Accelerating effect of meta substituents in the ester-mediated nucleophilic aromatic substitution reaction

被引:26
作者
Hattori, T [1 ]
Takeda, A [1 ]
Suzuki, K [1 ]
Koike, N [1 ]
Koshiishi, E [1 ]
Miyano, S [1 ]
机构
[1] Tohoku Univ, Grad Sch Engn, Dept Biomol Engn, Aoba Ku, Sendai, Miyagi 9808579, Japan
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1998年 / 22期
关键词
D O I
10.1039/a807646d
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The ester-mediated nucleophilic aromatic substitution (SNAr) reaction of 2-methoxybenzoic ester 1 with Grignard reagents 11 is greatly accelerated by introduction of a methoxy or halo substituent at the 3-position of the benzoate ring (7-10). The substituent effects of these groups at the 3-position are compared with those at the 5-position to suggest that the activation mechanism of the methoxy substituent is different from that of the halo substituent; the ligating ability of the 3-methoxy group plays a crucial role in enhancing the reactivity of the 2-methoxy moiety, while the electron-withdrawing ability is more important in the case of the halo groups. It has also been found that introduction of an additional methoxy substituent at the meta-position (33, 34) enables the SNAr methoxy-displacement reaction even at the pal a-position to the ester activator. The accelerating effect of the 3-bromo substituent is advantageously utilized for regioselective allylation of 3-bromo-2,6-dimethoxybenzoic ester 55 at the 2-position to provide an easy access to a multisubstituted naphthol 59, which is a key compound for the syntheses of michellamines A-C and the related naphthylisoquinoline alkaloids.
引用
收藏
页码:3661 / 3671
页数:11
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