Abstract
AbstractRecent 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.
Highlights
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 silylation of arenes and heteroarenes as well as reductive cleavage of CÀO bonds in aryl ethers and CÀS bonds in aryl thioethers
Stoltz, Grubbs et al.[1] have discovered a simple and elegant system comprising Et3SiH (2) and KOtBu which achieves a number of remarkable reactions: 1) converting arenes and heteroarenes, and their alkylated counterparts, into silyl-substituted products, often with excellent regiocontrol[1a–c] (e.g. 1!3; Scheme 1); 2) achieving reductive CÀS bond cleavage in aryl thioethers (e.g. 4!5) in a reaction which has potential importance in removing sulfur traces from hydrocarbon fuels;[1d] 3) triggering reductive CÀO bond cleavage in aryl ethers (e.g. 6!7) in a reaction with potential applications to controlled lignin degradation.[1a,d] A number of intermediates likely arise from reaction of these two reagents, and spectroscopic evidence has resulted in informed proposals being made for their structures
These reactions have proved puzzling, but a recent coordinated study by synthetic, mechanistic, and computational chemists has allowed significant advances to be made.[1e,f] The conclusions are: 1) the combination of Et3SiH and KOtBu leads to triethylsilyl
Summary
International Edition: DOI: 10.1002/anie.201707914 German Edition: DOI: 10.1002/ange.201707914 Electron-Transfer and Hydride-Transfer Pathways in the Stoltz– Grubbs Reducing System (KOtBu/Et3SiH) Andrew J. Smith, Allan Young, Simon Rohrbach, Erin F. OConnor, Mark Allison, HongShuang Wang, Darren L. Poole, Tell Tuttle,* and John A. Murphy*
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