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Title: Facile solvolysis of a surprisingly twisted tertiary amide

Abstract

In this study, a bicyclo[2.2.2]octane derivative containing both a tertiary amide and a methyl ester was shown crystallographically to adopt a conformation in which the amide is in the cis configuration, which is sterically disfavored, but electronically favored. The steric strain induces a significant torsion (15.9°) of the amide, thereby greatly increasing the solvolytic lability of the amide to the extent that we see competitive amide solvolysis in the presence of the normally more labile methyl ester also present in the molecule.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Yale Univ., New Haven, CT (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1435717
Grant/Contract Number:  
SC0001059
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
New Journal of Chemistry
Additional Journal Information:
Journal Volume: 40; Journal Issue: 3; Journal ID: ISSN 1144-0546
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bloomfield, Aaron J., Chaudhuri, Subhajyoti, Mercado, Brandon Q., Batista, Victor S., and Crabtree, Robert H. Facile solvolysis of a surprisingly twisted tertiary amide. United States: N. p., 2016. Web. doi:10.1039/c5nj02449h.
Bloomfield, Aaron J., Chaudhuri, Subhajyoti, Mercado, Brandon Q., Batista, Victor S., & Crabtree, Robert H. Facile solvolysis of a surprisingly twisted tertiary amide. United States. doi:10.1039/c5nj02449h.
Bloomfield, Aaron J., Chaudhuri, Subhajyoti, Mercado, Brandon Q., Batista, Victor S., and Crabtree, Robert H. Tue . "Facile solvolysis of a surprisingly twisted tertiary amide". United States. doi:10.1039/c5nj02449h. https://www.osti.gov/servlets/purl/1435717.
@article{osti_1435717,
title = {Facile solvolysis of a surprisingly twisted tertiary amide},
author = {Bloomfield, Aaron J. and Chaudhuri, Subhajyoti and Mercado, Brandon Q. and Batista, Victor S. and Crabtree, Robert H.},
abstractNote = {In this study, a bicyclo[2.2.2]octane derivative containing both a tertiary amide and a methyl ester was shown crystallographically to adopt a conformation in which the amide is in the cis configuration, which is sterically disfavored, but electronically favored. The steric strain induces a significant torsion (15.9°) of the amide, thereby greatly increasing the solvolytic lability of the amide to the extent that we see competitive amide solvolysis in the presence of the normally more labile methyl ester also present in the molecule.},
doi = {10.1039/c5nj02449h},
journal = {New Journal of Chemistry},
number = 3,
volume = 40,
place = {United States},
year = {Tue Jan 05 00:00:00 EST 2016},
month = {Tue Jan 05 00:00:00 EST 2016}
}

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Cited by: 1 work
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Works referenced in this record:

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965