Copper-Catalyzed Reductive Ireland–Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates

The copper-catalyzed reductive Ireland–Claisen rearrangement of propargylic acrylates led to 3,4-allenoic acids. The use of silanes or pinacolborane as stoichiometric reducing agents and triethylphosphite as a ligand facilitated the divergent and complementary selectivity for the synthesis of diaste...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2022-01, Vol.87 (1), p.429-452
Main Authors: Guo, Siyuan, Wong, Kong Ching, Scheeff, Stephan, He, Zhuo, Chan, Wesley Ting Kwok, Low, Kam-Hung, Chiu, Pauline
Format: Article
Language:English
Subjects:
Acrylates
Catalysis
Copper
Silanes
Stereoisomerism
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 copper-catalyzed reductive Ireland–Claisen rearrangement of propargylic acrylates led to 3,4-allenoic acids. The use of silanes or pinacolborane as stoichiometric reducing agents and triethylphosphite as a ligand facilitated the divergent and complementary selectivity for the synthesis of diastereomeric anti- and syn-rearranged products, respectively. Copper-catalyzed reductive Ireland–Claisen rearrangement of allylic 2,3-allenoates proceeded effectively only when pinacolborane was used as a reductant to generate various 1,5-dienes in excellent yields and with good diastereoselectivities in some cases. Mechanistic studies showed that the silyl and boron enolates, rather than the copper enolate, underwent a stereospecific rearrangement via a chairlike transition state to afford the corresponding Claisen rearrangement products.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.1c02455