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Updated: Aug 10, 2026

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Intramolecular allenolate acylations in studies toward a synthesis of FR182877
C D Vanderwal1, D A Vosburg, E J Sorensen
1The Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Abstract:
During our efforts to synthesize the cytotoxic natural product FR182877, we discovered intramolecular reductive acylations that offer a stereocontrolled alternative to the classical Knoevenagel condensation for the formation of alpha-alkylidene beta-keto-delta-lactones. Other progress toward a synthesis of FR182877 includes a pi-allyl Stille coupling and a bromo Horner-Wadsworth-Emmons reaction that forms a 12-membered ring. Structural relationships among FR182877, hexacyclinic acid, macquarimicin A, and cochleamycin A are also discussed. [reaction: see text]
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