B(C6F5)3-Catalyzed Direct Deoxygenative Alkenylation of Ketones with Pinacolborane

B(C6F5)3-Catalyzed Direct Deoxygenative Alkenylation of Ketones with Pinacolborane | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 18 June 2025 V1 Latest version Share on B(C6F5)3-Catalyzed Direct Deoxygenative Alkenylation of Ketones with Pinacolborane Authors : Wenwen Chen , Wenjie Zheng , Moke Xu , Rong Jiang , Yinlin Shao 0000-0003-1935-0345 [email protected] , and Fangjun Zhang Authors Info & Affiliations https://doi.org/10.22541/au.175025733.34425425/v1 Published The Journal of Organic Chemistry Version of record Peer review timeline 154 views 107 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract This investigation presents an innovative methodology for the direct deoxygenative alkenylation of ketones, utilizing pinacolborane as the reducing agent in the presence of B(C 6 F 5 ) 3 catalyst. A series of aryl ketones containing different functional groups such as hydroxyl, amino, alkynyl, vinyl, and ester groups were found to be well-tolerated. This transformation has also been nicely applied to the gram-scale late-stage functionalization of pharmacologically significant compounds sertraline and conivaptan. Comprehensive mechanistic investigations have elucidated a plausible reaction pathway that proceeds through sequential carbonyl hydroboration, deboration, and deprotonation processes. Cite this paper: Chin. J. Chem. 2024 , 42 , XXX—XXX. DOI: 10.1002/cjoc.202400XXX B(C 6 F 5 ) 3 -Catalyzed Direct Deoxygenative Alkenylation of Ketones with Pinacolborane Wenwen Chen, a,b Wenjie Zheng, b Moke Xu, b Rong Jiang, a Yinlin Shao* b,c and Fangjun Zhang * a a School of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou 325035, China. b College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou, 325035, China. c Institute of New Materials & Industrial Technology, Wenzhou University, Wenzhou 325035, China. Deoxygenative alkenylation | Ketone | Pinacolborane | B(C 6 F 5 ) 3 -catalyzed | Carbocation | Metal-free | Reduction | Synthetic methods Comprehensive Summary Background and Originality Content The intramolecular synthesis of olefins from ketones has garnered significant attention in organic synthesis, particularly due to its pivotal role in the construction of natural products and fine chemicals where the installation of carbon-carbon double bonds without carbon atom addition is essential. [1] A well-established approach involves the conversion of ketones into their corresponding hydrazones, which subsequently undergo decomposition through Shapiro or Bamford-Stevens reaction pathways under strongly basic conditions to yield alkenes. [2] Recent advancements have led to the development of improved methodologies in this domain. [3] Alternatively, ketones can be transformed into olefins via a two-step process involving reduction to alcohols followed by dehydration. [4] Nevertheless, these conventional strategies are often limited by their multistep nature, the requirement for organometallic reagents, and the necessity of employing strong acids or bases, which collectively result in cumbersome operational procedures. Scheme 1 Comparison of prior work to the current work Deoxygenative olefination of ketones represents a pivotal methodology in synthetic organic chemistry, offering versatile access to alkenes for subsequent functionalization. However, there are only a few examples of direct conversion from ketones to alkenes. As early as in 1996, a reliable a modified Clemmensen reduction strategy realized the conversion of ketones to alkenes. [5] Subsequent advancements were achieved by Fernandes and colleagues, who developed a transition-metal-catalyzed deoxygenative reduction strategy utilizing either phenylsilane [6a] or 3-pentanol (via reductive hydrogen transfer) [6b] as hydrogen donors (Scheme 1, i and ii). Recently, the Yuan group discovered that a synergistic combination of triflic acid and silane could effectively