Late-Stage Derivatization of Buflavine by Nickel-Catalyzed Direct Substitution of a Methoxy Group via C–O Bond Activation

Dedicated to Professor Shinji Murai for his contribution to bond activation.

Abstract

The nickel-catalyzed cross-coupling of methoxyarenes was applied to buflavine, which allows for the selective monosubstitution of one of the two methoxy groups in the molecule, leading to the formation of 2- and 3-substituted isomers. Trimethylsilylmethyl (TMSCH₂), phenyl, and alkynyl groups can be introduced into buflavine using this method. The resulting TMSCH₂ analogue of buflavine can also be converted into several other derivatives.

Key words

C–O bond activation - cross-coupling - nickel - natural product - late-stage functionalization

Publication History

Received: 10 March 2021

Accepted after revision: 25 March 2021

Accepted Manuscript online:
25 March 2021

Article published online:
21 April 2021

• References

• 1 Carlson EE. ACS Chem. Biol. 2010; 5: 639
• 2a White MC, Zhao J. J. Am. Chem. Soc. 2018; 140: 13988
• 2b Karimov RR, Hartwig JF. Angew. Chem. Int. Ed. 2018; 57: 4234
• 2c Cernak T, Dykstra KD, Tyagarajan S, Vachal P, Krska SW. Chem. Soc. Rev. 2016; 45: 546
• 3a Tobisu M, Chatani N. Acc. Chem. Res. 2015; 48: 1717
• 3b Tobisu M, Chatani N. Top. Organomet. Chem. 2013; 44: 35
• 3c Tobisu M, Chatani N. Nickel-Catalyzed Cross-Coupling Reactions of Unreactive Phenolic Electrophiles via C–O Bond Activation. In Ni- and Fe-Based Cross-Coupling Reactions . Correa A. Springer; Cham: 2017: 129-156
• 3d Tobisu M, Chatani N. Metal-Catalyzed Aromatic C–O Bond Activation/Transformation. In Organometallics for Green Catalysis. Topics in Organometallic Chemistry, Vol. 63. Dixneuf PH, Soulé J.-F. Springer; Cham: 2018: 103-140
• 3e Tobisu M. C–O Bond Transformations. In Nickel Catalysis in Organic Synthesis: Methods and Reactions . Ogoshi S. Wiley-VCH; Weinheim: 2020: 123-150

Reviews from other groups:
• 3f Li B.-J, Yu D.-G, Sun C.-L, Shi Z.-J. Chem. Eur. J. 2011; 17: 1728
• 3g Rosen BM, Quasdorf KW, Wilson DA, Zhang N, Resmerita A.-M, Garg NK, Percec V. Chem. Rev. 2011; 111: 1346
• 3h Yamaguchi J, Muto K, Itami K. Eur. J. Org. Chem. 2013; 19
• 3i Cornella J, Zarate C, Martin R. Chem. Soc. Rev. 2014; 43: 8081
• 3j Qiu Z, Li C.-J. Chem. Rev. 2020; 120: 10454
• 4a Tobisu M, Takahira T, Chatani N. Org. Lett. 2015; 17: 4352
• 4b Tobisu M, Takahira T, Ohtsuki A, Chatani N. Org. Lett. 2015; 17: 680
• 4c Tobisu M, Yasutome A, Kinuta H, Nakamura K, Chatani N. Org. Lett. 2014; 16: 5572
• 4d Morioka T, Nishizawa A, Nakamura K, Tobisu M, Chatani N. Chem. Lett. 2015; 44: 1729
• 4e Tobisu M, Takahira T, Morioka T, Chatani N. J. Am. Chem. Soc. 2016; 138: 6711
• 4f Igarashi T, Haito A, Chatani N, Tobisu M. ACS Catal. 2018; 8: 7475
• 5a Álvarez-Bercedo P, Martin R. J. Am. Chem. Soc. 2010; 132: 17352
• 5b Wang C, Ozaki T, Takita R, Uchiyama M. Chem. Eur. J. 2012; 18: 3482
• 5c Leiendecker M, Hsiao C.-C, Guo L, Alandini N, Rueping M. Angew. Chem. Int. Ed. 2014; 53: 12912
• 5d Wang T.-H, Ambre R, Wang Q, Lee W.-C, Wang P.-C, Liu Y, Zhao L, Ong T.-G. ACS Catal. 2018; 8: 11368
• 6 Isolation of 1: Viladomat F, Bastida J, Codina C, Campbell WE, Mathee S. Phytochemistry 1995; 40: 307

Biological activity of 1:
• 7a Ishida Y, Sasaki Y, Kimura Y, Watanabe K. J. Pharmacobio-Dyn. 1985; 8: 917
• 7b Ishida Y, Watanabe K, Kobayashi S, Kihara M. Chem. Pharm. Bull. 1977; 25: 1851

Unique reactivity of IMes^Me in nickel-catalyzed inert bond activation:
• 8a Tobisu M, Yasui K, Aihara Y, Chatani N. Angew. Chem. Int. Ed. 2017; 56: 1877
• 8b Morioka T, Nishizawa A, Furukawa T, Tobisu M, Chatani N. J. Am. Chem. Soc. 2017; 139: 1416
• 8c Yasui K, Chatani N, Tobisu M. Org. Lett. 2018; 20: 2108
• 8d See also ref. 4f
• 9a Das M, O’Shea DF. Tetrahedron 2013; 69: 6448
• 9b Zhang W.-X, Ding C.-H, Luo Z.-B, Hou X.-L, Dai L.-X. Tetrahedron Lett. 2006; 47: 8391
• 10a Barreiro EJ, Kümmerle AE, Fraga CA. M. Chem. Rev. 2011; 111: 5215
• 10b Schönherr H, Cernak T. Angew. Chem. Int. Ed. 2013; 52: 12256
• 11 Kinuta H, Tobisu M, Chatani N. J. Am. Chem. Soc. 2015; 137: 1593
• 12 Kosama S, Takita H, Kajimoto T, Nishide K, Node M. Tetrahedron 2004; 60: 4901
• 13 Dong Z, Wang J, Dong G. J. Am. Chem. Soc. 2015; 137: 5887
• 14 Wertz S, Leifert D, Studer A. Org. Lett. 2013; 15: 928
• 15 Bariwal JB, Ermolat’ev DS, Glasnov TN, Hecke KV, Mehta VP, Meervelt LV, Kappe CO, Van der Eycken EV. E. Org. Lett. 2010; 12: 2774
• 16 Jian Y, Sun G, Li J, Su D, Li C, Zhong G. Chin. J. Chem. 2011; 29: 1423