Asymmetric Total Synthesis of Streptoglycerides A and B

Dedication

Dedicated to Professor S. Chandrasekharan on the occasion of his 80th birthday.

Abstract

A unified strategy for the asymmetric total synthesis of streptoglycerides A and B has been established and has confirmed their proposed absolute configurations. Key to our strategy is the synthesis of a bicyclic scaffold, employing a gold-catalyzed cascade cyclization of 1,6-diyn-ol operating through a 6-endo/5-exo-dig mechanism and its one-pot dihydroxylation followed trans-glycosylation to forge the central tricyclic core of these natural products. Noyori’s asymmetric transfer hydrogenation of an α, β-acetylenic ketones has been employed to install the key propargyl alcohol center with the desired absolute configuration. The pendant conjugated trans-1,3,5-triene/trans-1,3-diene side chains were introduced from a propanaldehyde unit following [Pd]-catalyzed oxidative dehydrogenation, Takai olefination, and Stille cross-coupling.

Keywords

Total synthesis - Noyori’s transfer hydrogenation - Gold-catalysis - Oxidative dehydrogenation - Takai olefination - Stille cross-coupling

Publication History

Received: 23 September 2025

Accepted after revision: 04 November 2025

Accepted Manuscript online:
04 November 2025

Article published online:
27 November 2025

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