Transition-Metal-Free Synthesis of Borylated Thiophenes via Formal Thioboration

被引：18

作者：

Abed, Hassen Bel ^{[1
]}

Blum, Suzanne A. ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92617 USA

来源：

ORGANIC LETTERS | 2018年 / 20卷 / 21期

基金：

美国国家科学基金会;

关键词：

C-H BORYLATION; LATE-STAGE FUNCTIONALIZATION; SUBSTITUTED THIOPHENES; MODULAR SYNTHESIS; BUILDING-BLOCKS; ARYL HALIDES; BORONIC ACID; SIGMA-BONDS; ALKYNES; ESTERS;

D O I：

10.1021/acs.orglett.8b02727

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A simple, regiocontrolled, and transition-metal-free approach to access exclusively 3-borylated thiophene derivatives is reported. The commercially available B-chlorocatecholborane reagent (ClBcat) acts as a carbophilic Lewis acid to activate the alkyne in readily synthesized (Z)-organylthioenyne substrates. This boron-induced activation initiates the formal thioboration and subsequent sulfur dealkylation, leading to the formation of 3-borylated thiophenes in good yields. The resulting borylated thiophenes are isolable as boronic esters (Bpin) and boronamides (Bdan). These borylated products are amenable to diverse downstream functionalization reactions, i.e., C-C bond formation through cross-coupling, azidation, bromination, and C-H activation.

引用

页码：6673 / 6677

页数：5

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