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Title: Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols

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.

Authors:
 [1];  [2];  [3];  [2];  [2];  [1]
  1. Purdue Univ., West Lafayette, IN (United States)
  2. Stanford Univ., Stanford, CA (United States)
  3. New York Univ. (NYU), NY (United States)
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1467609
Grant/Contract Number:  
SC0005430
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 33; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Davis, Dexter C., Walker, Katherine L., Hu, Chunhua, Zare, Richard N., Waymouth, Robert M., and Dai, Mingji. Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols. United States: N. p., 2016. Web. doi:10.1021/jacs.6b06573.
Davis, Dexter C., Walker, Katherine L., Hu, Chunhua, Zare, Richard N., Waymouth, Robert M., & Dai, Mingji. Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols. United States. doi:10.1021/jacs.6b06573.
Davis, Dexter C., Walker, Katherine L., Hu, Chunhua, Zare, Richard N., Waymouth, Robert M., and Dai, Mingji. Tue . "Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols". United States. doi:10.1021/jacs.6b06573. https://www.osti.gov/servlets/purl/1467609.
@article{osti_1467609,
title = {Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols},
author = {Davis, Dexter C. and Walker, Katherine L. and Hu, Chunhua and Zare, Richard N. and Waymouth, Robert M. and Dai, Mingji},
abstractNote = {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.},
doi = {10.1021/jacs.6b06573},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 138,
place = {United States},
year = {2016},
month = {7}
}

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