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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:
Journal Article: 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. https://doi.org/10.1021/jacs.6b06573
Davis, Dexter C., Walker, Katherine L., Hu, Chunhua, Zare, Richard N., Waymouth, Robert M., and Dai, Mingji. 2016. "Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1467609}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 33,
volume = 138,
place = {United States},
year = {Tue Jul 26 00:00:00 EDT 2016},
month = {Tue Jul 26 00:00:00 EDT 2016}
}

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Cited by: 89 works
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Works referencing / citing this record:

Divergent ring-opening coupling between cyclopropanols and alkynes under cobalt catalysis
journal, January 2018


Total Syntheses of Bisdehydroneostemoninine and Bisdehydrostemoninine by Catalytic Carbonylative Spirolactonization
journal, October 2018


Total Synthesis of trans-Resorcylide via Macrocyclic Stille Carbonylation
journal, February 2019


N‐Heterocyclic Carbene Catalyzed (5+1) Annulations Exploiting a Vinyl Dianion Synthon Strategy
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Modern Developments in the Chemistry of Homoenolates: Modern Developments in the Chemistry of Homoenolates
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Synthesis of benzannulated spiroketals with gold-catalyzed cycloisomerization/spiroketalization cascade
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Recent advances in the synthesis of oxaspirolactones and their application in the total synthesis of related natural products
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Pd-Catalyzed Selective Remote Ring Opening of Polysubstituted Cyclopropanols
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N‐Heterocyclic Carbene Catalyzed (5+1) Annulations Exploiting a Vinyl Dianion Synthon Strategy
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Total Syntheses of Bisdehydroneostemoninine and Bisdehydrostemoninine by Catalytic Carbonylative Spirolactonization
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Copper-Catalyzed Aerobic Oxidative Cyclization Cascade to Construct Bridged Skeletons: Total Synthesis of (−)-Suaveoline
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