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

Younes Fegheh-Hassanpour; Tanzeel Arif; Herman O. Sintim; Hamad H. Al Mamari; David M. Hodgson

doi:10.1021/acs.orglett.7b01513

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

Younes Fegheh-Hassanpour, Tanzeel Arif, Herman O. Sintim, Hamad H. Al Mamari, David M. Hodgson^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	3540-3543
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	13
DOIs	https://doi.org/10.1021/acs.orglett.7b01513
Publication status	Published - Jul 7 2017

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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title = "Synthesis of (-)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition-Rearrangement and Cross-electrophile Coupling",

abstract = "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.",

author = "Younes Fegheh-Hassanpour and Tanzeel Arif and Sintim, {Herman O.} and {Al Mamari}, {Hamad H.} and Hodgson, {David M.}",

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T1 - Synthesis of (-)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition-Rearrangement and Cross-electrophile Coupling

AU - Fegheh-Hassanpour, Younes

AU - Arif, Tanzeel

AU - Sintim, Herman O.

AU - Al Mamari, Hamad H.

AU - Hodgson, David M.

PY - 2017/7/7

Y1 - 2017/7/7

N2 - 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.

AB - 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.

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

Abstract

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