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A Regio‐ and Stereoselective Carbonylative Approach to Alkyl ( Z )‐2‐[3‐Oxoisobenzofuran‐1‐(3 H )‐ylidene]acetates
Author(s) -
Mancuso Raffaella,
Ziccarelli Ida,
Fini Francesco,
Della Ca' Nicola,
Marino Nadia,
Carfagna Carla,
Gabriele Bartolo
Publication year - 2019
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201801308
Subject(s) - chemistry , carbonylation , stereoselectivity , trimethylsilyl , alcohol , alkyl , medicinal chemistry , nucleophile , benzoic acid , stereochemistry , carbon monoxide , catalysis , organic chemistry
The first example of the oxidative carbonylation of 2‐ethynylbenzoic acid derivatives, leading to alkyl ( Z )‐2‐[3‐oxoisobenzofuran‐1‐(3 H )‐ylidene]acetates in a regio‐ and stereoselective manner, is reported. Under the catalytic action of PdI 2 (2 mol%) in conjuction with KI (20 mol%), different 2‐[(trimethylsilyl)ethynyl]benzoic acids were converted into the corresponding isobenzofuranones in high to excellent yields (70–98%). The proposed reaction mechanism involves syn 5‐ exo ‐dig cyclization, carbon monoxide insertion, and nucleophilic displacement by an alcohol. Desilylation occurred under the reaction conditions. The structure of a representative product, that is, methyl ( Z )‐2‐[3‐oxoisobenzofuran‐1(3 H )‐ylidene]acetate, was confirmed by XRD analysis.