Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group, and base-solvent on the nitrile-forming transition states

Sang Yong Pyuna; Bong Rae Chob

doi:10.3998/ark.5550190.0011.709

Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group, and base-solvent on the nitrile-forming transition states

Sang Yong Pyuna
, Bong Rae Chob^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

This account summarizes the results of mechanism studies on the nitrile-forming eliminations from (E)- and (Z)-arylaldehyde O-benzoyloximes promoted by 1,8-diazabicyclo-[5.4.0]undec-7- ene (DBU) in MeCN, R1R2NH in MeCN, and R1R2NH/R1R2NH2 + in 70mol% MeCN(aq). The rate of anti-elimination was 36,000-fold faster than that of syn-elimination. The change of the β- aryl group from Ph to thienyl to furyl shifted the E2 transition state slightly towards product-like. When (E)-2,4-dinitrobenzaldehyde O-benzoyloxime was employed as the reactant and R1R2NH/R1R2NH2 + in 70mol% MeCN(aq) was used as the base-solvent, the (E1cb)irr was observed.

Original language	English
Pages (from-to)	118-137
Number of pages	20
Journal	Arkivoc
Volume	2010
Issue number	7
DOIs	https://doi.org/10.3998/ark.5550190.0011.709
Publication status	Published - 2010 Jul 15

Keywords

E1cb mechanism
E2 mechanism
Elimination
Transition state

ASJC Scopus subject areas

Organic Chemistry

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10.3998/ark.5550190.0011.709

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title = "Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group, and base-solvent on the nitrile-forming transition states",

abstract = "This account summarizes the results of mechanism studies on the nitrile-forming eliminations from (E)- and (Z)-arylaldehyde O-benzoyloximes promoted by 1,8-diazabicyclo-[5.4.0]undec-7- ene (DBU) in MeCN, R1R2NH in MeCN, and R1R2NH/R1R2NH2 + in 70mol\% MeCN(aq). The rate of anti-elimination was 36,000-fold faster than that of syn-elimination. The change of the β- aryl group from Ph to thienyl to furyl shifted the E2 transition state slightly towards product-like. When (E)-2,4-dinitrobenzaldehyde O-benzoyloxime was employed as the reactant and R1R2NH/R1R2NH2 + in 70mol\% MeCN(aq) was used as the base-solvent, the (E1cb)irr was observed.",

keywords = "E1cb mechanism, E2 mechanism, Elimination, Transition state",

author = "Pyuna, \{Sang Yong\} and Chob, \{Bong Rae\}",

year = "2010",

month = jul,

day = "15",

doi = "10.3998/ark.5550190.0011.709",

language = "English",

volume = "2010",

pages = "118--137",

journal = "Arkivoc",

issn = "1551-7012",

publisher = "Arkat",

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T1 - Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group, and base-solvent on the nitrile-forming transition states

AU - Pyuna, Sang Yong

AU - Chob, Bong Rae

PY - 2010/7/15

Y1 - 2010/7/15

N2 - This account summarizes the results of mechanism studies on the nitrile-forming eliminations from (E)- and (Z)-arylaldehyde O-benzoyloximes promoted by 1,8-diazabicyclo-[5.4.0]undec-7- ene (DBU) in MeCN, R1R2NH in MeCN, and R1R2NH/R1R2NH2 + in 70mol% MeCN(aq). The rate of anti-elimination was 36,000-fold faster than that of syn-elimination. The change of the β- aryl group from Ph to thienyl to furyl shifted the E2 transition state slightly towards product-like. When (E)-2,4-dinitrobenzaldehyde O-benzoyloxime was employed as the reactant and R1R2NH/R1R2NH2 + in 70mol% MeCN(aq) was used as the base-solvent, the (E1cb)irr was observed.

AB - This account summarizes the results of mechanism studies on the nitrile-forming eliminations from (E)- and (Z)-arylaldehyde O-benzoyloximes promoted by 1,8-diazabicyclo-[5.4.0]undec-7- ene (DBU) in MeCN, R1R2NH in MeCN, and R1R2NH/R1R2NH2 + in 70mol% MeCN(aq). The rate of anti-elimination was 36,000-fold faster than that of syn-elimination. The change of the β- aryl group from Ph to thienyl to furyl shifted the E2 transition state slightly towards product-like. When (E)-2,4-dinitrobenzaldehyde O-benzoyloxime was employed as the reactant and R1R2NH/R1R2NH2 + in 70mol% MeCN(aq) was used as the base-solvent, the (E1cb)irr was observed.

KW - E1cb mechanism

KW - E2 mechanism

KW - Elimination

KW - Transition state

UR - https://www.scopus.com/pages/publications/84866616026

U2 - 10.3998/ark.5550190.0011.709

DO - 10.3998/ark.5550190.0011.709

M3 - Article

AN - SCOPUS:84866616026

SN - 1551-7012

VL - 2010

SP - 118

EP - 137

JO - Arkivoc

JF - Arkivoc

IS - 7

ER -

Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group, and base-solvent on the nitrile-forming transition states

Abstract

Keywords

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