Total Synthesis and Structural Confirmation of Malayamycin A:  A Novel Bicyclic C-Nucleoside from Streptomyces malaysiensis

Abstract

[reaction: see text] The stereocontrolled synthesis of malayamycin A, a novel naturally occurring bicyclic C-nucleoside of the perhydrofuropyran type, is described.

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

“… Advanced intermediate 71 - 1 incorporating a 1-methylhexene oxide moiety was treated with sodium azide to provide a mixture of trans - and cis -decalins 71 - 2 and 71 - 3 , both equipped with an identical 1,2-azido alcohol function corresponding to nucleophilic attack on the less hindered secondary site of epoxide 71 - 1 . A similar principle based on steric hindrance for the introduction of stereogenic carbon–nitrogen bonds by epoxide opening is applied in the syntheses of malayamycin A by Hanessian , and azithromycin by Kim and Kang …”

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“…The malayamycin synthesis story is all the more relevant when one considers that the natural product itself was isolated over a decade ago,47d and it remained in the proprietary domain until the opportunity arose for structural confirmation through synthesis 48e. 130 The potential for biological activity for natural and unnatural analogues of compounds relating to malaymycin A with applications for human use remains to be explored.…”

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“…Soon after its disclosure, a first total synthesis of malayamycin A (20; see Scheme 4) was published by the group of Hanessian and the relative and absolute stereochemistry could be confirmed. 13 Consequently, joint efforts were undertaken by the Hanessian group and Syngenta scientists to access synthetic derivatives of 20 and establish an SAR of this compound class. 14 The synthesis of malayamycin A started from D-ribonolactone (21) which was converted into intermediate 22 by acetal protection of the hydroxyl groups followed by addition of 5-lithio-2,4-dimethoxypyrimidine to the lactone moiety.…”