A Dearomatization/Debromination Strategy for the [4+1] Spiroannulation of Bromophenols with α,β-Unsaturated Imines

被引：49

作者：

Ge, Yicong ^{[1
]}

Qin, Cheng ^{[1
]}

Bai, Lu ^{[1
]}

Hao, Jiamao ^{[1
]}

Liu, Jingjing ^{[1
]}

Luan, Xinjun ^{[1
]}

机构：

[1] Northwest Univ, Coll Chem & Mat Sci, Minist Educ, Key Lab Synthet & Nat Funct Mol, Xian 710127, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 43期

基金：

美国国家科学基金会;

关键词：

bromophenol; dearomatization; debromination; spiroannulation; synthetic methods; NUCLEOPHILIC-SUBSTITUTION REACTIONS; ASYMMETRIC ALLYLIC DEAROMATIZATION; INTRAMOLECULAR DEAROMATIZATION; ENANTIOSELECTIVE DEAROMATIZATION; OXIDATIVE DEAROMATIZATION; BETA-NAPHTHOLS; EFFICIENT; CONSTRUCTION; CHLORINATION; 2-NAPHTHOLS;

D O I：

10.1002/anie.202008130

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel [4+1] spiroannulation ofo- &p-bromophenols with alpha,beta-unsaturated imines has been developed for the direct synthesis of a new family of azaspirocyclic molecules. Notably, several other halophenols (X=Cl, I) were also applicable for this transformation. Moreover, a catalytic asymmetric version of the reaction was realized with 1-bromo-2-naphthols by using a chiral Sc-III/Py-Box catalyst. Mechanistic studies revealed that this domino reaction proceeded through electrophile-triggered dearomatization of phenol derivatives at their halogenated positions and followed by halogen-displacement withN-nucleophiles via a radical-based S(RN)1 mechanism.

引用

页码：18985 / 18989

页数：5

共 75 条

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