45458,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/c23e6173c05a1804f96dfee2.docx"},{"id":15867117,"identity":"f7127be9-db5a-4b8a-b6f9-48aaedf7626d","added_by":"auto","created_at":"2021-11-24 14:50:40","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":91178,"visible":true,"origin":"","legend":"","description":"","filename":"Table2.docx","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/277bde37012368d9038bb1dd.docx"},{"id":15867370,"identity":"fd100965-470a-4da5-917f-3023b110cca3","added_by":"auto","created_at":"2021-11-24 14:53:40","extension":"docx","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":56067,"visible":true,"origin":"","legend":"","description":"","filename":"Table3.docx","url":"https://assets-eu.researchsquare.com/files/rs-1080113/v1/336f3a81192c0c575e35af49.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Cu-Catalyzed, Mn-Mediated Propargylation and Allenylation of Aldehydes with Propargyl Bromides","fulltext":[{"header":"Introduction","content":"\u003cp\u003ePropargyl and allenyl groups are not only valuable building blocks for further manipulations and organic transformations in organic synthesis,\u003csup\u003e1\u003c/sup\u003e but also sever as active structural moieties in plentiful functional molecules which are important in bioactive molecules, pharmaceuticals agents and natural products.\u003csup\u003e2\u003c/sup\u003e Thus, this interesting and promising synthetic method has been attracting a great deal of attentions.\u003csup\u003e3\u0026nbsp;\u003c/sup\u003eNumerous methods have been established by using propargyl halides and metals to produce the nucleophilic character of the propargyl metal species.\u003csup\u003e4\u003c/sup\u003e When the nucleophilic receptor is an aldehyde, the homopropargyl alcohol can be obtained by the nucleophilic addition of propargyl metal species and aldehyde.\u003csup\u003e5\u003c/sup\u003e Variety of metals, including In,\u003csup\u003e6\u003c/sup\u003e Sb,\u003csup\u003e7\u003c/sup\u003e Pb,\u003csup\u003e8\u003c/sup\u003e Ti,\u003csup\u003e9\u003c/sup\u003e Cr,\u003csup\u003e10\u003c/sup\u003e Ga,\u003csup\u003e11\u003c/sup\u003e Sn,\u003csup\u003e12\u003c/sup\u003e Zn\u003csup\u003e13\u003c/sup\u003e Mn,\u003csup\u003e14\u003c/sup\u003e and Sc\u003csup\u003e15\u003c/sup\u003e, have been used for this coupling reaction which could afford the corresponding homopropargyl alcohols. While, the by-product allenyl alcohol is inevitable, which can be owned to the rearrangement of the crucial intermediate progargyl metal species to allenyl metal species.\u003csup\u003e16\u003c/sup\u003e Therefore, a mixture of homopropargyl alcohol and allenyl alcohol were generally obtained. Despite the encouraging progress has been made, long reaction time-cost, moderate yields and low chemo-selectivity has limited the applications. Therefore, there is still demands for the improved method with respect to selectivities for homopropargyl alcohol and allenyl alcohols.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAs we known, Cu catalyst, is not only abundant, easy to utilize, and relatively insensitive to water and air, but also has advantageous for the controllable access to Cu(0), Cu(I), Cu(II), and Cu(III) oxidation states;\u003csup\u003e17\u003c/sup\u003e possibly because of its single-electron transfer (SET) and two-electron processes (TEPs) pathway,\u003csup\u003e18\u003c/sup\u003e which make the catalytic system with high catalytic activities and rate. Moreover, Manganese has been widely used in organic reactions by virtue of its environmentally benign and sustainable nature, low cost and versatile reactivity\u003csup\u003e19\u003c/sup\u003e However, Mn-mediated proparylation reaction was discovered with only few examples. The combination of Cu-catalyst and Mn powder may increase the catalytic efficiency.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn this paper, we developed the first example of Cu-catalyzed and Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides under a novel catalytic system, which is covered with advantages of high efficiency, good chemo-selectivity, and wide substrates scopes under mild reaction conditions (Figure 1).