mediate the transformation of ketones to alkenes (Scheme 1, iii). [7] Additionally, Zhao et al. demonstrated a rhodium-catalyzed olefination of ketones with B 2 pin 2 , wherein vinylboronates were generated to facilitate the deoxygenation process (Scheme 1, iv). [8] Stephan’s research group reported the direct hydrogenation of acetophenones to alkenes using B(C 6 F 5 ) 3 as a catalyst (Scheme 1, v). [9] While these methodologies have significantly advanced the field, certain limitations persist, including the requirement for excessive base and/or complex catalysts, high-pressure reactors, and show low chemoselectivity and regioselectivity, which have constrained their broader application in synthetic chemistry. Recently, our group reported a LuCl 3 /B(C 6 F 5 ) 3 cocatalytic system enabling the reductive deoxygenation of ketones to alkanes via in situ generation of cationic intermediates using pinacolborane. [10] Building on this work, we postulated that under a B(C 6 F 5 ) 3 /pinacolborane reduction system, ketones would undergo a sequential carbonyl hydroboration-deboration process, yielding reactive carbocation species capable of direct alkene synthesis from the corresponding ketone precursors. As part of our ongoing efforts to develop borylative reduction strategies for unsaturated compounds, [11] herein we report a B(C 6 F 5 ) 3 -catalyzed direct deoxygenative alkenylation protocol that enables the efficient conversion of ketones to olefins using pinacolborane as the reductant. Results and Discussion Table 1 Optimization of reaction conditions a a Reaction conditions: 1a (0.5 mmol), HBpin (0.9 mmol), B(C 6 F 5 ) 3 (5 mol%), hexane (1.0 mL), a sealed Schlenk tube equipped a Teflon cap under N 2 , 80 o C, 12 h. b Isolated yield. c Yield of 1-([1,1’-biphenyl]-4-yl)ethan-1-ol ( 2a-1 ) was in parenthese. d Yield of 4-ethyl-1,1’-biphenyl ( 2a-2 ) was in parenthese. We used 1-([1,1’-biphenyl]-4-yl)ethan-1-one (1a) as a model substrate in our deoxygenative alkenylation reduction study; the results are summarized in Table 1. Extensive screening showed that the optimal conditions were 5 mol % B(C 6 F 5 ) 3 and HBpin (1.8 equiv.) in hexane at 80 °C for 12 h. Under the optimal conditions, 4-vinyl-1,1’-biphenyl (2a) was generated from 1a in 94% isolated yield (Table 1, entry 1). Initially, the quantity of HBpin was meticulously calibrated, as variations in its concentration can significantly influence the reduction process of carbonyl compounds. Specifically, an excess of HBpin may not only facilitate the reduction to alcohols [12] but also induce over-reduction, [10] resulting in the formation of alkanes. The experimental results demonstrated that the optimal reaction conditions were achieved when employing 1.8 equivalents of HBpin, yielding a maximum conversion efficiency of 94% (Table 1, entries 2-5). Both excessive and insufficient quantities of HBpin were observed to detrimentally impact the reaction efficiency. Notably, the sole by-product detected under these conditions was the corresponding alcohol 1-([1,1’-biphenyl]-4-yl)ethan-1-ol (2a-1); no alkane 4-ethyl-1,1’-biphenyl (2a-2) was observed. This phenomenon may be attributed to the dual role of HBpin in both the catalytic cycle and potential side reactions, where deviations from the optimal concentration could lead to either incomplete substrate activation or competitive inhibition pathways. Other solvents (e.g., toluene, 1,4-dioxane, and THF) were less suitable for achieving efficient deoxygenative alkenylation conversion of ketone 1a (Table 1, entries 6-8). It is noteworthy that the utilization of THF and 1,4-dioxane as reaction solvents results in the partial substantial formation of over-reduced alkane byproducts 2a-2. Reducing the amount of B(C 6 F 5 ) 3 adversely affected the efficiency of the deoxygenative alkenylation process (Table 1, entry 9). The reaction did not proceed in the absence of B(C 6 F 5 ) 3 (Table 1, entry 10). The yield of 2a dropped from 94 to 41% when the reaction was performed at 60 °C instead of 80 °C (Table 1, entry 11). The yield of 2a decreased to 58% when the reaction time was shortened to 6 h (Table 1, entry 12). Scheme 2 Substrate scope a a Reaction conditions: 1 (0.5 mmol), HBpin (0.9 mmol), B(C 6 F 5 ) 3 (5 mol%), hexane (1 mL), under N 2 , 80 o C, 12 h, isolated yield. b HBpin (1.8 mmol) was used. c LuCl 3 (10 mol%) was added . Upon optimization of reaction conditions, the substrate scope was systematically explored (Scheme 2). 