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Copper Carbenoid, Reactant and Catalyst for One‐Pot Diazo Ester Coupling Cascade Rearrangement of Enediynes: Formation of Two Contiguous Tetrasubstituted Stereocenters
Author(s) -
Mondal Shovan,
Nechab Malek,
Campolo Damien,
Vanthuyne Nicolas,
Bertrand Michèle P.
Publication year - 2012
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.201200045
Subject(s) - stereocenter , carbenoid , chemistry , diazo , isomerization , copper , catalysis , iodide , cascade , medicinal chemistry , photochemistry , stereochemistry , enantioselective synthesis , organic chemistry , rhodium , chromatography
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.