\u003c/p\u003e\n\u003cp\u003eWe initiated our investigation using benzaldehyde (\u003cstrong\u003e1a\u003c/strong\u003e) and propargyl bromide (\u003cstrong\u003e2a\u003c/strong\u003e) as model substrates which catalyzed by copper salts and Mn powder (Table 1). Without Mn, only trace amount of desired product was observed which indicated that Mn powder is indispensable (Table 1, entry 1). While in the absence of CuBr\u003csub\u003e2\u003c/sub\u003e, 16% of \u003cstrong\u003e3a\u003c/strong\u003e was produced which demonstrated the great importance of Cu catalyst (entry 2). Screening of different solvents illustrated that MeCN is the best reaction medium, giving the desired product \u003cstrong\u003e3a\u003c/strong\u003e in 47% yield (entries 3). While, only trace amount of product was observed in THF or DCM and 24% in EtOH (entries 4-6). The yield of products dropped sharply when the reaction was carried out in the open system (entry 7). Meanwhile, without the addition of CF\u003csub\u003e3\u003c/sub\u003eCOOH, only 13% yield of \u003cstrong\u003e3a\u003c/strong\u003e was achieved (entry 8). Subsequently, extensive experiments were conducted to investigate the effects of different copper salts on the reaction. \u0026nbsp;Series of Cu catalysts, including CuSO\u003csub\u003e4\u003c/sub\u003e, CuCl, CuCl\u003csub\u003e2\u003c/sub\u003e, CuBr and CuI were tested and CuCl gave the best result (entries 9-13). Adding 5 equiv. Mn powder, a remarkable increase has been presented (entry 14). Simultaneously, a light increase of yield was observed by increasing the amount of catalyst (entry 15). Further studies indicated that extending the reaction time to 24 h, \u003cstrong\u003e1a\u003c/strong\u003e can be transformed to \u003cstrong\u003e3a\u003c/strong\u003e completely under the standard conditions (entry 16).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eWith the optimized setup in hand, we next explored the substrates scope of aldehydes with different functional groups as shown in Table 2. It is pleasing that substrates bearing both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) can proceed smoothly. For example, substrates \u003cstrong\u003e3c\u003c/strong\u003e, \u003cstrong\u003e3e\u003c/strong\u003e, \u003cstrong\u003e3f\u003c/strong\u003e, \u003cstrong\u003e3g\u003c/strong\u003e, \u003cstrong\u003e3h\u003c/strong\u003e, \u003cstrong\u003e3i\u003c/strong\u003e and \u003cstrong\u003e3k\u003c/strong\u003e with alkyl and alkoxy groups can be transformed to the corresponding products in excellent yield. Substrates containing the halogen (\u003cstrong\u003e3b\u003c/strong\u003e, \u003cstrong\u003e3d\u003c/strong\u003e, \u003cstrong\u003e3i\u003c/strong\u003e, \u003cstrong\u003e3j\u003c/strong\u003e) can also deliver the corresponding products with excellent yields. In addition, disubstituted benzaldehydes, such as 2,4-dimethyl (\u003cstrong\u003e3l\u003c/strong\u003e), 2,3-dimethyl (\u003cstrong\u003e3o\u003c/strong\u003e), 2,5-difluoro (\u003cstrong\u003e3m\u003c/strong\u003e), 2,3-difluoro (\u003cstrong\u003e3n\u003c/strong\u003e), 2-methoxy-4-methyl (\u003cstrong\u003e3p\u003c/strong\u003e) 3-chloro-5-fluoro (\u003cstrong\u003e3q\u003c/strong\u003e), 3-methoxy-4-fluoro (\u003cstrong\u003e3r\u003c/strong\u003e) \u0026nbsp;and 3-methyl-4-fluor (\u003cstrong\u003e3s\u003c/strong\u003e) benzaldehydes were found to be compatible with the reaction in 85%- 95% yields. To further expand the scopes of the present catalytic system, reactions of heteroaromatic aldehydes including thiophenecarboxaldehyde (\u003cstrong\u003e3u\u003c/strong\u003e), pyridylaldehydes (\u003cstrong\u003e3v\u003c/strong\u003e and \u003cstrong\u003e3w\u003c/strong\u003e) and quinolinecarboxaldehyde (\u003cstrong\u003e3x\u003c/strong\u003e) which contain aromatic heterocycle in the molecules were also explored. Interesting, all of these substrates were compatible with the reaction conditions and produced the homopropargyl alcohols in excellent yield. Naphthyl compounds is also effective for the transformation converted to \u003cstrong\u003e3y\u003c/strong\u003e and \u003cstrong\u003e3z\u003c/strong\u003e in the yield of 94% and 96% respectively.