Bromine-Radical-Mediated Site-Selective Allylation of C(sp³)–H Bonds

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

The C(sp³)–H allylation of alkanes is investigated by using allyl bromides under radical reaction conditions. In many cases, methine C–H allylation preceded methylene and methyl C–H allylation with complete or a high degree of site selectivity. The C–H allylation of allylic compounds, such as allylbenzene, gives 1,5-dienes with the S_H2′ reactions of the allyl radicals occurring at the less hindered carbon.

Key words

C(sp³)–H allylation - bromine radicals - S_H2 reaction - S_H2′ reaction - site selectivity

• References


For reviews on site-selective C(sp³)–H functionalization, see:
• 1a Zhou M, Crabtree RH. Chem. Soc. Rev. 2011; 40: 1875
• 1b Che C.-M, Lo VK.-Y, Zhou C.-Y, Huang J.-S. Chem. Soc. Rev. 2011; 40: 1950
• 1c Brückl T, Baxter RD, Ishihara Y, Baran PS. Acc. Chem. Res. 2012; 45: 826
• 1d Liu W, Groves JT. Acc. Chem. Res. 2015; 48: 1727
• 1e Hartwig JF, Larsen MA. ACS. Cent. Sci. 2016; 2: 281
• 1f C–H Activation . In Topics in Current Chemistry . Vol. 292. Yu J.-Q, Shi Z. Springer-Verlag; Berlin: 2010
• 1g Milan M, Salamone M, Costas M, Bietti M. Acc. Chem. Res. 2018; 51: 1984
• 1h White MC, Zhao J. J. Am. Chem. Soc. 2018; 140: 13988

For selected recent papers on site-selective C(sp³)–H functionalization, see:
• 2a Adams AM, Du Bois J, Malik HA. Org. Lett. 2015; 17: 6066
• 2b Cuthbertson JD, MacMillan DW. C. Nature 2015; 519: 74
• 2c Lee M, Sanford MS. J. Am. Chem. Soc. 2015; 137: 12796
• 2d Miao J, Yang K, Kurek M, Ge H. Org. Lett. 2015; 17: 3738
• 2e Huang X, Groves JT. ACS Catal. 2016; 6: 751
• 2f Chu JC. K, Rovis T. Nature 2016; 539: 272
• 2g Kawamata Y, Yan M, Liu Z, Bao D.-H, Chen J, Starr JT, Baran PS. J. Am. Chem. Soc. 2017; 139: 7448
• 2h Mbofana CT, Chong E, Lawniczak J, Sanford MS. Org. Lett. 2016; 18: 4258
• 2i Liu Y, Ge H. Nat. Chem. 2017; 9: 26
• 2j Nanjo T, de Lucca EC. Jr, White MC. J. Am. Chem. Soc. 2017; 139: 14586
• 2k Liao K, Pickel TC, Boyarskikh V, Bacsa J, Musaev DG, Davies HM. L. Nature 2017; 551: 609
• 3a Okada M, Fukuyama T, Yamada K, Ryu I, Ravelli D, Fagnoni M. Chem. Sci. 2014; 5: 2893
• 3b Okada M, Yamada K, Fukuyama T, Ravelli D, Fagnoni M, Ryu I. J. Org. Chem. 2015; 80: 9365
• 3c Yamada K, Okada M, Fukuyama T, Ravelli D, Fagnoni M, Ryu I. Org. Lett. 2015; 17: 1292
• 3d Yamada K, Fukuyama T, Fujii S, Ravelli D, Fagnoni M, Ryu I. Chem. Eur. J. 2017; 23: 8615
• 3e Quattrini MC, Fujii S, Yamada K, Fukuyama T, Ravelli D, Fagnoni M, Ryu I. Chem. Commun. 2017; 53: 2335
• 3f Fukuyama T, Nishikawa T, Yamada K, Ravelli D, Fagnoni M, Ryu I. Org. Lett. 2017; 19: 6436
• 3g Fukuyama T, Yamada K, Nishikawa T, Ravelli D, Fagnoni M, Ryu I. Chem. Lett. 2018; 47: 207
• 4 For a perspective, see: Ravelli D, Fagnoni M, Fukuyama T, Nishikawa T, Ryu I. ACS Catal. 2018; 8: 701
• 5 Manabe Y, Fukase K, Matsubara H, Hino Y, Fukuyama T, Ryu I. Chem. Eur. J. 2014; 20: 12750

