Copper Carbenoid, Reactant and Catalyst for One-Pot Diazo Ester Coupling Cascade Rearrangement of Enediynes: Formation of Two Contiguous Tetrasubstituted Stereocenters

The copper‐catalyzed reaction of enediynes with diazo esters leads to cyclic amino esters bearing two contiguous tetrasubstituted stereogenic centers through a one‐pot, five‐step cascade. Copper iodide catalyzes the formation of an intermediate 3‐alkynoate and copper carbenoid promotes its reversibl...

Full description

Saved in:
Bibliographic Details
Published in:Advanced synthesis & catalysis 2012-07, Vol.354 (10), p.1987-2000
Main Authors: Mondal, Shovan, Nechab, Malek, Campolo, Damien, Vanthuyne, Nicolas, Bertrand, Michèle P.
Format: Article
Language:English
Subjects:
allenes
carbenoids
Cascades
Catalysis
Catalysts: preparations and properties
Chemical Sciences
Chemistry
diazo compounds
enediyne rearrangement
Exact sciences and technology
Free radicals chemistry
General and physical chemistry
memory of chirality
Organic chemistry
radical reactions
Reactivity and mechanisms
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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 reaction of enediynes with diazo esters leads to cyclic amino esters bearing two contiguous tetrasubstituted stereogenic centers through a one‐pot, five‐step cascade. Copper iodide catalyzes the formation of an intermediate 3‐alkynoate and copper carbenoid promotes its reversible isomerization to the corresponding allenoate. The alkynoate‐allenoate equilibrium is completely shifted to the right by the rapid consumption of the allenoate by Myers–Saito cyclization. This is followed by 1,5‐H atom transfer and recombination of the resulting biradical. Memory of chirality phenomenon explains the high enantioselectivity.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201200045