Synthesis, Table of Contents Synthesis 2020; 52(02): 311-319DOI: 10.1055/s-0039-1690717 paper © Georg Thieme Verlag Stuttgart · New YorkA Simplified Protocol for the Stereospecific Nickel-Catalyzed C–S Vinylation Using NiX2 Salts and Alkyl Phosphites Authors Author Affiliations Austin D. Marchese Bijan Mirabi Egor M. Larin Mark Lautens ∗ Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada Email: mark.lautens@utoronto.ca Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract A Ni-catalyzed C–S cross-coupling using only NiI2 (0.5–2.5 mol%) and P(OiPr)3 (2.0–10.0 mol%) is reported. Using an air-stable Ni(II) precatalyst, and a cheap and commercially available ligand, a scalable and robust method was developed to cross-couple various thiophenols and styryl bromides, including some sterically encumbered thiols, an α-bromocinnamaldehyde as well as a thiolation-cyclization. Key words Key wordsnickel - cross-coupling - scalable - heterocycles Full Text References References For select reviews and references therein, see: 1a Gandeepam P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192 1b Petrone DA, Ye J, Lautens M. Chem. Rev. 2016; 116: 8003 1c Miao J, Ge H. Eur. J. Org. Chem. 2015; 7859 1d Jana R, Pathak TP, Sigman MP. Chem. Rev. 2011; 111: 1417 Relevant Ni-catalyzed C–S coupling reactions: 2a Jones KD, Power DJ, Bierer D, Gericke KM, Stewart SG. Org. Lett. 2018; 20: 208 2b Xu X.-B, Liu J, Zhang J.-J, Wang Y.-W, Peng Y. Org. Lett. 2013; 15: 550 2c Jammi S, Barua P, Rout L, Saha P, Punniyamurthy T. Tetrahedron Lett. 2008; 49: 1484 2d Yatsumonji Y, Okada O, Tsubouchi A, Takeda T. Tetrahedron 2006; 62: 9981 2e Gendre F, Yand M, Diaz P. Org. Lett. 2005; 7: 2719 2f Cristau HJ, Chabaud B, Labaudiniere R, Christol H. J. Org. Chem. 1986; 51: 875 3a Marchese A, Kersting L, Lautens M. Org. Lett. 2019; 21: 7163 3b Marchese AD, Lind F, Mahon Á, Yoon H, Lautens M. Angew. Chem. Int. Ed. 2019; 58: 5095 3c Yoon H, Marchese AD, Lautens M. J. Am. Chem. Soc. 2018; 140: 10950 4 Yatsumonji Y, Ishida Y, Tsubouchi A, Takeda T. Org. Lett. 2007; 9: 4603 Metal-catalyzed oxidative coupling of thiols to disulfides, thus reducing the metal, may be a potential method. For a review of metal-catalyzed oxidative coupling of thiols using metals, see: 5a Mandal B, Basu B. RSC Adv. 2014; 4: 13854 For a specific example pertaining to Ni, see: 5b Saxena A, Kumar A, Mozumdar S. J. Mol. Catal. A: Chem. 2007; 269: 35 For an example of disulfide reduction using phosphines or phosphites, see: 6a Burns JA, Butler JC, Moran J, Whitesides GM. J. Org. Chem. 1991; 56: 2648 6b Schäfer K, Asmus A.-D. J. Phys. Chem. 1980; 84: 2156 For intra-inter molecular cyclizations with Pd generating benzothiophenes, see: 7a Zhang M, Weng Z. Org. Lett. 2019; 21: 5838 7b Bryan CS, Braunger JA, Lautens M. Angew. Chem. Int. Ed. 2009; 48: 7064 7c Newman SG, Aureggi V, Bryan CS, Lautens M. Chem. Commun. 2009; 5236 7d Fang YQ, Lautens M. Org. Lett. 2005; 7: 3549 For recent examples of Pd cyclizations of gem-dibromo olefins generating indoles, see: 7e Zeidan N, Bognar S, Lee S, Lautens M. Org. Lett. 2017; 19: 5058 7f Newman SG, Lautens M. J. Am. Chem. Soc. 2010; 132: 11416 8 You H.-Y, Lee K.-J. Synlett 2001; 105 9 Qiu C, Yao K, Zhang X, Gong H. Org. Biomol. Chem. 2016; 14: 11332 10 Tu H.-Y, Hu B.-L, Deng C.-L, Zhang X.-G. Chem. Commun. 2015; 51: 15558 11 Choudhuri K, Pramanik M, Mandal A, Mal P. Asian J. Org. Chem. 2018; 7: 1849 12 Yong Y, Rioux RM. Chem. Commun. 2011; 47: 6557 13 Savarin C, Srogl J, Liebeskind LS. Org. Lett. 2002; 4: 4309 14 Kabir MS, Lorenz M, Van Linn ML, Namjoshi OA, Ara S, Cook JM. J. Org. Chem. 2010; 75: 3626 15 Chu C.-M, Tu Z, Wu P, Wang C.-C, Liu J.-T, Kuo C.-W, Shin Y.-H, Yao C.-F. Tetrahedron 2009; 65: 3978 16 He L, Guo H, Li Y.-Z, Du G.-F, Dai B. Chem. Commun. 2014; 50: 3719 17 Cristau HJ, Chabaud B, Labaudiniere R, Christol H. J. Org. Chem. 1985; 51: 875 18 Sim JU, Son HS, Yong J, Baek YM. (Doosan Corp.) Patent KR20150027443 (A), 2015 19 Li X, Xu Y, Wu W, Jiang C, Qi C, Jiang H. Chem. Eur. J. 2014; 20: 7911 Supplementary Material Supplementary Material Supporting Information (PDF)
