Electron‐Transfer and Hydride‐Transfer Pathways in the Stoltz–Grubbs Reducing System (KOtBu/Et3SiH)

• Published in: Angewandte Chemie International Edition 2017-10, Vol.56 (44), p.13747-13751
• Main Authors: Smith, Andrew J., Young, Allan, Rohrbach, Simon, O'Connor, Erin F., Allison, Mark, Wang, Hong‐Shuang, Poole, Darren L., Tuttle, Tell, Murphy, John A.
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Chemical bonds; Communication; Communications; Computer applications; density-functional calculations; Electron transfer; Ethers; hydrides; Intermediates; Potassium; reaction mechanisms; silicon; Thioethers
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201707914

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. Transfers: Triethylsilane and potassium tert‐butoxide react to form a highly attractive and versatile system. The work herein highlights the reductive transformations which lead to 1) C−N bond cleavage in N‐benzyl‐ and N‐allylindoles and 2) reduction of polycyclic arenes to their dihydro derivatives.