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
|
Plain Text (licence)
Available under License : See the attached license file.
Download (1kB)
|
Abstract
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.
Share
Citation/Export: |
|
Social Networking: |
|
Details
Item Type: |
Article
|
Status: |
Published |
Creators/Authors: |
Creators | Email | Pitt Username | ORCID |
---|
Pan, X | | | | Vallet, AL | | | | Schweizer, S | | | | Dahbi, K | | | | Delpech, B | | | | Blanchard, N | | | | Graff, B | | | | Geib, SJ | geib@pitt.edu | GEIB | 0000-0002-9160-7857 | Curran, DP | curran@pitt.edu | CURRAN | | 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: |
12 Jun 2021 22:56 |
URI: |
http://d-scholarship-dev.library.pitt.edu/id/eprint/27586 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Altmetric.com
Actions (login required)
|
View Item |