A Regio‐ and Stereoselective Carbonylative Approach to Alkyl (Z)‐2‐[3‐Oxoisobenzofuran‐1‐(3H)‐ylidene]acetates

The first example of the oxidative carbonylation of 2‐ethynylbenzoic acid derivatives, leading to alkyl (Z)‐2‐[3‐oxoisobenzofuran‐1‐(3H)‐ylidene]acetates in a regio‐ and stereoselective manner, is reported. Under the catalytic action of PdI2 (2 mol%) in conjuction with KI (20 mol%), different 2‐[(tr...

Full description

Saved in:
Bibliographic Details
Published in:Advanced synthesis & catalysis 2019-02, Vol.361 (4), p.690-695
Main Authors: Mancuso, Raffaella, Ziccarelli, Ida, Fini, Francesco, Della Ca', Nicola, Marino, Nadia, Carfagna, Carla, Gabriele, Bartolo
Format: Article
Language:English
Subjects:
2-ethynylbenzoic acids
Acetates
Benzoic acid
Carbon monoxide
carbonylation
Carbonyls
Catalysis
cyclization
isobenzofuranones
palladium
Reaction mechanisms
Stereoselectivity
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The first example of the oxidative carbonylation of 2‐ethynylbenzoic acid derivatives, leading to alkyl (Z)‐2‐[3‐oxoisobenzofuran‐1‐(3H)‐ylidene]acetates in a regio‐ and stereoselective manner, is reported. Under the catalytic action of PdI2 (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(3H)‐ylidene]acetate, was confirmed by XRD analysis.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201801308