Bromine-Radical-Mediated Bromoallylation of C–C Unsaturated Bonds: A Facile Access to 1,4-, 1,5-, 1,6-, and 1,7-Dienes and Related Compounds

Abstract

The radical bromoallylation of alkynes, allenes, and vinylidene cyclopropanes proceeds efficiently in the presence of a radical initiator to give 2-bromo-substituted 1,4-, 1,5-, and 1,6-diene derivatives, respectively. Three-component reactions comprised of allenes, electron-deficient alkenes, and allyl bromides give 1,7-dienes in good yields. The bromoallylation of an arylalkene can override β-scission of the bromine radical from β-bromoalkyl radicals to give 5-bromoalkenes, whilst the bromoallylation of vinylcyclopropanes is accompanied by 5-exo ring closure to give 1-(bromomethyl)-2-vinylcyclopentane derivatives in good yields. All of the products contain a reactive vinyl bromide moiety, which can be readily functionalized by Pd-catalyzed cross-coupling and radical cascade reactions.

1 Introduction

2 Synthesis of 1,4-Dienes by Bromoallylation of Acetylenes

3 Synthesis of 1,5-Dienes by Bromoallylation of Allenes

4 Synthesis of 1,6-Dienes by Bromoallylation of Methylenecyclopropanes

5 Synthesis of 1,7-Dienes by Bromoallylation of Allenes and Electron-Deficient Alkenes

6 Bromoallylation of Arylalkenes and Vinylcyclopropanes

7 Conclusion

Key words

dienes - radical allylation - Br radical - allyl bromides - alkynes - allenes - methylenecyclopropanes - vinylcyclopropanes

Publication History

Received: 07 November 2022

Accepted after revision: 15 December 2022

Accepted Manuscript online:
15 December 2022

Article published online:
13 January 2023

• References

• 1a Free-Radical Chain Reaction . Huyser ES. John Wiley & Sons; New York: 1970
• 1b Free Radicals, Vols. 1 and 2. Kochi JK. John Wiley & Sons; New York: 1973
• 1c Taniguchi T. Synthesis 2017; 49: 3511
• 2a Wohl A. Ber. Dtsch. Chem. Ges. 1919; 52: 51
• 2b Wohl A, Jaschinowski K. Ber. Dtsch. Chem. Ges. 1921; 54: 476
• 2c Ziegler K, Späth A, Schaaf E, Schumann W, Winkelmann E. Justus Liebigs Ann. Chem. 1942; 551: 80

For reviews, see:
• 2d Djerassi C. Chem. Rev. 1948; 43: 271
• 2e Horner L, Winkelmann EH. Angew. Chem. 1959; 71: 349

For recent work, see:
• 3a Qu C.-H, Huang R, Liu Y, Liu T, Song G.-T. Org. Chem. Front. 2022; 9: 4135
• 3b Wang Q.-L, Sun Z, Huang H, Mao G, Deng G.-J. Green Chem. 2022; 24: 3293
• 4 Manabe Y, Kitawaki Y, Nagasaki M, Fukase K, Matsubara H, Hino Y, Fukuyama T, Ryu I. Chem. Eur. J. 2014; 20: 12750
• 5a Talukdar R. Org. Biomol. Chem. 2020; 18: 8294
• 5b Huan L, Shu X, Zu W, Zhong D, Huo H. Nat. Commun. 2021; 12: 3536
• 5c Wang H, Liu H, Wang M, Huang M, Shi X, Wang T, Cong X, Yan J, Wu J. iScience 2021; 24: 102693
• 5d Wang C, Shi H, Deng G.-J, Huang H. Org. Biomol. Chem. 2021; 19: 9177
• 5e Dongbang S, Doyle AG. J. Am. Chem. Soc. 2022; 144: 20067
• 5f Wang Q.-L, Huang H, Mao G, Deng G.-J. Green Chem. 2022; 24: 8324
• 6 For the abstraction of allylic C–H bonds by bromine radicals, see: Sumino S, Fusano A, Ryu I. Org. Lett. 2013; 15: 2826

