Visible-Light-Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS2 or CO2: Direct Synthesis of Bis-Dithiocarbamates/Carbamates

Visible-Light-Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS2 or CO2: Direct Synthesis of Bis-Dithiocarbamates/Carbamates | 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 Search Search ADVANCED SEARCH SCROLL Chinese Journal of Chemistry This is a preprint and has not been peer reviewed. Data may be preliminary. 13 March 2025 V1 Latest version Share on Visible-Light-Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS2 or CO2: Direct Synthesis of Bis-Dithiocarbamates/Carbamates Authors : Xue-Cen Xu , Yue-Gong , Jie Wang , Yu-Xuan Meng , and Yulong Zhao 0000-0001-6577-1074 [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.174183327.77961036/v1 Published Chinese Journal of Chemistry Version of record Peer review timeline 312 views 291 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract A visible-light photoredox-catalyzed difunctionalization of diazomethyl radicals with two heteroatomic nucleophiles (saturated bonds) generated in situ from the reaction of secondary amines with CS 2 or CO 2 has been developed for the first time. This reaction provides a new and modular approach for the synthesis of valuable but difficultly accessible S-alkyl di-dithiocarbamates and O -alkyl di-carbamates from readily available starting materials in a single step. Cite this paper: Chin. J. Chem. 2024 , 42 , XXX—XXX. DOI: 10.1002/cjoc.202400XXX Visible-Light-Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS 2 or CO 2 : Direct Synthesis of Bis-Dithiocarbamates/Carbamates Xue-Cen Xu, Yue-Gong, Jie Wang, Yu-Xuan Meng and Yu-Long Zhao* Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China Photocatalytic |α-Diazosulfonium triflates | Diazomethyl radical | O -Alkyl di-carbamates | S -Alkyl di-dithiocarbamates | Comprehensive Summary Background and Originality Content Dithiocarbamate scaffold is one of the most important sulfur-containing organic frameworks in many biologically active pharmaceuticals, agrochemicals and natural products. [1] As important members of these families, S-alkyl dithiocarbamates not only show some important biological activities, [2] but also are useful and versatile synthons for the synthesis of various sulfur-containing compounds. [3] Consequently, many methods, such as the reactions of alkylthio-carbamyl chloride with thiolates, [4] multicomponent coupling reactions between carbon disulfide, amines, with electrophiles/nucleophiles, [5] difunctionalization of styrenes, [6] coupling reactions of amines with toxic thiophosgenes/isothiocyanates/carbonyl sulphide, [7] and the reactions of alkyl halides or N -hydroxyphthalimide esters with tetramethylthiuram disulfide, [8] have been developed. Recently, the visible-light-induced multicomponent reactions of carbon disulfide, amines and radical acceptors have emerged as a powerful method for the synthesis of S-alkyl dithiocarbamates. [9] However, all these reactions are limited to the preparation of S-alkyl mono-dithiocarbamates. In addition, carbon dioxide (CO 2 ) has emerged as an ideal C1 building block in organic synthesis because of its abundance, easy availability, non-toxicity, and renewability. [10] In recent years, visible-light photocatalytic transformation of CO 2 into value-added products has attracted considerable attention as an efficient, versatile and sustainable strategy under mild reaction conditions. [11] In this field, considering the importance of organic carbamates in organic synthesis, medical chemistry, and natural product chemistry, [12] several visible-light-induced methods for the construction of carbamates employing CO 2 as a C1 source has been reported. [13] However, these reactions are still limited to the incorporation of a single CO 2 unit to give the O-alkyl/aryl mono-carbamides. Thus, realizing the visible-light-induced direct synthesis of S-alkyl bis-dithiocarbamates and O-alkyl bis-carbamates employing SO 2 and CO 2 as a C1 source by the incorporation of double CO 2 or CS 2 units is highly desired. Diazo compounds are versatile and powerful reagents that have been extensively applied in modern synthetic organic chemistry. [14] In this field, the intermolecular difunctionalization of diazo compounds has attracted particular attention and many effective methods of difunctionalization of diazo compounds have been developed. [15] With the development of photochemistry in recent years, the