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Catalyst-controlled doubly enantioconvergent coupling of racemic alkyl nucleophiles and electrophiles

Huo, Haohua and Gorsline, Bradley J. and Fu, Gregory C. (2020) Catalyst-controlled doubly enantioconvergent coupling of racemic alkyl nucleophiles and electrophiles. Science, 367 (6477). pp. 559-564. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20200130-135407173

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Abstract

Stereochemical control in the construction of carbon-carbon bonds between an alkyl electrophile and an alkyl nucleophile is a persistent challenge in organic synthesis. Classical substitution reactions via S_N1 and S_N2 pathways are limited in their ability to generate carbon-carbon bonds (inadequate scope, due to side reactions such as rearrangements and eliminations) and to control stereochemistry when beginning with readily available racemic starting materials (racemic products). Here, we report a chiral nickel catalyst that couples racemic electrophiles (propargylic halides) with racemic nucleophiles (β-zincated amides) to form carbon-carbon bonds in doubly stereoconvergent processes, affording a single stereoisomer of the product from two stereochemical mixtures of reactants.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1126/science.aaz3855DOIArticle
https://science.sciencemag.org/content/suppl/2020/01/29/367.6477.559.DC1PublisherSupplementary Materials
https://doi.org/10.1021/cen-09805-scicon7Featured InC&EN
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2020 American Association for the Advancement of Science. This is an article distributed under the terms of the Science Journals Default License. Received 4 September 2019; accepted 26 November 2019. We thank S. H. Jungbauer, S. C. Virgil, L. M. Henling, D. G. Vander Velde, H. Yin, D. J. Freas, W. Zhang, and Z. Yang for assistance and discussions. Funding: Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R37-GM62871). H.H. thanks the Resnick Sustainability Institute at Caltech for fellowship support. Author contributions: H.H. and B.J.G. performed all experiments. H.H. and G.C.F. wrote the manuscript. All authors contributed to the analysis and the interpretation of the results. The authors declare no competing interests. Data and materials availability: The data that support the findings of this study are available in the paper, in its supplementary materials (experimental procedures and characterization data), and from the Cambridge Crystallographic Data Centre (CCDC) (www.ccdc.cam.ac.uk/structures; crystallographic data are available free of charge under CCDC reference numbers 1935944 and 1935945).
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
NIHR37-GM62871
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:6477
Record Number:CaltechAUTHORS:20200130-135407173
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200130-135407173
Official Citation:Catalyst-controlled doubly enantioconvergent coupling of racemic alkyl nucleophiles and electrophiles. BY HAOHUA HUO, BRADLEY J. GORSLINE, GREGORY C. FU. SCIENCE 31 JAN 2020: 559-564; doi: 10.1126/science.aaz3855
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:101007
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Jan 2020 23:01
Last Modified:02 Apr 2020 17:37

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