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Nickel/Bis(oxazoline)-Catalyzed Asymmetric Negishi Arylations of Racemic Secondary Benzylic Electrophiles to Generate Enantioenriched 1,1-Diarylalkanes

Do, Hien-Quang and Chandrashekar, E. R. R. and Fu, Gregory C. (2013) Nickel/Bis(oxazoline)-Catalyzed Asymmetric Negishi Arylations of Racemic Secondary Benzylic Electrophiles to Generate Enantioenriched 1,1-Diarylalkanes. Journal of the American Chemical Society, 135 (44). pp. 16288-16291. ISSN 0002-7863. PMCID PMC3869004. http://resolver.caltech.edu/CaltechAUTHORS:20131205-082734303

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Abstract

A tertiary stereogenic center that bears two different aryl substituents is found in a variety of bioactive compounds, including medicines such as Zoloft and Detrol. We have developed an efficient method for the synthesis of enantioenriched 1,1-diarylalkanes from readily available racemic benzylic alcohols. Formation of a benzylic mesylate (which is not isolated), followed by treatment with an arylzinc reagent, LiI, and a chiral nickel/bis(oxazoline) catalyst, furnishes the Negishi cross-coupling product in high ee and good yield. A wide array of functional groups (e.g., an aryl iodide, a thiophene, and an N-Boc-indole) are compatible with the mild reaction conditions. This method has been applied to a gram-scale synthesis of a precursor to Zoloft.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja408561b DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja408561bPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3869004/PubMed CentralArticle
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2013 American Chemical Society. Received: August 18, 2013; Published: October 28, 2013. Support has been provided by the NIH (National Institute of General Medical Sciences: R01-GM62871) and Dr. Reddy’s Laboratories (E.R.R.C.). We thank Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) and Dr. Nathan D. Schley for assistance.
Funders:
Funding AgencyGrant Number
NIHR01-GM62871
Dr. Reddy's LaboratoriesUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
PubMed Central ID:PMC3869004
Record Number:CaltechAUTHORS:20131205-082734303
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20131205-082734303
Official Citation:Nickel/Bis(oxazoline)-Catalyzed Asymmetric Negishi Arylations of Racemic Secondary Benzylic Electrophiles to Generate Enantioenriched 1,1-Diarylalkanes Hien-Quang Do, E. R. R. Chandrashekar, and Gregory C. Fu Journal of the American Chemical Society 2013 135 (44), 16288-16291
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42845
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:05 Dec 2013 17:38
Last Modified:12 Dec 2016 21:03

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