visible-light-induced carbene transfer reactions provide alternative methods for the intermolecular difunctionalization of diazo compounds. [16] However, these intermolecular difunctionalization reactions are limited to the insertion of two carbon atoms or one carbon atom and one heteroatom. To the best of our knowledge, the visible-light-induced difunctionalization of diazo compounds by the direct insertion of two heteroatoms has not been reported. In addition, since the first formation of diazomethyl radical from hypervalent iodine diazo compounds in 2018 by Suero and co-workers, [17] several applications of diazomethyl radicals have been developed and attracted much attention. [18] However, all of these reactions were limited to the transformation reaction of various unsaturated bonds with diazomethyl radicals. Therefore, development of new radical reaction of saturated bonds with diazomethyl radicals is still a challenging task. As a continuation of our studies on the applications of diazo compounds [19] and visible-light-induced radical reactions, [20] herein we report a visible-light photoredox-catalyzed intermolecular difunctionalization of diazomethyl radical with two heteroatomic nucleophiles (saturated bonds) generated in situ from the reaction of secondary amines with CS 2 or CO 2 for the first time. This reaction provides a new and straightforward approach to synthesize various S-alkyl di-dithiocarbamates and O -alkyl di-carbamates from readily available starting materials in a single step. Results and Discussion Initially, the model reaction of α-diazosulfonium triflates 1a , carbon disulfide CS 2 and diethylamine 2a was investigated to optimize the reaction conditions (Table 1). We found that the visible-light-induced catalytic coupling reaction of 1a (0.2 mmol), CS 2 (30 µL) and 2a (0.4 mmol) proceeded smoothly to give the S-alkyl di-dithiocarbamate 3aa in 58% yield in the presence of Mes·Acr + ClO 4 - (2 mol%) and Cs 2 CO 3 (1.0 equiv) under irradiation of a 15 W blue LED in DCE at room temperature for 6 h (entry 1). The yield of 3aa was raised to 68% in the presence of Mes·Acr + ClO 4 - (3 mol %) under otherwise identical conditions (entry 2). Decreasing the amount of Cs 2 CO 3 led to comparatively lower yield of 3aa (entry 3). Other photocatalysts and bases, such as Eosin Y, fac -Ir(ppy) 3 , Ru(ppy) 3 Cl 2 , 4CzIPN, DBU, NaHCO 3, KH 2 PO 4 and K 2 CO 3 , were less effective (entries 4-12). Further solvent screening revealed that DCE was superior to other solvents, such as DCM, THF, CH 3 CN and chlorobenzene (entries 13–16). To our delight, the desired product 3aa was obtained in 88% yield by raising the ratio of 2a/1a to 3:1 under otherwise identical conditions (entry 17). Table 1 Optimization of reaction conditions a 1 Mes·Acr + ClO 4 - (2) Cs 2 CO 3 (1.0) 1:2 DCE 58 2 3 Mes·Acr + ClO 4 - (3) Mes·Acr + ClO 4 - (3) Cs 2 CO 3 (1.0) Cs 2 CO 3 (0.5) 1:2 1:2 DCE DCE 68 52 4 Eosin Y (3) Cs 2 CO 3 (1.0) 1:2 DCE 48 5 fac -Ir (ppy) 3 (3) Cs 2 CO 3 (1.0) 1:2 DCE 58 6 Ru(ppy) 3 Cl 2 (3) Cs 2 CO 3 (1.0) 1:2 DCE 30 7 4CzIPN (3) Cs 2 CO 3 (1.0) 1:2 DCE 48 8 Mes·Acr + ClO 4 (3) Na 2 CO 3 (1.0) 1:2 DCE 60 9 Mes·Acr + ClO 4 (3) NaHCO 3 (1.0) 1:2 DCE 63 10 Mes·Acr + ClO 4 (3) KH 2 PO 4 (1.0) 1:2 DCE 56 11 Mes·Acr + ClO 4 (3) K 2 CO 3 (1.0) 1:2 DCE 58 12 Mes·Acr + ClO 4 (3) DBU (1.0) 1:2 DCE 58 13 Mes·Acr + ClO 4 (3) Cs 2 CO 3 (1.0) 1:2 DCM 56 14 Mes·Acr + ClO 4 (3) Cs 2 CO 3 (1.0) 1:2 CH 3 CN 72 15 Mes·Acr + ClO 4 (3) Cs 2 CO 3 (1.0) 1:2 THF 58 16 17 Mes·Acr + ClO 4 (3) Mes·Acr + ClO 4 (3) Cs 2 CO 3 (1.0) Cs 2 CO 3 (1.0) 1:2 1:3 Toluene DCE 66 88 c a Reaction conditions: 1a (0.2 mmol), 2a (0.4-0.6 mmol), CS 2 (30 µL), catalyst (2 or 3 mol%), base (0.5 or 1.0 equiv), solvent (2.0 mL), blue light (15 W), under N 2 , at room temperature for 4 h. b Estimated by 1 H NMR spectroscopy using dibromomethane as an internal standard. c Isolated yield. After establishing the optimal conditions (Table 1, entry 17), the scope and generality of the difunctionalization reaction was investigated and the results are summarized in Scheme 1. All selected symmetrical and unsymmetrical acyclic secondary aliphatic amines, such as diethylamine 2a , dipropylamine 2b , and N -methylbutan-1-amine 2c , reacted smoothly with α-diazosulfonium triflates 1a and CS 2 to give the corresponding S-alkyl di-dithiocarbamates 3aa-c in good to high yields. Similarly, all N -methylbenzylamine 2d-o with electron-rich and electron-deficient groups in the para -, meta -or