\u003c/p\u003e\n\u003cp\u003eWhen 1-bromo-2-pentyne (\u003cstrong\u003e4a\u003c/strong\u003e) was used instead of propargyl bromide, the rearrangement product allenyl alcohol was achieved with good yield under the same reaction conditions (Table 3). Importantly, the direct propargylation product was not detected in this catalytic system, which indicated that the chemo-selectivity for this reaction is quite good. For example, substrates which substituted by isopropyl-(\u003cstrong\u003e5a\u003c/strong\u003e), methyl-(\u003cstrong\u003e5b\u003c/strong\u003e) and fluoro-(\u003cstrong\u003e5c\u003c/strong\u003e) groups on the aromatic ring, reacted well and provided the corresponding products in moderate yields. In addition, heteroaromatic aldehyde is also worked for the transformation and an allenyl substituted alcohol (\u003cstrong\u003e5e\u003c/strong\u003e) was obtained with 85% yield.\u003c/p\u003e\n\u003cp\u003eTo demonstrate the synthetic applications of our protocols, we tried to scale up the reaction of benzaldehyde (\u003cstrong\u003e1a)\u003c/strong\u003e with 3-bromo-1-propyne (\u003cstrong\u003e2a\u003c/strong\u003e) or 1-bromo-2-pentyne (\u003cstrong\u003e4a\u003c/strong\u003e) independently under standard conditions (Figure 2). The corresponding products \u003cstrong\u003e3a\u003c/strong\u003e or \u003cstrong\u003e5a\u003c/strong\u003e was obtained in a gram-scale, which highlightened the potential applicability of this transformation in organic synthesis.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cp\u003e\u003cstrong\u003eProcedure for the synthesis of homopropargyl alcohol\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn a 10 mL Schlenk tube, a mixture of aldehyde (0.5 mmol), was added to a stirred solution of 3-bromo-1-propyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), CF\u003csub\u003e3\u003c/sub\u003eCOOH (25 mol%) and MeCN (2 mL) at room temperature under N\u003csub\u003e2\u003c/sub\u003e atmosphere. After 24 hours, the mixture was extracted with EtOAc (3 \u0026times; 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eProcedure for the synthesis of allenyl alchols\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn a 10 mL Schlenk tube, a mixture of aldehyde (0.5 mmol), was added to a stirred solution of 1-bromo-2-pentyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), CF\u003csub\u003e3\u003c/sub\u003eCOOH (25 mol%) and MeCN (2 mL) at room temperature under N\u003csub\u003e2\u003c/sub\u003e atmosphere. After 24 hours, the mixture was extracted with EtOAc (3 \u0026times; 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-phenylbut-3-yn-1-ol (3a)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e98% yield (71.6 mg), colourless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.46-7.34 (m, 4H), 7.30 (ddd, J = 8.5, 3.6, 1.6 Hz, 1H), 4.88 (t, J = 5.4 Hz, 1H), 2.71-2.56 (m, 2H), 2.45 (s, 1H), 2.19-1.96 (m, 1H);\u0026nbsp;\u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;142.4, 128.5, 128.0, 125.8, 80.7, 72.3, 71.0, 29.5.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-chlorophenyl)but-3-yn-1-ol (3b)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 96% yield (86.7 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.33-7.25 (m, 4H), 4.80 (t, J = 5.1 Hz, 1H), 2.81 (s, 1H), 2.58 (dd, J = 6.4, 2.5 Hz, 2H), 2.06 (dd, J = 3.4, 1.7 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;140.9, 133.7, 128.6, 127.2, 80.3, 71.6, 71.4, 29.4.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(p-tolyl)but-3-yn-1-ol (3c)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e91% yield (72.8 mg), colorless oil.\u003csup\u003e\u0026nbsp;1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.25 (d, J = 7.7 Hz, 2H), 7.14 (d, J = 7.7 Hz, 2H), 4.79 (s, 1H), 2.58 (dd, J = 11.1, 8.7 Hz, 3H), 2.33 (s, 3H), 2.03 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;139.6, 137.7, 129.2, 125.8, 80.9, 72.2, 70.9, 29.3, 21.2.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-fluorophenyl)but-3-yn-1-ol (3d)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 97% yield (79.6 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.46-7.32 (m, 2H), 7.05 (t, J = 8.7 Hz, 2H), 4.86 (t, J = 5.5 Hz, 1H), 2.62 (dd, J = 6.3, 2.6 Hz, 2H), 2.49 (d, J = 2.5 Hz, 1H), 2.08 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 162.4 (d, J = 245 Hz), 138.2 (d, J = 3 Hz), 127.5 d, J = 8 Hz), 115.4 (d, J = 21 Hz), 80.4, 71.7, 71.2, 29.6.