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. doi:10.1021/ol5031537. https://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.
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| 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). | |||||||||||||||
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| Issue or Number: | 24 | |||||||||||||||
| PubMed Central ID: | PMC4275150 | |||||||||||||||
| DOI: | 10.1021/ol5031537 | |||||||||||||||
| Record Number: | CaltechAUTHORS:20141215-090404543 | |||||||||||||||
| Persistent URL: | https://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: | 10 Nov 2021 19:43 |
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