ortho -position of benzene ring reacted smoothly with α-diazosulfonium triflate 1a and CS 2 , and the corresponding products 3ad-o were obtained with moderate to high yields. In this transformation, the yield of product 3 from N -methylbenzylamine s with electron-deficient groups on the benzene ring is slightly lower. In addition, N -ethyl- and N -allyl-substituted benzylamines 2p and 2q proved to be effective coupling partners, providing the expected products 3ap and 3aq in 77% and 75% yields, respectively. Moreover, various cyclic aliphatic secondary amines with different ring size such as pyrrolidine 2r , piperidine 2s , azepane 2t , and azetidine 2u were also tolerated in this transformation, with the generation of products 3ar-u in 55-78% yields. [21] Notably, the difunctionalization reaction proceeded well with morpholine 2v and thiomorpholine 2w to give the desired products 3av and 3aw in 70% and 68% yields, respectively. However, no desired products were observed when primary amines such as butan-1-amine and phenylmethanamine were employed as coupling partners. In addition, various α-diazosulfonium triflates 1b-g bearing alkoxy carbonyl groups (with either electron-donating or electron-withdrawing groups on the benzene ring) could react efficiently with CS 2 and diethylamine 2a or pyrrolidine 2r to deliver the corresponding S-alkyl di-dithiocarbamates 3b-ha in good yields. Particularly, a variety of valuable functional groups, such as bromine, chlorine, trifluoromethyl, methyl and alkynyl groups, were effectively tolerated in this transformation, which could be utilized for further transformations. Similarly, α-diazosulfonium triflates 1h and 1i bearing aroyl groups also worked well to afford the desired products 3ia and 3ja in 58% and 52% yields, respectively (Scheme 1). On the basis of the above experimental results, along with the consideration of the structural similarity between carbon dioxide and carbon disulfide, we reasoned that the O -alkyl di-carbamates 4 can be constructed via the visible light-induced difunctionalization of α-diazosulfonium triflates 1 with secondary amines 2 and CO 2 . As expected, various symmetrical and unsymmetrical acyclic secondary aliphatic amines 2a , 2b and 2c reacted smoothly with α-diazosulfonium triflates 1a and CO 2 to give the desired O -alkyl di-carbamates 4a-c in good to high yields when DMF was used solvent under otherwise identical conditions as above (Scheme 2). Notably, all kinds of polysubstituted N -alkyl-1-phenylmethanamines 2 are also compatible in the reaction, and gave the desired O -alkyl di-carbamates 4d-l in 58-75% yields. Due to steric hindrance, the ortho -substituted N -methyl-1-phenylmethanamines 2e and 2f gave slightly lower yields. Similarly, cyclic aliphatic secondary amines such as piperidine 2s and azepane 2t were also compatible in the difunctionalization reaction and produced the desired products 4m and 4n in 70% and 79% yields, respectively. In addition, various selected α-diazosulfonium triflates 1b-g bearing alkoxy carbonyl groups participated efficiently in this coupling reaction and the corresponding O -alkyl di-carbamates 4o-t were obtained in good yields. More importantly, even using α-diazosulfonium triflate 1j bearing trifluoromethyl group as coupling partner, the difunctionalization reaction also worked well to afford the desired product 4u in 68% yield (Scheme 2). As a consequential development for this difunctionalization strategy, we questioned whether it could be adopted in radical four-component coupling reaction of α-diazosulfonium triflates 1 , secondary amines 2 , CS 2 and other nucleophiles. We found that the visible light-induced four-component coupling reaction of α-diazosulfonium triflate 1a , secondary aliphatic amines 2 , CS 2 and methanol 5a (5.0 equiv) proceeded smoothly to give the S-alkyl dithiocarbamates 6a-c in 43-60% yields under standard conditions as above (Scheme 3). Similarly, ethanol 5b was also compatible in the four-component reaction and the S-alkyl dithiocarbamate 6d was obtained in 52% yield. However, no desired product was observed when CO 2 was used as C1 source in the four-component coupling reaction. A scale-up reaction of 1a (5.0 mmol) and 2o (15.0 mmol) was performed for 12 h under otherwise identical conditions as above, furnishing 1.91 g of the desired product 3ao in 60% yield (Scheme 4). Furthermore, the synthetic utility of the S-alkyl dithiocarbamates 3 was explored. We found that S-alkyl dithiocarbamates 