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-methoxyphenyl)but-3-yn-1-ol (3e)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e89% yield (78.4 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.29 (d, J = 8.6 Hz, 2H), 6.95-6.80 (m, 2H), 4.80 (t, J = 6.4 Hz, 1H), 3.79 (s, 3H), 2.64-2.58 (m, 2H), 2.05 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 159.3, 134.8, 127.1, 113.9, 80.9, 72.0, 70.9, 55.3, 29.3.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-isopropylphenyl)but-3-yn-1-ol (3f)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e89% yield (83.7 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.30 (d, J = 8.1 Hz, 2H), 7.21 (d, J = 8.2 Hz, 2H), 4.82 (s, 1H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.06 (t, J = 2.6 Hz, 1H), 1.24 (d, J = 6.9 Hz, 6H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 148.7, 139.9, 126.6, 125.8, 81.0, 72.3, 70.9, 33.9, 29.3, 24.0.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(3-methoxyphenyl)but-3-yn-1-ol (3g)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e95% yield (83.6 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.27 (dd, J = 10.3, 5.9 Hz, 1H), 6.99-6.93 (m, 2H), 6.84 (ddd, J = 8.2, 2.5, 1.0 Hz, 1H), 4.85 (t, J = 6.3 Hz, 1H), 3.81 (s, 3H), 2.69-2.59 (m, 2H), 2.51 (s, 1H), 2.08 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 159.7, 144.2, 129.6, 118.1, 113.5, 111.3, 80.7, 72.3, 71.0, 55.3, 29.4.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(m-tolyl)but-3-yn-1-ol (3h)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e83% yield (66.5 mg),\u0026nbsp;colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.24 (t, J = 7.5 Hz, 1H), 7.21-7.14 (m, 2H), 7.10 (d, J = 7.4 Hz, 1H), 4.82 (t, J = 6.4 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.35 (s, 3H), 2.06 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 142.5, 138.2, 128.8, 128.4, 126.4, 122.9, 80.9, 72.4, 70.9, 29.4, 21.5.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2-chlorophenyl)but-3-yn-1-ol (3i)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e96% yield (86.4 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.62 (dd, J = 7.7, 1.4 Hz, 1H), 7.36-7.26 (m, 2H), 7.26-7.20 (m, 1H), 5.28 (dd, J = 7.8, 4.0 Hz, 1H), 2.80 (ddd, J = 16.9, 3.9, 2.7 Hz, 1H), 2.69 (s, 1H), 2.54 (ddd, J = 16.9, 7.8, 2.6 Hz, 1H), 2.10 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 139.7, 131.7, 129.4, 129.0, 127.1, 127.1, 80.3, 71.2, 68.7, 27.7.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2-fluorophenyl)but-3-yn-1-ol (3j)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e95% yield (79.9 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.52 (td, J = 7.5, 1.5 Hz, 1H), 7.26 (ddd, J = 7.1, 4.6, 1.9 Hz, 1H), 7.16 (td, J = 7.5, 0.8 Hz, 1H), 7.02 (ddd, J = 10.4, 8.2, 0.9 Hz, 1H), 5.18 (dd, J = 7.2, 4.9 Hz, 1H), 2.74 (ddd, J = 16.8, 4.7, 2.6 Hz, 1H), 2.62 (ddd, J = 16.8, 7.6, 2.6 Hz, 2H), 2.07 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 160.0 (d, J = 244 Hz), 129.5, 129.3 (d, J = 8 Hz), 127.2 (d, J = 4 Hz), 124.3 (d, J = 3 Hz), 115.3 (d, J = 22 Hz), 80.3, 71.1, 66.4 (d, J = 2 Hz), 28.2.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-propoxyphenyl)but-3-yn-1-ol (3k)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e85% yield (86.8 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.30 (d, J = 8.5 Hz, 2H), 6.88 (d, J = 8.5 Hz, 2H), 4.83 (t, J = 6.2 Hz, 1H), 3.91 (t, J = 6.6 Hz, 2H), 2.68-2.58 (m, 2H), 2.36 (s, 1H), 2.07 (d, J = 2.3 Hz, 1H), 1.80 (dd, J = 14.1, 7.0 Hz, 2H), 1.03 (t, J = 7.4 Hz, 3H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 158.9, 134.4, 127.0, 114.4, 80.9, 72.1, 70.8, 69.5, 29.4, 22.6, 10.5.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2,4-dimethylphenyl)but-3-yn-1-ol (3l)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e85% yield (74.0 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.36 (d, J = 7.9 Hz, 1H), 7.03 (d, J = 7.7 Hz, 1H), 6.95 (s, 1H), 5.04 (t, J = 6.4 Hz, 1H), 2.62-2.54 (m, 2H), 2.45 (d, J = 4.8 Hz, 1H), 2.30 (s, 3H), 2.29 (s, 3H), 2.05 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 137.6, 137.4, 134.6, 131.3, 127.0, 125.1, 81.1, 70.7, 68.8, 28.3, 21.0, 19.0.