Dexter C Davis1, Katherine L Walker2, Chunhua Hu3, Richard N Zare2, Robert M Waymouth2, Mingji Dai1. 1. Department of Chemistry and Center for Cancer Research, Purdue University , West Lafayette, Indiana 47907, United States. 2. Department of Chemistry, Stanford University , Stanford, California 94305, United States. 3. Department of Chemistry, New York University , New York, New York 10003, United States.
Abstract
A palladium-catalyzed cascade carbonylative spirolactonization of hydroxycyclopropanols has been developed to efficiently synthesize oxaspirolactones common to many complex natural products of important therapeutic value. The mild reaction conditions, high atom economy, broad substrate scope, and scalability of this new method were highlighted in expedient total syntheses of the Turkish tobacco natural products α-levantanolide and α-levantenolide in two and four steps, respectively. The hydroxycyclopropanol substrates are readily available in one step via a Kulinkovich reaction of the corresponding lactones. Mechanistic studies utilizing high-resolution electrospray ionization mass spectrometry (ESI-MS) identified several key intermediates in the catalytic cycle, as well as those related to catalyst decomposition and competitive pathways.
A palladium-catalyzed cascade n>an class="Chemical">carbonylative spirolactonization of hydroxycyclopropanols has been developed to efficiently synthesize oxaspirolactonescommon to many complex natural products of important therapeutic value. The mild reaction conditions, high atom economy, broad substrate scope, and scalability of this new method were highlighted in expedient total syntheses of the Turkish tobacco natural products α-levantanolide and α-levantenolide in two and four steps, respectively. The hydroxycyclopropanol substrates are readily available in one step via a Kulinkovich reaction of the corresponding lactones. Mechanistic studies utilizing high-resolution electrospray ionization mass spectrometry (ESI-MS) identified several key intermediates in the catalytic cycle, as well as those related to catalyst decomposition and competitive pathways.
Authors: Kevin Chung; Steven M Banik; Antonio G De Crisci; David M Pearson; Timothy R Blake; Johan V Olsson; Andrew J Ingram; Richard N Zare; Robert M Waymouth Journal: J Am Chem Soc Date: 2013-05-09 Impact factor: 15.419
Authors: Natalia Girón; Elisa Pérez-Sacau; Raquel López-Fontal; Juan M Amaro-Luis; Sonsoles Hortelano; Ana Estevez-Braun; Beatriz de Las Heras Journal: Eur J Med Chem Date: 2010-04-14 Impact factor: 6.514
Authors: Dexter C Davis; Dominic G Hoch; Li Wu; Daniel Abegg; Brandon S Martin; Zhong-Yin Zhang; Alexander Adibekian; Mingji Dai Journal: J Am Chem Soc Date: 2018-12-06 Impact factor: 15.419
Authors: Hunter S Sims; Pedro de Andrade Horn; Ryota Isshiki; Melissa Lim; Yan Xu; Robert H Grubbs; Mingji Dai Journal: Angew Chem Int Ed Engl Date: 2021-12-14 Impact factor: 15.336