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A Catalytic, Enantioselective Formal Synthesis of (+)-Dichroanone and (+)-Taiwaniaquinone H

Shockley, Samantha E. and Holder, Jeffrey C. and Stoltz, Brian M. (2014) A Catalytic, Enantioselective Formal Synthesis of (+)-Dichroanone and (+)-Taiwaniaquinone H. Organic Letters, 16 (24). pp. 6362-6365. ISSN 1523-7060. PMCID PMC4275150. http://resolver.caltech.edu/CaltechAUTHORS:20141215-090404543

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Abstract

A catalytic, enantioselective formal synthesis of (+)-dichroanone and (+)-taiwaniaquinone H is reported. The all-carbon quaternary stereocenter was constructed by asymmetric conjugate addition catalyzed by a palladium(II) (S)-tert-butylpyridinooxazoline complex. The unexpected formation of a [3.2.1] bicyclic intermediate required the identification of a new route. Analysis of the Hammett constants for para-substituted arenes enabled the rational design of a highly enantioselective conjugate addition substrate that led to the completion of the formal synthesis.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ol5031537DOIArticle
http://pubs.acs.org/doi/suppl/10.1021/ol5031537PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ol5031537PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4275150/PubMed CentralArticle
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2014 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: October 28, 2014. Publication Date (Web): December 9, 2014. The authors thank NIH-NIGMS (B.M.S., R01 GM080269), Caltech, and the American Chemical Society Division of Organic Chemistry (predoctoral fellowship J.C.H) for financial support. Dr. Scott Virgil is thanked for helpful discussions and assistance with chiral chromatography. Dr. David VanderVelde of the Caltech NMR facility is thanked for invaluable assistance with NMR experiments and helpful discussions. Lawrence Henling and Dr. Michael K. Takase (Caltech) are gratefully acknowledged for X-ray crystallographic structural determination. Dr. Mona Shahgholi is thanked for mass spectroscopy determination. Niklas B. Thompson is thanked for his assistance with crystallographic and Hammett plot analysis. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to Caltech. The Varian 400 MHz NMR spectrometer at Caltech was purchased via an NIH grant (RR027690).
Funders:
Funding AgencyGrant Number
NIHR01 GM080269
CaltechUNSPECIFIED
American Chemical SocietyUNSPECIFIED
NSFUNSPECIFIED
NIHRR027690
PubMed Central ID:PMC4275150
Record Number:CaltechAUTHORS:20141215-090404543
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20141215-090404543
Official Citation:A Catalytic, Enantioselective Formal Synthesis of (+)-Dichroanone and (+)-Taiwaniaquinone H Samantha E. Shockley, Jeffrey C. Holder, and Brian M. Stoltz Organic Letters 2014 16 (24), 6362-6365
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52799
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:15 Dec 2014 17:11
Last Modified:20 Jul 2017 21:06

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