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2,5-difluorophenyl)but-3-yn-1-ol (3m)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e94% yield (85.6 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.26 (ddd, J = 8.8, 5.8, 3.0 Hz, 1H), 7.10-6.79 (m, 2H), 5.24-5.07 (m, 1H), 2.83-2.48 (m, 3H), 2.10 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;158.9 (dd, J = 241, 2 Hz), 155.3 (dd, J = 238, 3 Hz), 131.2 (dd, J = 16, 7 Hz), 116.3 (dd, J = 24, 8 Hz), 115.5 (dd, J = 24, 9 Hz), 113.9 (dd, J = 25, 4 Hz), 79.7, 71.6, 65.9, 28.2 (d, J = 1 Hz).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2,3-difluorophenyl)but-3-yn-1-ol (3n)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e87% \u0026nbsp;yield (79.2 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.33-7.23 (m, 1H), 7.18-7.01 (m, 2H), 5.19 (dd, J = 6.9, 5.2 Hz, 1H), 2.82 (s, 1H), 2.74 (ddd, J = 16.8, 4.8, 2.6 Hz, 1H), 2.63 (ddd, J = 16.8, 7.4, 2.5 Hz, 1H), 2.08 (t, J = 2.5 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 150.2 (dd, J = 246, 12 Hz), 147.6 (dd, J = 246, 13), 131.9 (d, J = 10 Hz), 124.2 (dd, J = 7, 5 Hz), 121.8 (t, J = 3 Hz), 116.5 (d, J = 2 Hz), 79.8, 71.4, 66. 0 (t, J = 2 Hz), 28.2.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2,3-dimethylphenyl)but-3-yn-1-ol (3o)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e87% \u0026nbsp;yield (75.7 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.36 (d, J = 7.4 Hz, 1H), 7.17-7.04 (m, 2H), 5.15 (dd, J = 7.6, 5.0 Hz, 1H), 2.61-2.51 (m, 2H), 2.28 (s, 3H), 2.22 (s, 3H), 2.07 (d, J = 2.4 Hz, 1H), 1.97 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 140.4, 137.0, 133.2, 129.4, 125.8, 122.9, 81.2, 70.7, 69.3, 28.3, 20.7, 14.7.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(2-methoxy-4-methylphenyl)but-3-yn-1-ol (3p)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e85% yield (80.8 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.25 (d, J = 7.6 Hz, 1H), 6.77 (d, J = 7.6 Hz, 1H), 6.68 (s, 1H), 5.09- 4.96 (m, 1H), 3.83 (d, J = 6.7 Hz, 3H), 2.98 (s, 1H), 2.67 (dddd, J = 24.2, 10.1, 6.3, 2.6 Hz, 2H), 2.34 (s, 3H), 2.03 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 156.2, 138.9, 127.4, 126.8, 121.2, 111.4, 81.5, 70.4, 68.9, 55.2, 27.5, 21.6.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(3-chloro-5-fluorophenyl)but-3-yn-1-ol (3q)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e95% \u0026nbsp;yield (94.1 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.19 (s, 1H), 7.07-6.99 (m, 2H), 4.84 (t, J = 4.6 Hz, 1H), 2.65-2.61 (m, 1H), 2.59 (dd, J = 6.5, 3.0 Hz, 1H), 2.11 (t, J = 2.6 Hz, 1H), 1.68 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 163.7 (d, J = 248 Hz), 146.2 (d, J = 7 Hz), 135.1 (d, J = 10 Hz), 121.9 (d, J = 4 Hz), 115.6 (d, J = 25 Hz), 111.4 (d, J = 22 Hz), 79.6, 71.8, 71.2 (d, J = 2 Hz), 29.4.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-fluoro-3-methoxyphenyl)but-3-yn-1-ol (3r)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e88% \u0026nbsp;yield (85.4 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.09-7.01 (m, 2H), 6.88 (ddd, J = 8.3, 4.3, 2.1 Hz, 1H), 4.83 (t, J = 6.3 Hz, 1H), 3.89 (d, J = 5.9 Hz, 3H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.55 (s, 1H), 2.09 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 151.914.7 (d, J = 244 Hz), 147.6 (d, J = 11 Hz), 138.8 (d, J = 3 Hz), 118.1 (d, J = 7 Hz), 115.8 (d, J = 19 Hz), 110.9 (d, J = 2 Hz), 80.4, 71.9, 71.3, 56.2, 29.6.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-fluoro-3-methylphenyl)but-3-yn-1-ol (3s)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 88% yield (78.4 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.24-7.08 (m, 2H), 6.97 (t, J = 8.9 Hz, 1H), 4.81 (t, J = 6.3 Hz, 1H), 2.61 (dd, J = 6.3, 2.4 Hz, 2H), 2.45 (s, 1H), 2.27 (s, 3H), 2.08 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 160.9 (d, J = 243 Hz), 137.87, 128.9 (d, J = 2 Hz), 125.0, 124.7(d, J = 8 Hz), 114.9 (d, J = 22 Hz), 80.6, 71.8, 71.1, 29.5, 14.7(d, J = 4 Hz)\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2-(benzo[d][1,3]dioxol-4-yl)but-3-yn-1-ol (3t)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 85% yield (80.8 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;6.95-6.89 (m, 1H), 6.84 (t, J = 7.8 Hz, 1H), 6.78 (dd, J = 7.6, 1.0 Hz, 1H), 5.96 (dd, J = 9.2, 1.1 Hz, 2H), 4.98 (dd, J = 10.2, 6.3 Hz, 1H), 2.84-2.58 (m, 3H), 2.06 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 147.4, 144.1, 124.1, 121.8, 119.3, 108.2, 101.0, 80.5, 70.9, 68.3, 27.6.