Enantiodivergent Formal Total Synthesis of Aspercyclide C from l-(+)-Tartaric Acid

Abstract

The enantiodivergent formal syntheses of both enantiomers of aspercyclide C is accomplished. Starting from L-(+)-tartaric acid, the key protected allylic alcohol, (3R,4R)-4-(methoxymethoxy)non-1-en-3-ol is prepared, and is then elaborated into both enantiomers of 3-[(4-methoxybenzyl)oxy]non-1-en-4-ol via Mitsunobu inversion. Esterification with a known biaryl acid, followed by ring-closing metathesis and deprotection completes the syntheses.

γ‐Hydroxy Amides from Tartaric Acid: Versatile Chiral Building Blocks for the Total Synthesis of Natural Products

“…The diols were employed in the total synthesis of several natural products including macrolactones such as cladospolides, palmerolide A, microcarpalide and aspercyclide C (Scheme 5). [23–30] …”

Enantioselective synthesis of C1-C4 and C5-C14 fragments of cytospolide D

“…The Yamaguchi esterification of acid fragment 12 and alkenol derivative 11a could also lead to the required bis-olefin derivative 10. 31 The bis-olefin derivative 10 could then be converted into the target compound cytospolide D 4 by the Grubbs RCM and deprotection of both protecting group following the standard organic transformations. Ramana et al reported the synthesis of Cytospolide E 5 with similar fargments with different stereochemistry.…”

Stereodivergent routes in organic synthesis: marine natural products, lactones, other natural products, heterocycles and unnatural compounds

“…They exhibit moderate activity in IgE receptor binding related to allergic disorders. Prasad and co-workers 35 described enantiodivergent routes to aspercyclide C enantiomers from L-tartaric acid. The key common intermediate is the protected allylic alcohol (3R,4R)-4-(methoxymethoxy)non-1-en-3-ol, which after protection as PMB ether and MOM deprotection, the configuration of the alcohol was inverted under Mitsunobu conditions (Scheme 24).…”