4-Phenylacetophenones bearing electron-donating (Me) or halogen (F, Cl, Br) substituents on the phenyl ring were efficiently converted into the corresponding conjugated olefins (2b–2f) with good to excellent yields (83–95%). By contrast, introduction of a strong electron-withdrawing nitro group (NO 2 ) on the phenyl ring significantly impeded the reaction, affording the target alkene 2g in a markedly reduced yield (67%). Notably, sterically hindered substrates, exemplified by 2h (2-Ph), afforded slightly lower yields (75%) due to increased steric congestion. Furthermore, the reduction of aryl methyl ketones demonstrated comparable efficacy irrespective of the steric hindrance or the existence of labile functional groups (2i-2q). Notably, methyl ketones bearing diverse functional groups, including 2-naphthalenyl (1r) and 1-naphthalenyl (1s) moieties, redox-sensitive hydroxyl (1t), alkynyl (1u), ester (1v), and heterocyclic benzo[b]furan-2-yl (1w) substituents, all underwent efficient deoxygenative alkenylation without compromising conversion efficiency. Notably, when vinyl ketones (1x–1z) were employed as substrates, conjugated olefins were achieved via the B(C 6 F 5 ) 3 -catalyzed direct deoxygenative alkenylation strategy, with moderate yields ranging from 59% to 68%. Systematic screening experiments revealed that electronic effects played a pivotal role in dictating reaction activity: electron-donating 1-(4-methoxyphenyl)ethan-1-one (1aa) and electron-withdrawing 1-(4-nitrophenyl)ethan-1-one (1ab) both failed to afford the corresponding alkene products under the optimized conditions, highlighting the necessity for balanced substituent electronics to achieve successful transformation. Upon treatment of diketones 1ac and 1ad with 3.6 equivalents of HBpin, dialkenylation products 2ac and 2ad were generated in isolated yields of 64% and 32%, respectively. Notably, a series of arylbenzyl ketones bearing diverse functional groups, including 1,2-diphenylethan-1-one (1ae), 1-(4-tert-butylphenyl)-2-phenylethan-1-one (1af), 1-(4-methoxyphenyl)-2-phenylethan-1-one (1ag), and 1-(4-chlorophenyl)-2-phenylethan-1-one (1ah), underwent the transformation to afford the corresponding alkenylated products 2ae-2ah in 22-64% yields. To enhance the catalytic efficiency of this transformation, we systematically screened various lanthanide salts as additives (see Supporting Information). Remarkably, the addition of 10 mol% LuCl₃ led to a significant yield improvement of alkenes 2ae-2ah, reaching 47-94% under modified optimized conditions. Building on this finding, we extended the scope to substrates 1ai–1al in the presence of LuCl₃, affording the corresponding alkene products 2ai–2al in yields ranging from 39% to 82%. Furthermore, aryl alkyl ketones bearing diverse chain lengths and branched alkyl moieties were subjected to the modified protocol, yielding products 2am–2ap in 67–95% yields. This methodology was also applicable to benzocyclic ketones, including five- (e.g., 2aq-2at), six- (2au-2ay), and seven-membered (2az) ring systems, affording the desired alkene products in good to excellent yields. Systematic investigation revealed that substituent electronic effects exert substantial influence on the reaction efficiency, wherein both strongly electron-donating (e.g., 1ar, 1aw) and electron-withdrawing groups (e.g., 1ay) invariably resulted in diminished yields compared to other substrates. Given the exceptional tolerance of our methodology