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(thiophen-2-yl)but-3-yn-1-ol (3u)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e88% yield (66.9 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.32-7.22 (m, 1H), 6.99 (ddd, J = 11.1, 6.1, 2.5 Hz, 2H), 5.11 (d, J = 3.7 Hz, 1H), 2.79-2.68 (m, 3H), 2.11 (dd, J = 5.2, 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 146.2, 126.7, 125.0, 124.2, 80.1, 71.5, 68.5, 29.5.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-chloropyridin-2-yl)but-3-yn-1-ol (3v)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e93% \u0026nbsp;yield (84.1 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;8.46 (d, J = 5.3 Hz, 1H), 7.49 (d, J = 1.7 Hz, 1H), 7.26 (dd, J = 5.4, 2.0 Hz, 1H), 4.88 (t, J = 6.0 Hz, 1H), 2.78-2.65 (m, 2H), 2.06 (t, J = 2.6 Hz, 1H), 1.25 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 162.0, 149.4, 144.9, 123.3, 121.2, 80.0, 71.3, 71.1, 28.2.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(pyridin-3-yl)but-3-yn-1-ol (3w)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e95% yield (69.9 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;8.54 (d, J = 2.0 Hz, 1H), 8.47 (dd, J = 4.8, 1.5 Hz, 1H), 7.79 (dt, J = 7.9, 1.8 Hz, 1H), 7.33-7.26 (m, 1H), 4.92 (t, J = 6.4 Hz, 1H), 2.70-2.65 (m, 2H), 2.08 (t, J = 2.6 Hz, 1H), 1.35 \u0026ndash; 1.23 (m, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 148.9, 147.6, 138.3, 133.9, 123.5, 79.9, 71.5, 70.0, 29.3.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(quinolin-2-yl)but-3-yn-1-ol (3x)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e93% yield (92.0 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;8.19 (d, J = 8.5 Hz, 1H), 8.09 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 8.4, 1.4 Hz, 1H), 7.59-7.49 (m, 2H), 5.07 (t, J = 5.9 Hz, 1H), 2.80 (ddd, J = 5.9, 2.5, 1.7 Hz, 2H), 2.02 (t, J = 2.7 Hz, 1H), 1.25 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 160.0, 146.5, 137.0, 129.9, 128.9, 127.8, 127.7, 126.7, 118.5, 80.5, 71.0, 71.0, 28.3.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(naphthalen-2-yl)but-3-yn-1-ol (3y)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 94% yield (92.5 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.87-7.70 (m, 4H), 7.56-7.36 (m, 3H), 4.98 (t, J = 6.3 Hz, 1H), 2.75 (s, 1H), 2.69 (dd, J = 6.4, 2.6 Hz, 2H), 2.05 (t, J = 2.6 Hz, 1H).\u003csup\u003e\u0026nbsp;13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 139.9, 133.2, 133.2, 128.4, 128.1, 127.8, 126.3, 126.1, 124.8, 123.8, 80.8, 72.5, 71.2, 29.4.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(naphthalen-1-yl)but-3-yn-1-ol (3z)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 96% \u0026nbsp;yield (94.1 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;8.04 (d, J = 8.2 Hz, 1H), 7.89-7.83 (m, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.69 (d, J = 7.2 Hz, 1H), 7.54-7.44 (m, 3H), 5.63 (dd, J = 8.2, 4.2 Hz, 1H), 2.87 (ddd, J = 17.0, 4.2, 2.7 Hz, 1H), 2.73 (ddd, J = 17.0, 8.2, 2.6 Hz, 2H), 2.12 (t, J = 2.6 Hz, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 137.8, 133.8, 130.2, 129.1, 128.5, 126.3, 125.7, 125.4, 123.0, 122.8, 81.0, 71.3, 69.3, 28.7.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-isopropylphenyl)-2-methyl-3\u003c/strong\u003e\u003cstrong\u003e\u0026lambda;\u003c/strong\u003e\u003cstrong\u003e5-buta-2,3-dien-1-ol (5a)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e76% yield (76.8 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.30 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 5.07 (s, 1H), 4.96-4.85 (m, 2H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.18 (s, 1H), 1.58 (t, J = 3.0 Hz, 3H), 1.24 (d, J = 7.0 Hz, 6H).\u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 204.6, 148.6, 139.2, 126.6, 126.5, 102.7, 77. 9, 74.5, 33.9, 24.0, 14.7.