%0 Journal Article
%A Fegheh-Hassanpour, Younes
%A Arif, Tanzeel
%A Sintim, Herman O.
%A Al Mamari, Hamad H.
%A Hodgson, David M.
%D 2017
%T Synthesis of (−)-6,7-Dideoxysqualestatin H5
by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile
Coupling
%U https://acs.figshare.com/articles/journal_contribution/Synthesis_of_-6_7-Dideoxysqualestatin_H5_by_Carbonyl_Ylide_Cycloaddition_Rearrangement_and_Cross-electrophile_Coupling/5119996
%R 10.1021/acs.orglett.7b01513.s001
%2 https://ndownloader.figshare.com/files/8702752
%K hydrazone
%K diazo functionality
%K Csp
%K facilitation
%K co-generation
%K cross-electrophile
%K β- hydroxy -α-ketoester motif
%K Rh
%K tartrate acetonide enolate
%K Ylide
%K Cross-electrophile
%K alkylation
%K synthesis
%K stereoretentive
%K oxidation
%K diastereoselective n
%K tricarboxylate core
%K ylide
%K formation
%K dideoxysqualestatin
%K Dideoxysqualestatin
%K Key features
%K Ni-catalyzed
%K carbonyl
%K entry
%K cyclic
%K Carbonyl
%K ozonolysi
%K side chain
%K Synthesi
%K Cycloaddition
%X An asymmetric synthesis
of (−)-6,7-dideoxysqualestatin H5
is reported. Key features of the synthesis include the following:
(1) highly diastereoselective n-alkylation of a tartrate
acetonide enolate and subsequent oxidation–hydrolysis to provide
an asymmetric entry to a β-hydroxy-α-ketoester motif;
(2) facilitation of Rh(II)-catalyzed cyclic carbonyl ylide formation–cycloaddition
by co-generation of keto and diazo functionality through ozonolysis
of an unsaturated hydrazone; and (3) stereoretentive Ni-catalyzed
Csp3–Csp2 cross-electrophile coupling
between tricarboxylate core and unsaturated side chain to complete
the natural product.
%I ACS Publications