For a review on radical hydrobromination, see:
• 7a Stacey FW, Harris JF. Jr. Org. React. 1963; 13: 150
• 7b See also: Matsubara H, Tsukida M, Ishihara D, Kuniyoshi K, Ryu I. Synlett 2010; 13: 2014
• 8a Kharasch MS, Sage M. J. Org. Chem. 1949; 14: 79
• 8b Kharasch MS, Büchi G. J. Org. Chem. 1949; 14: 84
• 8c Breuilles P, Uguen D. Tetrahedron Lett. 1990; 31: 357
• 9a Tanko JM, Sadeghipour M. Angew. Chem. Int. Ed. 1999; 38: 159
• 9b Struss JA, Sadeghipour M, Tanko JM. Tetrahedron Lett. 2009; 50: 2119
• 10 Kippo T, Kimura Y, Ueda M, Fukuyama T, Ryu I. Synlett 2017; 28: 1733
• 11a Ueda M, Maeda A, Hamaoka K, Sasano M, Fukuyama T, Ryu I. Synthesis 2019; 51: 1171
• 11b Kippo T, Kimura Y, Maeda A, Matsubara H, Fukuyama T, Ryu I. Org. Chem. Front. 2014; 1: 755
• 12 Kawasaki T, Ishida N, Murakami M. J. Am. Chem. Soc. 2020; 142: 3366
• 13a Kippo T, Fukuyama T, Ryu I. Org. Lett. 2010; 12: 4006
• 13b Kippo T, Hamaoka K, Ueda M, Fukuyama T, Ryu I. Tetrahedron 2016; 72: 7866
• 14 Kippo T, Fukuyama T, Ryu I. Org. Lett. 2011; 13: 3864
• 15 Kippo T, Hamaoka K, Ryu I. J. Am. Chem. Soc. 2013; 135: 632
• 16 Kippo T, Ryu I. Chem. Commun. 2014; 50: 5993
• 17 Kippo T, Hamaoka K, Ueda M, Fukuyama T, Ryu I. Org. Lett. 2017; 19: 5198
• 18 Fukuyama T, Kippo T, Hamaoka K, Ryu I. Sci. China Chem. 2019; 62: 1525
• 19a Walbiner M, Wu JQ, Fischer H. Helv. Chim. Acta 1995; 78: 910
• 19b Zytowski T, Fischer H. J. Am. Chem. Soc. 1997; 119: 12869
• 19c Fischer H, Radom L. Angew. Chem. Int. Ed. 2001; 40: 1340
• 19d Fischer H, Radom L. Macromol. Symp. 2002; 182: 1
• 20a Miura K, Saito H, Itoh D, Matsuda T, Fujisawa N, Wang D, Hosomi A. J. Org. Chem. 2001; 66: 3348
• 20b Miura K, Saito H, Fujisawa N, Wang D, Nishikori H, Hosomi A. Org. Lett. 2001; 3: 4055
• 21 SOLARBOX 1500, is a solar simulator fitted with a 1.5 kW xenon lamp. We set the light intensity to 350 W/m² (300–800 nm) for the experiments; see: https://cofomegra.it/en/solarbox-1500-3000 (accessed Dec. 30, 2022)
• 22a Taylor DR. Chem. Rev. 1967; 67: 317
• 22b Pasto DJ. Tetrahedron 1984; 40: 2805
• 22c Modern Allene Chemistry, Vols. 1 and 2. Krause N, Hashmi AS. K. Wiley-VCH; Weinheim: 2004
• 22d Ma S. Chem. Rev. 2005; 105: 2829
• 22e Ma S. Aldrichimica 2007; 40: 91

