Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile

William J. Spillane; Paul McGrath; Chris Brack; Keith Barry

doi:10.1039/a801505h

Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile

William J. Spillane
, Paul McGrath
, Chris Brack
, Keith Barry

Cellular & Molecular Medicine

University of Galway

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

10 Citations (Scopus)

Abstract

The observation of biphasic Brønsted plots (β₁ ca. 0.7 and β₂ ca. 0) in the aminolysis (alicyclic amines, pyridines) of 4-nitrophenyl N-benzylsulfamate 1a in MeCN is interpreted as being due to a mechanistic change from (ElcB)_irrev to (ElcB)_rev; the change in rate-determining step occurs at approximately the pK_a of 1a and other more basic substrates give straight line plots; an entropy study supports the change from a bimolecular to a unimolecular mechanism.

Original language	English
Pages (from-to)	1017-1018
Number of pages	2
Journal	Chemical Communications
Issue number	9
DOIs	https://doi.org/10.1039/a801505h
Publication status	Published - 7 May 1998

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title = "Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile",

abstract = "The observation of biphasic Br{\o}nsted plots (β1 ca. 0.7 and β2 ca. 0) in the aminolysis (alicyclic amines, pyridines) of 4-nitrophenyl N-benzylsulfamate 1a in MeCN is interpreted as being due to a mechanistic change from (ElcB)irrev to (ElcB)rev; the change in rate-determining step occurs at approximately the pKa of 1a and other more basic substrates give straight line plots; an entropy study supports the change from a bimolecular to a unimolecular mechanism.",

author = "Spillane, \{William J.\} and Paul McGrath and Chris Brack and Keith Barry",

year = "1998",

month = may,

day = "7",

doi = "10.1039/a801505h",

language = "English",

pages = "1017--1018",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

number = "9",

}

TY - JOUR

T1 - Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile

AU - Spillane, William J.

AU - McGrath, Paul

AU - Brack, Chris

AU - Barry, Keith

PY - 1998/5/7

Y1 - 1998/5/7

N2 - The observation of biphasic Brønsted plots (β1 ca. 0.7 and β2 ca. 0) in the aminolysis (alicyclic amines, pyridines) of 4-nitrophenyl N-benzylsulfamate 1a in MeCN is interpreted as being due to a mechanistic change from (ElcB)irrev to (ElcB)rev; the change in rate-determining step occurs at approximately the pKa of 1a and other more basic substrates give straight line plots; an entropy study supports the change from a bimolecular to a unimolecular mechanism.

AB - The observation of biphasic Brønsted plots (β1 ca. 0.7 and β2 ca. 0) in the aminolysis (alicyclic amines, pyridines) of 4-nitrophenyl N-benzylsulfamate 1a in MeCN is interpreted as being due to a mechanistic change from (ElcB)irrev to (ElcB)rev; the change in rate-determining step occurs at approximately the pKa of 1a and other more basic substrates give straight line plots; an entropy study supports the change from a bimolecular to a unimolecular mechanism.

UR - https://www.scopus.com/pages/publications/0002352521

U2 - 10.1039/a801505h

DO - 10.1039/a801505h

M3 - Article

SN - 1359-7345

SP - 1017

EP - 1018

JO - Chemical Communications

JF - Chemical Communications

IS - 9

ER -

Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile

Abstract

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