Borylation of Alkenyl Carbamates by Means of Sodium Metal

Abstract

Treatment of alkenyl carbamates with sodium dispersion and a co-existing boron electrophile affords alkenylboronates via the reductive cleavage of the vinylic C–O bond. The key to this borylation is an instant trapping of reactive organosodium species with the co-existing boron electrophile.

Key words

alkenyl carbamate - sodium dispersion - borylation - alkenylboronate - electron transfer

Publication History

Received: 13 September 2022

Accepted after revision: 31 October 2022

Accepted Manuscript online:
31 October 2022

Article published online:
29 November 2022

• References


Selected reviews on transformations of C–O bonds including reactions of carbamates:
• 1a Rosen BM, Quasdorf KW, Wilson DA, Zhang N, Resmerita A, Garg NK, Percec V. Chem. Rev. 2011; 111: 1346
• 1b Li B, Yu D, Sun C, Shi Z. Chem. Eur. J. 2011; 17: 1728
• 1c Zeng H, Qiu Z, Domínguez-Huerta A, Hearne Z, Chen Z, Li C. ACS Catal. 2017; 7: 510
• 1d Qiu Z, Li C. Chem. Rev. 2020; 120: 10454
• 2a Kocienski P, Dixon NJ. Synlett 1989; 52
• 2b Sengupta S, Leite M, Raslan DS, Quesnelle C, Snieckus V. J. Org. Chem. 1992; 57: 4066
• 2c Madec D, Pujol S, Henryon V, Férézou JP. Synlett 1995; 435
• 2d Porée F, Clavel A, Betzer J, Pancrazi A, Ardisson J. Tetrahedron Lett. 2003; 44: 7553
• 2e Xu L, Li B, Wu Z, Lu X, Guan B, Wang B, Zhao K, Shi Z. Org. Lett. 2010; 12: 884
• 2f Muto K, Hatakeyama T, Yamaguchi J, Itami K. Chem. Sci. 2015; 6: 6792
• 2g Guo L, Hsiao C, Yue H, Liu X, Rueping M. ACS Catal. 2016; 6: 4438
• 2h Rivera AC. P, Still R, Frantz DE. Angew. Chem. Int. Ed. 2016; 55: 6689
• 2i Ogawa H, Yang Z, Minami H, Kojima K, Saito T, Wang C, Uchiyama M. ACS Catal. 2017; 7: 3988
• 2j Li J, Ren Q, Cheng X, Karaghiosoff K, Knochel P. J. Am. Chem. Soc. 2019; 141: 18127
• 2k Chen Z, So CM. Org. Lett. 2020; 22: 3879
• 3a Huang K, Yu D, Zheng S, Wu Z, Shi Z. Chem. Eur. J. 2011; 17: 786
• 3b Geng S, Zhang J, Chen S, Liu Z, Zeng X, He Y, Feng Z. Org. Lett. 2020; 22: 5582
• 4a Murugesan V, Balakrishnan V, Rasappan R. J. Catal. 2019; 377: 293
• 4b Zhang J, Zhang Y, Geng S, Chen S, Liu Z, Zeng X, He Y, Feng Z. Org. Lett. 2020; 22: 2669
• 5 Takise R, Itami K, Yamaguchi J. Org. Lett. 2016; 18: 4428
• 6 Liard A, Marek I. J. Org. Chem. 2000; 65: 7218
• 7a Takahashi F, Nogi K, Sasamori T, Yorimitsu H. Org. Lett. 2019; 21: 4739
• 7b Fukazawa M, Takahashi F, Nogi K, Sasamori T, Yorimitsu H. Org. Lett. 2020; 22: 2303
• 7c Ito S, Fukazawa M, Takahashi F, Nogi K, Yorimitsu H. Bull. Chem. Soc. Jpn. 2020; 93: 1171
• 7d Wang S, Kaga A, Yorimitsu H. Synlett 2021; 32: 219
• 7e Fukazawa M, Takahashi F, Yorimitsu H. Org. Lett. 2021; 23: 4613
• 7f Wang S, Kaga A, Yorimitsu H. Heterocycles 2021; 103: 1057
• 7g Wang S, Kaga A, Kurogi T, Yorimitsu H. Org. Lett. 2022; 24: 1105
• 7h Takahashi F, Kurogi T, Yorimitsu H. ChemRxiv 2022; preprint
• 8a Tsuchiya S, Saito H, Nogi K, Yorimitsu H. Org. Lett. 2019; 21: 3855
• 8b Kaga A, Iida H, Tsuchiya S, Saito H, Nakano K, Yorimitsu H. Chem. Eur. J. 2021; 27: 4567
• 8c Ozaki T, Kaga A, Saito H, Yorimitsu H. Synthesis 2021; 53: 3019
• 8d Ito S, Takahashi F, Yorimitsu H. Asian J. Org. Chem. 2021; 10: 1440
• 8e Koyama S, Takahashi F, Saito H, Yorimitsu H. Org. Lett. 2021; 23: 8590

