Chromium-Catalyzed Allylic Defluorinative Ketyl Olefin Coupling

Herein we report a chromium-catalyzed allylic defluorinative ketyl olefin coupling between aldehydes and α-trifluoromethyl alkenes, which provides novel and efficient access to diverse gem-difluorohomoallylic alcohols. Remarkably, the high chemoselectivity of this reaction enables the conversion of...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 143; no. 30; pp. 11602 - 11610
Main Authors Zhang, Chang, Lin, Zhiyang, Zhu, Yufei, Wang, Chuan
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 04.08.2021
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
ELECTROORGANIC CHEMISTRY
KETONES
NUCLEOPHILIC 5-ENDO-TRIG CYCLIZATION
BIOLOGICAL-ACTIVITY
FUNCTIONALIZED GEM-DIFLUOROALKENES
DIAZO-COMPOUNDS
ALDEHYDES
ORGANOLITHIUM REAGENTS
C-F
CONCISE SYNTHESIS
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Summary:Herein we report a chromium-catalyzed allylic defluorinative ketyl olefin coupling between aldehydes and α-trifluoromethyl alkenes, which provides novel and efficient access to diverse gem-difluorohomoallylic alcohols. Remarkably, the high chemoselectivity of this reaction enables the conversion of the formyl moiety in the presence of various easily reducible functionalities including ketone, organohalides, aziridine, sulfone, alkyne, and unactivated alkene. The utility of this method is demonstrated by various simple derivatizations of the attached hydroxyl group of the coupling products. The preliminary mechanistic investigations suggest a reaction pathway with a rate-limiting C–C forming step followed by facile β-fluoro elimination.
Bibliography:ObjectType-Article-1
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c04531