Macrocyclic Lactone Formation through Sulfide Contraction: Synthesis of (±)-Diplodialide A

Author: Brown, Frank Ripley, Jr.

Year: 1980

Degree: Dissertation (Ph.D.)

Advisor: Ireland, Robert E.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/t4z3-ef78

Abstract

A methodology for the synthesis of macrocyclic β-ketolactones from ω-hydroxythioamides is described. The hydroxythioamides were esterified with chloroacetyl chloride, and the resulting chloroesters underwent Eschenmoser sulfide contraction when treated with sodium iodide, diisopropylethylamine, and triethyl phosphite in acetonitrile. The β-ketolactones were obtained in 25-58% yield. The utility of the method was demonstrated by the synthesis of diplodialide A.

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