Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Smith, Andrew J. and Young, Allan and Rohrbach, Simon and O'Connor, Erin F. and Allison, Mark and Wang, Hong-Shuang and Poole, Darren L. and Tuttle, Tell and Murphy, John A. (2017) Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH). Angewandte Chemie International Edition, 56 (44). 13747–13751. ISSN 1433-7851

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    Abstract

    Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.