Synthesis of Simplified 2-Desmethyl Sanctolide A Analogs.

A one-pot, sequential phosphate tether-mediated method for the synthesis of simplified 2-desmethyl sanctolide A analogs is reported. Western side-chain diversification was achieved using a pot-efficient, sequential cross metathesis (CM)/ring-closing metathesis (RCM)/H/dephosphorylation procedure. Further diversification was achieved by MeAl-mediated amide formation, Yamaguchi esterification, and RCM macrocyclization to access five C11/C12 -configured, 2-des-methyl sanctolide A analogs with improved stability.

Total Synthesis of Sanctolide A and Formal Synthesis of (2)-Sanctolide A.

Two synthetic strategies employing phosphate tether-mediated one-pot sequential protocols for the total synthesis of the polyketide nonribosomal peptide macrolide, sanctolide A, and the formal synthesis of the (2)-epimer of sanctolide A are reported. In this work, a phosphate tether-mediated one-pot sequential ring-closing metathesis/cross metathesis/substrate-controlled "H"/tether removal approach was developed to accomplish the total synthesis of the natural product sanctolide A.

A modular phosphate tether-mediated divergent strategy to complex polyols.

An efficient and divergent synthesis of polyol subunits utilizing a phosphate tether-mediated, one-pot, sequential RCM/CM/reduction process is reported. A modular, 3-component coupling strategy has been developed, in which, simple "order of addition" of a pair of olefinic-alcohol components to a pseudo-C 2-symmetric phosphoryl chloride, coupled with the RCM/CM/reduction protocol, yields five polyol fragments. Each of the product polyols bears a central 1,3-anti-diol subunit with differential olefinic geometries at the periphery.