For radical hydrobromination of allenes, see:
• 23a Kovachic D, Leitch LC. Can. J. Chem. 1961; 39: 363
• 23b Griesbaum K, Oswald AA, Hall DN. J. Org. Chem. 1964; 29: 2404
• 23c Abell PI, Anderson RS. Tetrahedron Lett. 1964; 5: 3727
• 23d Tien RY, Abell PI. J. Org. Chem. 1970; 35: 956
• 23e Moorthy SN, Singh A, Devaprabhakara D. J. Org. Chem. 1975; 40: 3452

For selected reviews, see:
• 24a Lautens M, Klute W, Tam W. Chem. Rev. 1996; 96: 49
• 24b Rubin M, Rubina M, Gevorgyan V. Chem. Rev. 2007; 107: 3117
• 24c Brandi A, Cicchi S, Cordero FM, Goti A. Chem. Rev. 2014; 114: 7317
• 25 For radical bromination of methylenecyclopropanes, see: Yu L, Chen B, Huang X, Wu LL. Chin. Chem. Lett. 2007; 18: 121

For reviews on radical carbonylation, see:
• 26a Ryu I, Sonoda N. Angew. Chem. Int. Ed. 1996; 35: 1050
• 26b Ryu I. Chem. Soc. Rev. 2001; 30: 16
• 26c Sumino S, Fusano A, Fukuyama T, Ryu I. Acc. Chem. Res. 2014; 47: 1563
• 26d Matsubara H, Kawamoto T, Fukuyama T, Ryu I. Acc. Chem. Res. 2018; 51: 2023
• 26e Kawamoto T, Fukuyama T, Picard B, Ryu I. Chem. Commun. 2022; 58: 7608
• 26f For a review on acyl radicals, see: Chatgilialoglu C, Crich D, Komatsu M, Ryu I. Chem. Rev. 1999; 99: 1991
• 27 Sumino S, Fukuyama T, Ryu I. In The Chemical Transformations of C1 Compounds, Vol. 2. Ding K, Wu X.-F, Han B, Liu Z. Wiley-VCH; Weinheim: 2022: 567
• 28a Maillard B, Forrest D, Ingold KU. J. Am. Chem. Soc. 1976; 98: 7024
• 28b Newcomb M, Glenn AG. J. Am. Chem. Soc. 1989; 111: 275
• 28c Hollis R, Hughes L, Bowry VW, Ingold KU. J. Org. Chem. 1992; 57: 4284
• 28d Horner JH, Tanaka N, Newcomb M. J. Am. Chem. Soc. 1998; 120: 10379

For reviews, see:
• 29a Ryu I, Sonoda N, Curran DP. Chem. Rev. 1996; 96: 177
• 29b Fusano A, Ryu I. In Science of Synthesis: Multicomponent Reactions 2 . Muller TJ. J. Georg Thieme Verlag; Germany: 2014: 409
• 29c Godineau E, Landais Y. Chem. Eur. J. 2009; 15: 3044
• 30 Mizuno K, Ikeda M, Toda S, Otsuji Y. J. Am. Chem. Soc. 1988; 110: 1288
• 31 For bromine-radical-catalyzed [3+2] cyclizations of vinylidene cyclopropanes with alkenes, see: Chen D.-F, Chrisman CH, Miyake GM. ACS Catal. 2020; 10: 2609
• 32a Feldman KS, Romanelli AL, Ruckle RE. Jr, Miller RF. J. Am. Chem. Soc. 1988; 110: 3300
• 32b Miura K, Fugami K, Oshima K, Utimoto K. Tetrahedron Lett. 1988; 29: 5135
• 32c Feldman KS, Romanelli AL, Ruckle RE. Jr, Jean G. J. Org. Chem. 1992; 57: 100
• 32d Hashimoto T, Kawamata Y, Maruoka K. Nat. Chem. 2014; 6: 702
• 33a Curran DP, Xu J, Lazzarini E. J. Am. Chem. Soc. 1995; 117: 6603
• 33b Curran DP, Xu J, Lazzarini E. J. Chem. Soc., Perkin Trans. 1 1995; 3049