towards a wide range of functional groups, we aimed to illustrate the practical applicability of this operationally straightforward strategy in the gram-scale late-stage functionalization of pharmacologically significant compounds sertraline and conivaptan, which yielded corresponding drug analogs 2ba and 2bb with favorable efficiency (Scheme 3). Scheme 3 Practical synthetic application: gram-scale deoxygenation of sertraline and conivaptan To elucidate the reaction pathway, several control experiments were conducted. When ketone 1a was subjected to hydroboration with an equimolar amount of HBpin in the presence of B(C 6 F 5 ) 3 as the catalyst for 2 hours, alcohol 2a-1 was obtained in a 15% isolated yield, while the remaining 1a was recovered (Scheme 4a). Additionally, borate ester 2a-3 was successfully converted to alkene 2a using 0.8 equivalents of HBpin catalyzed by B(C 6 F 5 ) 3 (Scheme 4b). These findings indicate that the borate ester serves as an intermediate in the deoxygenative alkenylation process. When aryl ketone 1bc was treated with HBpin, the formation of rearranged olefin product 2bc suggested the involvement of a cationic intermediate (Scheme 4c). To investigate the potential involvement of a radical mechanism, a trapping experiment was performed under standard reaction conditions. When the radical scavenger TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) was introduced, the reaction yielded the desired product 2a in only 21% yield, accompanied by significant formation of alcohol 2a-1 (41%), alkane 2a-2 (14%), and recovered starting material 1a (Scheme 4d). The detection of these TEMPO-addition products and the substantial recovery of starting material strongly suggest that the reaction does not proceed via a radical-mediated pathway. To gain deeper mechanistic insights, deuterium-labeling experiments were performed. When 1a- d was treated with HBpin, exclusive deuterium incorporation (99%) was observed at the β-position of 2a (Scheme 4e). Conversely, the reaction of 1a with DBpin led to near-quantitative deuterium incorporation (99%) at the α-position of 2a (Scheme 4f). These results unambiguously demonstrate that the α-hydrogen in 2a originates from HBpin, while the β-hydrogen is derived from the ketone substrate. Additionally, O(Bpin)₂ was obtained in 76% yield from the model reaction. Scheme 4 Mechanistic studies Combining our experimental results with literature reports, [13] we propose a mechanism for the B(C 6 F 5 ) 3 - catalyzed deoxygenative alkenylation of aryl methyl ketone 1 with HBpin (Scheme 5). The catalytic cycle initiates with B(C 6 F 5 ) 3 activation of HBpin via B···H interaction, forming the weak adduct A. Intramolecular hydroboration of the ketone substrate by HBpin then yields intermediate B while regenerating the B(C 6 F 5 ) 3 catalyst. Subsequent coordination of A to B generates the activated complex C. This undergoes transformation to produce the diboryl oxonium ion E along with borohydride species D. The critical C-O bond cleavage step liberates O(Bpin) 2 and forms the key cationic intermediate F, which upon deprotonation affords the final alkene product 2. (See Supporting Information for mechanistic details of the B(C 6 F 5 ) 3 /LuCl 3 -cocatalyzed deoxygenative alkenylation with pinacolborane) Scheme 5 Proposed mechanism Conclusions In summary, we have developed an environmentally benign, B(C 6 F 5 ) 3 -catalyzed direct deoxygenative alkenylation of ketones using pinacolborane for the efficient synthesis of aryl alkenes. This methodology offers significant advantages including operational simplicity, mild reaction conditions, broad substrate scope, excellent safety profile, and readily available reagents, making it particularly attractive for practical applications. Notably, the protocol enables late-stage functionalization of pharmaceutical compounds and demonstrates excellent scalability potential. Mechanistic investigations reveal that the transformation proceeds via