relation: http://d-scholarship-dev.library.pitt.edu/27586/
title: Mechanistic and preparative studies of radical chain homolytic substitution reactions of n-heterocyclic carbene boranes and disulfides
creator: Pan, X
creator: Vallet, AL
creator: Schweizer, S
creator: Dahbi, K
creator: Delpech, B
creator: Blanchard, N
creator: Graff, B
creator: Geib, SJ
creator: Curran, DP
creator: Lalevée, J
creator: Lacoîte, E
description: Reactions of 1,3-dimethylimidazol-2-ylidene-borane (diMe-Imd-BH 3) and related NHC-boranes with diaryl and diheteroaryl disulfides provide diverse NHC-boryl monosulfides (diMe-Imd-BH2SAr) and NHC-boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC-borane in the primary NHC-boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure. Most substitution reactions are thought to proceed through radical chains in which homolytic substitution of a disulfide by an NHC-boryl radical is a key step. However, with electrophilic disulfides under dark conditions, a competing ionic path may also be possible. © 2013 American Chemical Society.
date: 2013-07-17
type: Article
type: PeerReviewed
format: text/plain
language: en
rights: attached
identifier: http://d-scholarship-dev.library.pitt.edu/27586/1/licence.txt
identifier:   Pan, X and Vallet, AL and Schweizer, S and Dahbi, K and Delpech, B and Blanchard, N and Graff, B and Geib, SJ and Curran, DP and Lalevée, J and Lacoîte, E  (2013) Mechanistic and preparative studies of radical chain homolytic substitution reactions of n-heterocyclic carbene boranes and disulfides.  Journal of the American Chemical Society, 135 (28).  10484 - 10491.  ISSN 0002-7863     
relation: 10.1021/ja403627k