%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