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2-methyl-1-(p-tolyl)-3\u003c/strong\u003e\u003cstrong\u003e\u0026lambda;\u003c/strong\u003e\u003cstrong\u003e5-buta-2,3-dien-1-ol (5b)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e83% yield (54.9 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta;\u0026nbsp;7.25 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 7.9 Hz, 2H), 5.05 (s, 1H), 4.96-4.82 (m, 2H), 2.34 (s, 3H), 2.30 (s, 1H), 1.56 (t, J = 3.1 Hz, 3H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 204.7, 138.9, 137.5, 129.1, 126. 6, 102.7, 77.8, 74.5, 21.2, 14.7.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1-(4-fluorophenyl)-2-methyl-3\u003c/strong\u003e\u003cstrong\u003e\u0026lambda;\u003c/strong\u003e\u003cstrong\u003e5-buta-2,3-dien-1-ol (5c)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e 73% yield (73 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.34 (dd, J = 8.4, 5.6 Hz, 2H), 7.03 (t, J = 8.7 Hz, 2H), 5.08 (s, 1H), 4.93-4.86 (m, 2H), 2.39 (s, 1H), 1.55 (t, J = 3.1 Hz, 3H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 162.3(d, J = 244 Hz), 137.5 (d, J = 3 Hz), 128.3 (d, J = 8 Hz), 115.2 (d, J = 21 Hz), 102.6, 78.1, 77.4, 74.0, 14.5.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2-methyl-1-(thiophen-2-yl)-3\u003c/strong\u003e\u003cstrong\u003e\u0026lambda;\u003c/strong\u003e\u003cstrong\u003e5-buta-2,3-dien-1-ol (5d)\u003csup\u003e20\u003c/sup\u003e\u003c/strong\u003e\u003cstrong\u003e：\u003c/strong\u003e76% yield (63.1 mg), colorless oil. \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;\u0026delta;\u0026nbsp;7.29-7.25 (m, 1H), 7.02 (d, J = 3.1 Hz, 1H), 6.99-6.95 (m, 1H), 5.35 (s, 1H), 4.99-4.86 (m, 2H), 2.34 (d, J = 4.4 Hz, 1H), 1.69 (t, J = 3.0 Hz, 3H). \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) \u0026delta; 204.4, 146.1, 126.6, 125.2, 125.0, 102.6, 78.6, 70.7, 14.7.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn conclusion, we have established the first Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides. The unique combination of the Cu catalyst and Mn powder present a novel and effective catalyst system in the preparation of homopropargylation alcohols and allenyl alcohols. The overall transformation is highly efficient with mild conditions, large substrate scope, and excellent chem-selectivity. \u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eEthics approval and consent to participate\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for publication\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNA.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and materials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data generated or analyzed during this study are included in this published and its supplementary information files.\u003c/p\u003e\n\u003cp\u003eFunding\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe authors thank the National Natural Science Foundation of China (22161003) and the Project of Science and Technology of Xuzhou Government (No. KC16SG250)\u003c/p\u003e\n\u003cp\u003eAcknowledgement\u003c/p\u003e\n\u003cp\u003eNA\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor details\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eXuzhou Medical University, Tongshan Road 209, Xuzhou, 221004, China. \u003csup\u003e2\u003c/sup\u003eSchool of Pharmaceutical Sciences, Gannan Medical University, Ganzhou 341000, China\u003c/p\u003e\n\u003cp\u003eAuthors\u0026rsquo; contributions\u003c/p\u003e\n\u003cp\u003eZRL contributed to the conception of the study. XY and OL performed the experiment. ZRL and YYC contributed to analysis and manuscript preparation. All authors read and approved the final manuscript.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003e(a) Alami, M.; Hamze, A.; Provot, O.; \u003cem\u003eACS Catal.\u003c/em\u003e \u003cstrong\u003e2019\u003c/strong\u003e, 9, 3437. (b) Parker, K. D. J.; Fryzuk, M. D. \u003cem\u003eOrganometallics\u003c/em\u003e \u003cstrong\u003e2015\u003c/strong\u003e, 34, 2037. (c) Corpas, J.; Maule\u0026oacute;n, P.; G\u0026oacute;mez Array\u0026aacute;, M.; Carretero, J. C. \u003cem\u003eACS Catal.\u003c/em\u003e \u003cstrong\u003e2021\u003c/strong\u003e, 11, 7513. (d) Gilmore, K.; Alabugin, I. V. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e2011\u003c/strong\u003e, 111, 6513. (e) Liu, L.; Ward, R. M.; Schomaker, J. M.