The Catalytic Alkylative Desymmetrization of Anhydrides in a Formal Synthesis of Ionomycin

Kevin M. Oberg; Brian M. Cochran; Matthew J. Cook; Tomislav Rovis

doi:10.1055/s-0037-1610108

Synthesis, Table of Contents

Synthesis 2018; 50(22): 4343-4350
DOI: 10.1055/s-0037-1610108

paper

The Catalytic Alkylative Desymmetrization of Anhydrides in a Formal Synthesis of Ionomycin

Kevin M. Oberg

^aDepartment of Chemistry, Colorado State University, Fort Collins, CO 80523, USA

,

Brian M. Cochran

^aDepartment of Chemistry, Colorado State University, Fort Collins, CO 80523, USA

,

Matthew J. Cook

^aDepartment of Chemistry, Colorado State University, Fort Collins, CO 80523, USA

,

Tomislav Rovis *

^aDepartment of Chemistry, Colorado State University, Fort Collins, CO 80523, USA

^bDepartment of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA Email: tr2504@columbia.edu

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Dedicated to Professor Scott Denmark on the occasion of his 65^th birthday.

Published as part of the Special Section dedicated to Scott E. Denmark on the occasion of his 65^th birthday.

Abstract

The catalytic desymmetrization of anhydrides with zinc reagents provides access to deoxypolypropionate and polypropionate synthons. A synthesis of ionomycin was pursued in which three of the four fragments were assembled using this methodology. Two of the strategies (enol silane/oxocarbenium coupling and reductive cyclization) were not successful at installing the C23 stereocenter, but this stereochemical issue was overcome through a reduction/S_N2 approach. In addition to the synthesis of a protected diastereomer of ionomycin, the synthesis of a C17–C32 fragment constitutes a formal total synthesis.

Key words

total synthesis - rhodium - enantioselective synthesis - anhydride desymmetrization - diastereoselectivity

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References

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