For site-selective radical C–H bromination, see:
• 6a Kharasch MS, Hered W, Mayo FR. J. Org. Chem. 1941; 6: 818
• 6b Jiang X, Shen M, Tang Y, Li C. Tetrahedron Lett. 2005; 46: 487
• 6c Russell GA, Brown HC. J. Am. Chem. Soc. 1955; 77: 4025
• 6d Schmidt VA, Quinn RK, Brusoe AT, Alexanian EJ. J. Am. Chem. Soc. 2014; 136: 14389
• 7a Tanko JM, Sadeghipour M. Angew. Chem. Int. Ed. 1999; 38: 159
• 7b Struss JA, Sadeghipour M, Tanko JM. Tetrahedron Lett. 2009; 50: 2119
• 8a Kippo T, Fukuyama T, Ryu I. Org. Lett. 2010; 12: 4006
• 8b Kippo T, Fukuyama T, Ryu I. Org. Lett. 2011; 13: 3864
• 8c Kippo T, Hamaoka K, Ryu I. J. Am. Chem. Soc. 2013; 135: 632
• 8d Kippo T, Ryu I. Chem. Commun. 2014; 50: 5993
• 8e Kippo T, Kimura Y, Maeda A, Matsubara H, Fukuyama T, Ryu I. Org. Chem. Front. 2014; 1: 755
• 8f Kippo T, Hamaoka K, Ueda M, Fukuyama T, Ryu I. Tetrahedron 2016; 72: 7866
• 8g Kippo T, Kimura Y, Ueda M, Ryu I. Synlett 2017; 28: 1733
• 8h Kippo T, Hamaoka K, Ueda M, Fukuyama T, Ryu I. Org. Lett. 2017; 19: 5198

For radical allylations of alkane C(sp³)–H bonds, see:
• 9a Xiang J, Evarts J, Rivkin A, Curran DP, Fuchs PL. Tetrahedron Lett. 1998; 39: 4163
• 9b Kamijo S, Kamijo K, Maruoka K, Murafuji T. Org. Lett. 2016; 18: 6516
• 9c Zhang J, Li Y, Zhang F, Hu C, Chen Y. Angew. Chem. Int. Ed. 2016; 55: 1872

For radical allylations of benzylic C(sp³)–H bonds and α-C(sp³)–H bonds of heteroatoms (N, O), see:
• 10a Patil S, Chen L, Tanko JM. Eur. J. Org. Chem. 2014; 502
• 10b Xuan J, Zeng T.-T, Feng Z.-J, Deng Q.-H, Chen J.-R, Lu L.-Q, Xiao W.-J, Alper H. Angew. Chem. Int. Ed. 2015; 54: 1625
• 10c Li Y, Zhang J, Li D, Chen Y. Org. Lett. 2018; 20: 3296 ; and reference 7 cited therein
• 11 In the reaction shown in Scheme 2 a, decrease of the amount of isooctane from 5 mL to 2.5 mL resulted in a decrease of the yields of products 3aa (39%) and 4aa (6%).
• 12 Sumino S, Fusano A, Ryu I. Org. Lett. 2013; 15: 2826
• 13 Lüthy M, Darmency V, Renaud P. Eur. J. Org. Chem. 2011; 547
• 14 Lévêque C, Chenneberg L, Corcé V, Ollivier C, Fensterbank L. Chem. Commun. 2016; 52: 9877
• 15 Corcé V, Chamoreau L.-M, Derat E, Goddard J.-P, Ollivier C, Fensterbank L. Angew. Chem. Int. Ed. 2015; 54: 11414
• 16 Reichle MA, Breit B. Angew. Chem. Int. Ed. 2012; 51: 5730