3 could react with two molecules of phenylmagnesium bromide in THF to generate tertiary alcohols 7a-c in 63-85% yields. In addition, the hydrolysis reaction of S-alkyl dithiocarbamates 3ah and 3ar proceeded easily to give the carboxylic acids 8a and 8b in 92% and 82% yields in the presence of LiOH (3.0 equiv) in THF/H 2 O mixed solvent, respectively (Scheme 4). Scheme 1 Visible light-induced tandem coupling reaction of α-diazosulfonium triflates 1 with secondary amines 2 and CS 2 a,b a Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol), CS 2 (30 µL), Mes-Acr + ClO 4 - (3 mol%), Cs 2 CO 3 (1.0 equiv), DCE (2.0 mL), blue light (15 W), under N 2 , at room temperature for 4 h. b Isolated yield. Scheme 2 Visible light-induced tandem coupling reaction of α-diazosulfonium triflates 1 with secondary amines 2 and CO 2 a,b a Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol), Mes-Acr + ClO 4 - (3 mol%), Cs 2 CO 3 (1.0 equiv), DMF (2.0 mL), blue light (15 W), under CO 2 (1 atm), at room temperature for 4 h. b Isolated yield. Scheme 3 Visible light-induced tandem coupling reaction of α-diazosulfonium triflate 1a with secondary amines 2 , alcohols 5 and CS 2 a,b a Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol), CS 2 (30 µL), 5 (1.0 mmol), Mes-Acr + ClO 4 - (3 mol%), Cs 2 CO 3 (1.0 equiv), DCE (2.0 mL), blue light (15 W), under N 2 , at room temperature for 6 h. b Isolated yield. Scheme 4 Applications of S-alkyl di-dithiocarbamates 3 To further probe the mechanisms for formation 3 , 4 and 6 , several control experiments were conducted (Scheme 5). As a result, we found that the product 3aa was obtained in 52% yield when TEMPO (2.0 equiv; 2,2,6,6-tetramethylpiperidinooxy) was employed as a radical inhibitor, whereas radical adduct 9 of diazomethyl radical intermediate I was successfully trapped and detected using high-resolution mass spectrometry (Scheme 5, (1)). In addition, base on previous reports on the formation of diazomethyl radical I , [17] we further investigated the transformation of α-diazosulfonium triflate 1a . No matter in the presence or absence of diethylamine 2a and CS 2 , we observe the generation of diethyl acetylenedicarboxylate 10 by high-resolution mass spectrometry (Scheme 5, (2) and (3)), which is supposed to be formed through a sequential radical homodimerization of intermediate I and dinitrogen elimination in bis-diazo intermediate II . These results indicate that the reaction might be a radical course and diazomethyl radical intermediate I may be generated and serve as intermediates for the reaction. No target product 3aa was observed when ethyl 2-diazoacetate 11 was treated with 2a and CS 2 under standard conditions (Scheme 5, (4)), indicating that ethyl 2-diazoacetate 11 was not involved in this transformation. Scheme 5 Control experiments for mechanistic studies On the basis of the mechanistic investigations and related literatures, [14-18] a plausible reaction mechanism for the photoredox-catalyzed three-component reaction is proposed (Scheme 6). Initially, under blue LED irradiation, Mes·Acr + ClO 4 - can access its excited state PC * , [1] which is sufficient to reduce the α-diazosulfonium triflates 1 to give diazomethyl radical intermediate A by losing of dibenzo[ b,d ]thiophene and − OTf. [17,18,19a] At the same time, secondary aliphatic amines 2 reacted with CS 2 or CO 2 to generate the anion intermediate B in the presence of Cs 2 CO 3 . Subsequently, intermediate B is oxidized by PC + to give radical intermediate C , which was is immediately captured by radical intermediate A to produce intermediate D . Finally, radical intermediate D reacts with intermediate B under visible-light-induced conditions to produce the desired products 3 and 4 (Scheme 6). [16] Scheme 6 Control experiments for mechanistic studies Conclusions In conclusion, we have developed a visible-light-induced photoredox-catalyzed direct difunctionalization of diazo compounds with two different heteroatomic nucleophiles generated in situ from the reaction of secondary amines with CS 2 or CO 2 for the first time. This reaction provides a new and modular approach for the exquisite assembly of structurally diverse, high-value mutiple-heteroatom-containing compounds such as S -alkyl di-dithiocarbamates and O -alkyl di-carbamates in a single step. This radical assembly strategy not only represents a significant advance in application of diazomethyl radicals in organic synthesis, but also opens up new avenues for the versatile