Selected examples of reductive transformations using sodium dispersion reported by other groups:
• 9a Gissot A, Becht J, Desmurs JR, Pevere V, Wagner A, Mioskowski C. Angew. Chem. Int. Ed. 2002; 41: 340
• 9b An J, Work DN, Kenyon C, Procter DJ. J. Org. Chem. 2014; 79: 6743
• 9c Asako S, Nakajima H, Takai K. Nat. Catal. 2019; 2: 297
• 9d Asako S, Takahashi I, Nakajima H, Ilies L, Takai K. Commun. Chem. 2021; 4: 76
• 9e Asako S, Takahashi I, Kurogi T, Murakami Y, Ilies L, Takai K. Chem. Lett. 2022; 51: 38
• 10 Review on sodium dispersion in organic synthesis: De PB, Asako S, Ilies L. Synthesis 2021; 53: 3180

Selected recent reviews on the OCF₃ group:
• 11a Hardy MA, Chachignon H, Cahard D. Asian J. Org. Chem. 2019; 8: 591
• 11b Romero AH. Top. Curr. Chem. 2019; 377: 9
• 11c Liu J, Lin W, Sorochinsky AE, Butler G, Landa A, Han J, Soloshonok VA. J. Fluorine Chem. 2022; 257–258: 109978
• 12 We experimentally confirmed that carbamate 1a gradually decomposed in a solution of 1-styryllithium even at –40 °C in the absence of B(OMe)₃.
• 13 Barsamian AL, Wua Z, Blakemore PR. Org. Biomol. Chem. 2015; 13: 3781
• 14 Stivanin ML, Fernandes AA. G, da Silva AF, Okada CY. Jr, Jurberg ID. Adv. Synth. Catal. 2020; 362: 1106
• 15 Enthaler S, Erre G, Junge K, Michalik D, Spannenberg A, Marras F, Gladiali S, Beller M. Tetrahedron: Asymmetry 2007; 18: 1288
• 16 Panella L, Feringa BL, de Vries JG, Minnaard AJ. Org. Lett. 2005; 7: 4177
• 17 Seijas JA, Vázquez-Tato MP, Crecente-Campo J. Synlett 2007; 2420
• 18 Shang W, Peng F, Feng Q, Fang F, Pan Z, Ji X, Xia C. Org. Chem. Front. 2022; 9: 2680
• 19 Zhang P, Suárez JM, Driant T, Derat E, Zhang Y, Ménand M, Roland S, Sollogoub M. Angew. Chem. Int. Ed. 2017; 56: 10821
• 20 Blasius CK, Vasilenko V, Matveeva R, Wadepohl H, Gade LH. Angew. Chem. Int. Ed. 2020; 59: 23010
• 21 Gao Y, Yazdani S, Kendrick AIV, Junor GP, Kang T, Grotjahn DB, Bertrand G, Jazzar R, Engle KM. Angew. Chem. Int. Ed. 2021; 60: 19871
• 22 Ping Y, Wang R, Wang Q, Chang T, Huo J, Lei M, Wang J. J. Am. Chem. Soc. 2021; 143: 9769
• 23 Hansen AL, Ebran J, Gøgsig TM, Skrydstrup T. Chem. Commun. 2006; 4137
• 24 Roche M, Salim SM, Bignon J, Levaique H, Brion J, Alami M, Hamze A. J. Org. Chem. 2015; 80: 6715