Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

Published on 2017-06-19T23:03:42Z (GMT) by
An asymmetric synthesis of (−)-6,7-dideoxysqualestatin H5 is reported. Key features of the synthesis include the following: (1) highly diastereoselective <i>n</i>-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 Csp<sup>3</sup>–Csp<sup>2</sup> cross-electrophile coupling between tricarboxylate core and unsaturated side chain to complete the natural product.

Cite this collection

Fegheh-Hassanpour, Younes; Arif, Tanzeel; Sintim, Herman O.; Al Mamari, Hamad H.; Hodgson, David M. (2017): Synthesis of (−)-6,7-Dideoxysqualestatin H5

by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile

Coupling. ACS Publications.

https://doi.org/10.1021/acs.orglett.7b01513

Retrieved: 12:10, Jun 24, 2017 (GMT)