\u003cem\u003e\u0026nbsp;Chem. Rev.\u003c/em\u003e \u003cstrong\u003e2019\u003c/strong\u003e, 119, 12422. 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Lett.\u0026nbsp;\u003c/em\u003e\u003cstrong\u003e2021\u003c/strong\u003e, 23, 5724\u0026minus;5728.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 1-3 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"bmc-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"ccjo","sideBox":"Learn more about [BMC Chemistry](https://bmcchem.biomedcentral.com/)","snPcode":"","submissionUrl":"https://www.editorialmanager.com/ccjo/default.aspx","title":"BMC Chemistry","twitterHandle":"BMC_series","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"em","reportingPortfolio":"BMC Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Propargylation, Allenylation, Mn powder, Cu-catalyzed, Gram scale","lastPublishedDoi":"10.21203/rs.3.rs-1080113/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-1080113/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"A simple, practical, and high chemo-selective method for the synthesis of propargyl alcohol and allenyl alcohols via Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides has been established. When 3-bromo-1-propyne was conducted under the standard condition, the aldehydes were transformed to the corresponding propargylation products completely, while when 1-bromo-2-pentyne was used, allenic alcohol was the only product. Variety of homopropargyl alcohols and allenyl alcohols were obtained in high yields and the reaction is compatible with broad substrate scopes. In addition, the large-scale reaction could also be proceeded smoothly indicating the potential synthetic applications of this transformation.","manuscriptTitle":"Cu-Catalyzed, Mn-Mediated Propargylation and Allenylation of Aldehydes with Propargyl Bromides","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2021-11-24 14:50:38","doi":"10.21203/rs.3.rs-1080113/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major revision","date":"2021-12-16T07:38:53+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2021-12-13T01:26:39+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"cdfdf47e-9cce-47c6-8701-2329ba2a900b","date":"2021-12-07T09:35:02+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"771c3de7-16ec-49d1-ba06-379b6510ea09","date":"2021-12-03T07:48:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"389063d1-d3b0-409c-800d-62b0104c6259","date":"2021-12-01T14:18:29+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2021-11-29T22:34:45+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2021-11-24T22:14:40+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2021-11-24T22:11:37+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2021-11-24T22:07:47+00:00","index":"","fulltext":""},{"type":"submitted","content":"BMC Chemistry","date":"2021-11-15T01:05:38+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"bmc-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"ccjo","sideBox":"Learn more about [BMC Chemistry](https://bmcchem.biomedcentral.com/)","snPcode":"","submissionUrl":"https://www.editorialmanager.com/ccjo/default.aspx","title":"BMC Chemistry","twitterHandle":"BMC_series","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"em","reportingPortfolio":"BMC Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"8eae4dcf-bd1d-4ab9-b870-5f61dacdfbe0","owner":[],"postedDate":"November 24th, 2021","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":8703582,"name":"Inorganic Chemistry"}],"tags":[],"updatedAt":"2022-03-18T16:48:47+00:00","versionOfRecord":{"articleIdentity":"rs-1080113","link":"https://doi.org/10.1186/s13065-022-00803-3","journal":{"identity":"bmc-chemistry","isVorOnly":false,"title":"BMC Chemistry"},"publishedOn":"2022-03-18 16:48:47","publishedOnDateReadable":"March 18th, 2022"},"versionCreatedAt":"2021-11-24 14:50:38","video":"","vorDoi":"10.1186/s13065-022-00803-3","vorDoiUrl":"https://doi.org/10.1186/s13065-022-00803-3","workflowStages":[]},"version":"v1","identity":"rs-1080113","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1080113","identity":"rs-1080113","version":["v1"]},"buildId":"-HB7Z8yhvgn0wM9Nzuekk","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}