a concerted carbonyl hydroboration-deboration-deprotonation cascade. We anticipate this sustainable and efficient approach will open new avenues for olefination chemistry in both academic and industrial settings. Experimental Procedure for the B(C 6 F 5 ) 3 -catalyzed direct deoxygenative alkenylation of ketone 1a with pinacolborane In a nitrogen-filled glovebox, B(C 6 F 5 ) 3 (10.2 mg, 0.02 mmol), 1a (98.1 mg, 0.5 mmol), HBpin (115.0 mg, 0.9 mmol) and hexane (1 mL) were added in sequence to a Schlenk tube equipped with a magnetic stirring bar and a Teflon cap. The sealed tube was taken out from the glovebox, and stirred at 80 ℃ for 12 h. After completion of the reaction, the tube was opened in air. The crude mixture was purified by flash column chromatography using PE/EtOAc as the eluent to give the product 2a . Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202400xxx. Acknowledgement We thank the National Natural Science Foundation of China (No. 22101209 and 22301222) and Wenzhou Association For Science and Technology (No. RKX2024-090) for financial support. We also thank Scientific Research Center of Wenzhou Medical University for consultation and instrument availability that supported this work. References 1. (a) Beller, M.; Seayad, J.; Tillack, A.; Jiao, H. Catalytic Markovnikov and anti-Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends. Angew. Chem., Int. Ed. 2004 , 43 , 3368-3398; (b) Dong, Z.; Ren, Z.; Thompson, S. J.; Xu, Y.; Dong, G. Transition-Metal-Catalyzed C–H Alkylation Using Alkenes. Chem. Rev. 2017 , 117 , 9333-9403; (c) Cui, X.; Burgess, K. 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Enantioselective Hydroboration of Ketones Catalyzed by Rare-Earth Metal Complexes Containing Trost Ligands. J. Org. Chem. 2020 , 85 , 10504-10513; (d) Lata, C. J.; Crudden, C. M. Dramatic Effect of Lewis Acids on the Rhodium-Catalyzed Hydroboration of Olefins. J. Am. Chem. Soc. 2010 , 132 , 131-137. Manuscript received: XXXX, 2024 Manuscript revised: XXXX, 2024 Manuscript accepted: XXXX, 2024 Version of record online: XXXX, 2024 not-yet-known not-yet-known not-yet-known unknown Left to Right: Wenwen Chen, Wenjie Zheng, Moke Xu, Rong Jiang, Yinlin Shao, Fangjun Zhang Entry for the Table of Contents not-yet-known not-yet-known not-yet-known unknown B(C6F5)3-Catalyzed Direct Deoxygenative Alkenylation of Ketones with PinacolboraneWenwen Chen, Wenjie Zheng, Moke Xu, Rong Jiang, Yinlin Shao* and Fangjun Zhang *Chin. J. Chem. 2024, 42, XXX—XXX. DOI: 10.1002/cjoc.202400XXX Information & Authors Information Version history V1 Version 1 18 June 2025 Peer review timeline Published The Journal of Organic Chemistry Version of Record 23 Oct 2025 Published Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords b(c6f5)3-catalyzed deoxygenative alkenylation ketone metal-free pinacolborane synthetic method Authors Affiliations Wenwen Chen Wenzhou Medical University School of Pharmaceutical Sciences View all articles by this author Wenjie Zheng Wenzhou University College of Chemistry and Materials Engineering View all articles by this author Moke Xu Wenzhou University College of Chemistry and Materials Engineering View all articles by this author Rong Jiang Wenzhou Medical University School of Pharmaceutical Sciences View all articles by this author Yinlin Shao 0000-0003-1935-0345 [email protected] Wenzhou University College of Chemistry and Materials Engineering View all articles by this author Fangjun Zhang Wenzhou Medical University School of Pharmaceutical Sciences View all articles by this author Metrics & Citations Metrics Article Usage 154 views 107 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Wenwen Chen, Wenjie Zheng, Moke Xu, et al. B(C6F5)3-Catalyzed Direct Deoxygenative Alkenylation of Ketones with Pinacolborane. Authorea . 18 June 2025. DOI: https://doi.org/10.22541/au.175025733.34425425/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . 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