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

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 thio...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2017-10, Vol.129 (44), p.13935-13939
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
Chemistry
Computer applications
Dichtefunktionalrechnungen
Electron transfer
Elektronentransfer
Ethers
Hydride
Intermediates
Potassium
Reaktionsmechanismen
Silicium
Thioethers
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Das vielseitige System Triethylsilan/Kalium‐tert‐butoxid wurde für die C‐N‐Bindungsspaltung in N‐Benzyl‐ (siehe Schema) und N‐Allylindolen sowie für die Reduktion polycyclischer Arene zu ihren Dihydroderivaten genutzt.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201707914