TY - JOUR
T1 - Development and Application of Ester-Mediated Nucleophilic Aromatic Substitution Reaction
AU - Hattori, Tetsutaro
AU - Miyano, Sotaro
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1997
Y1 - 1997
N2 - Nucleophilic aromatic substitution (SNAr) reactions of ortho-alkoxyarylcarboxylic esters by C-, N-, and O-nucleophiles, developed in our laboratory, are reviewed. Aryl Grignard reagents efficiently displaced the 1-methoxy group of 1-methoxy-2-naphthoates to afford the corresponding biaryls in excellent yields ; isopropyl ester is bulky enough to prevent the Grignard addition to the ester carbonyl function. 2-Methoxybenzoic esters derived from 2,6-dialkylphenols also underwent the SNAr reaction by proper choice of the bulk of the 2,6-dialkyl-substituents. High levels of asymmetric induction were achieved in these reactions by use of an enantiomeric menthoxy leaving group. As the electrondonating ability of the carbanion species increased, 1,4- or 1,6-conjugate addition of the nucleophiles to the 2-methoxybenzoates was found to compete with the SNAr reaction. Triarylamines were conveniently prepared by the reaction of a 2- or 4-fluorobenzoate with lithium diarylamides in THF-HMPA. 2-Sulfonyl- as well as 2-phosphinoyl-substituted 1-methoxynaphthalenes also underwent the SNAr reaction. Factors affecting the activating power of the 2-substituents are discussed.
AB - Nucleophilic aromatic substitution (SNAr) reactions of ortho-alkoxyarylcarboxylic esters by C-, N-, and O-nucleophiles, developed in our laboratory, are reviewed. Aryl Grignard reagents efficiently displaced the 1-methoxy group of 1-methoxy-2-naphthoates to afford the corresponding biaryls in excellent yields ; isopropyl ester is bulky enough to prevent the Grignard addition to the ester carbonyl function. 2-Methoxybenzoic esters derived from 2,6-dialkylphenols also underwent the SNAr reaction by proper choice of the bulk of the 2,6-dialkyl-substituents. High levels of asymmetric induction were achieved in these reactions by use of an enantiomeric menthoxy leaving group. As the electrondonating ability of the carbanion species increased, 1,4- or 1,6-conjugate addition of the nucleophiles to the 2-methoxybenzoates was found to compete with the SNAr reaction. Triarylamines were conveniently prepared by the reaction of a 2- or 4-fluorobenzoate with lithium diarylamides in THF-HMPA. 2-Sulfonyl- as well as 2-phosphinoyl-substituted 1-methoxynaphthalenes also underwent the SNAr reaction. Factors affecting the activating power of the 2-substituents are discussed.
KW - Aminophosphine
KW - Asymmetric ring-opening reaction
KW - Asymmetric synthesis
KW - Biaryl
KW - Conjugate addition
KW - Cyclophane
KW - Lignan
KW - Nucleophilic aromatic substitution
KW - Triarylamine
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U2 - 10.5059/yukigoseikyokaishi.55.121
DO - 10.5059/yukigoseikyokaishi.55.121
M3 - Article
AN - SCOPUS:0031070786
VL - 55
SP - 121
EP - 131
JO - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
JF - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
SN - 0037-9980
IS - 2
ER -