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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

Abstract : 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 MyersSaito cyclization. This is followed by 1,5-H atom transfer and recombination of the resulting biradical. Memory of chirality phenomenon explains the high enantioselectivity.
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Submitted on : Tuesday, February 7, 2017 - 4:39:19 PM
Last modification on : Thursday, January 23, 2020 - 6:22:05 PM

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Shovan Mondal, Malek Nechab, Damien Campolo, Nicolas Vanthuyne, Michèle P. Bertrand. Copper Carbenoid, Reactant and Catalyst for One-Pot Diazo Ester Coupling Cascade Rearrangement of Enediynes: Formation of Two Contiguous Tetrasubstituted Stereocenters. Advanced Synthesis and Catalysis, Wiley-VCH Verlag, 2012, 354 (10), pp.1987--2000. ⟨10.1002/adsc.201200045⟩. ⟨hal-01460406⟩

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