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Mechanistic and preparative studies of radical chain homolytic substitution reactions of n-heterocyclic carbene boranes and disulfides

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

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Abstract

Reactions of 1,3-dimethylimidazol-2-ylidene-borane (diMe-Imd-BH3) 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.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Pan, X
Vallet, AL
Schweizer, S
Dahbi, K
Delpech, B
Blanchard, N
Graff, B
Geib, SJgeib@pitt.eduGEIB0000-0002-9160-7857
Curran, DPcurran@pitt.eduCURRAN
Lalevée, J
Lacoîte, E
Date: 17 July 2013
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 135
Number: 28
Page Range: 10484 - 10491
DOI or Unique Handle: 10.1021/ja403627k
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
MeSH Headings: Boranes--chemistry; Disulfides--chemistry; Free Radicals--chemical synthesis; Free Radicals--chemistry; Heterocyclic Compounds--chemical synthesis; Heterocyclic Compounds--chemistry; Methane--analogs & derivatives; Methane--chemical synthesis; Methane--chemistry; Molecular Structure
PubMed ID: 23718209
Date Deposited: 06 Apr 2016 15:36
Last Modified: 02 Feb 2019 15:58
URI: http://d-scholarship.pitt.edu/id/eprint/27586

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