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Enantioselective Total Synthesis of the Reported Structures of (−)-9-epi-Presilphiperfolan-1-ol and (−)-Presilphiperfolan-1-ol: Structural Confirmation and Reassignment and Biosynthetic Insights

Hong, Allen Y. and Stoltz, Brian M. (2012) Enantioselective Total Synthesis of the Reported Structures of (−)-9-epi-Presilphiperfolan-1-ol and (−)-Presilphiperfolan-1-ol: Structural Confirmation and Reassignment and Biosynthetic Insights. Angewandte Chemie International Edition, 51 (38). pp. 9674-9678. ISSN 1433-7851. PMCID PMC3517068. https://resolver.caltech.edu/CaltechAUTHORS:20141217-142148376

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Abstract

The first total synthesis of the reported structures of 9-epi-presilphiperfolan-1-ol and presilphiperfolan-1-ol has been achieved. Key steps are a catalytic asymmetric alkylation of a novel diene-containing electrophile followed by a two-carbon ring contraction and an intramolecular Diels–Alder cycloaddition to form the stereochemically dense tricyclic core. The synthetic work has resulted in the structural revision of presilphiperfolan-1-ol (see scheme).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.201205276DOIArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3517068/PubMed CentralArticle
http://dx.doi.org/10.1002/anie.201300384DOIErratum
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:Copyright © 2012 WILEY-VCH. Received: July 4, 2012. Published online: August 22, 2012. In memory of Michael W. Day. The authors thank NIH-NIGMS (R01GM080269-01), Roche, Abbott Laboratories, Amgen, Boehringer Ingelheim, the Gordon and Betty Moore Foundation, and Caltech for awards and financial support. Prof. Suzana G. Leitão (Universidade Federale do Rio de Janeiro) generously provided NMR spectra for natural 2. Dr. Lawrence Henling is gratefully acknowledged for X-ray crystallographic structure determination. The Bruker KAPPA APEXII X-ray diffractometer used in this study was purchased through an NSF CRIF:MU award to Caltech (CHE-0639094). Prof. Sarah Reisman, Dr. Scott Virgil, Dr. Douglas C. Behenna, Robert J. Ely and Fang Gao (Boston College), and Jessica Y. Wu (Harvard University) are acknowledged for helpful discussions and suggestions. Dr. David VanderVelde and Dr. Scott Ross are acknowledged for NMR assistance.
Errata:Corrigendum: Corrigendum: Enantioselective Total Synthesis of the Reported Structures of (−)-9-epi-Presilphiperfolan-1-ol and (−)-Presilphiperfolan-1-ol: Structural Confirmation and Reassignment and Biosynthetic Insights Vol. 52, Issue 8, 2147
Funders:
Funding AgencyGrant Number
NIHR01GM080269-01
RocheUNSPECIFIED
Abbott LaboratoriesUNSPECIFIED
AmgenUNSPECIFIED
Boehringer IngelheimUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
NSFCHE-0639094
Subject Keywords:asymmetric catalysis; natural products; structure determination; terpenoids; total synthesis
Issue or Number:38
PubMed Central ID:PMC3517068
Record Number:CaltechAUTHORS:20141217-142148376
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141217-142148376
Official Citation:Hong, A. Y. and Stoltz, B. M. (2012), Enantioselective Total Synthesis of the Reported Structures of (−)-9-epi-Presilphiperfolan-1-ol and (−)-Presilphiperfolan-1-ol: Structural Confirmation and Reassignment and Biosynthetic Insights . Angew. Chem. Int. Ed., 51: 9674–9678. doi: 10.1002/anie.201205276
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52975
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:17 Dec 2014 23:05
Last Modified:23 Apr 2020 23:44

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