transformations of diazo compounds. Further investigation on synthetic application of α-diazosulfonium triflates is currently undergoing in due course. Experimental Substituted arenes 2 (0.6 mmol), α-diazosulfonium triflates 1 (0.2 mmol), Mes-Acr + ClO 4 - (0.0025g, 0.006 mmol), CS 2 (30 µL) and DCE (2.0 mL) were added to a 10 mL Schlenk tube. The mixture was then stirred at room temperature under N 2 atmosphere and irradiated with 15 W blue LEDs for 6 h. After 1 were consumed (monitored by TLC), the reaction mixture was concentrated, and the residue was purified by silica gel column chromatography to give the desired product 3 . Substituted arenes 2 (0.6 mmol), α-diazosulfonium triflates 1 (0.2 mmol), Mes-Acr + ClO 4 - (0.0025g, 0.006 mmol) and DMF (2.0 mL) were added to a 10 mL Schlenk tube. The mixture was then stirred at room temperature under CO 2 atmosphere and irradiated with 15 W blue LEDs for 4 h. After 1 were consumed (monitored by TLC), the reaction mixture was concentrated, and the residue was purified by silica gel column chromatography to give the desired product 4 . Substituted arenes 2 (0.4 mmol), α-diazosulfonium triflates 1a (0.2 mmol), alcohol 5 (1.0 mmol), Mes-Acr + ClO 4 - (0.0025g, 0.006 mmol), CS 2 (30 µL) and DCE (2.0 mL) were added to a 10 mL Schlenk tube. The mixture was then stirred at room temperature irradiated with 15 W blue LEDs for 6 h. After 1 were consumed (monitored by TLC), the reaction mixture was concentrated, and the residue was purified by silica gel column chromatography to give the desired product 6 . Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202400xxx. Acknowledgement Financial support of this research by the Natural Sciences Foundation of Jilin Province (20240101176JC) and National Natural Sciences Foundation of China (21871044) are greatly acknowledged. References 1. (a) Lincke, T.; Behnken, S.; Ishida, K.; Roth, M.; Hertweck, C. 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Dual Photoredox/Copper-Catalyzed Three-Component Alkylcyanation of Alkenes and 1,4-Alkylcyanation of 1,3-Enynes Employing Sulfoxonium Ylides as the Carbon Radical Precursors. Org. Lett. 2024 , 26 , 10576–10582. 21. CCDC 2394065 ( 3ar) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ddcd.cam.ac.uk/data_request/cif. Manuscript received: XXXX, 2024 Manuscript revised: XXXX, 2024 Manuscript accepted: XXXX, 2024 Version of record online: XXXX, 2024 Entry for the Table of Contents Visible-Light-Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS 2 or CO 2 : Direct Synthesis of Bis-Dithiocarbamates/Carbamates Xue-Cen Xu, Yue-Gong, Jie Wang, Yu-Xuan Meng and Yu-Long Zhao* Chin. J. Chem. 2024 , 42 , XXX—XXX. DOI: 10.1002/cjoc.202400XXX A visible-light photoredox-catalyzed difunctionalization of diazomethyl radicals with two heteroatomic nucleophiles (saturated bonds) generated in situ from the reaction of secondary amines with CS 2 or CO 2 has been developed for the first time. This reaction provides a new and modular approach for the synthesis of valuable but difficultly accessible S-alkyl di-dithiocarbamates and O -alkyl di-carbamates from readily available starting materials in a single step. Information & Authors Information Version history V1 Version 1 13 March 2025 Peer review timeline Published Chinese Journal of Chemistry Version of Record 19 May 2025 Published Copyright This work is licensed under a Non Exclusive No Reuse License. Collection Chinese Journal of Chemistry Keywords diazomethyl radical o-alkyl di-carbamates photocatalytic s-alkyl di-dithiocarbamates α-diazosulfonium triflates Authors Affiliations Xue-Cen Xu Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Yue-Gong Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Jie Wang Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Yu-Xuan Meng Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Yulong Zhao 0000-0001-6577-1074 [email protected] Northeast Normal University Jilin Key Laboratory of Organic Functional Molecule Design and Synthesis View all articles by this author Metrics & Citations Metrics Article Usage 312 views 291 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Xue-Cen Xu, Yue-Gong, Jie Wang, et al. Visible-Light-Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS2 or CO2: Direct Synthesis of Bis-Dithiocarbamates/Carbamates. Authorea . 13 March 2025. DOI: https://doi.org/10.22541/au.174183327.77961036/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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