Iridium-Catalyzed Enantioselective Alkene Hydroalkylation via a Heteroaryl-Directed Enolization–Decarboxylation Sequence

Upon exposure to a cationic Ir­(I)-complex modified with the chiral diphosphine DuanPhos, hydroalkylations of styrenes and α-olefins with diverse heteroaryl tert-butyl acetates occur with complete branched selectivity and very high enantioselectivity. The initial adducts undergo acid promoted decarb...

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Published inJournal of the American Chemical Society Vol. 145; no. 44; pp. 23918 - 23924
Main Authors Jing, Changcheng, Mao, Wenbin, Bower, John F.
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 08.11.2023
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Communication
Physical Sciences
Science & Technology
ETHERS
ACETAMIDES
ALKYLATION
H CONJUGATE ADDITION
ALLYLATION
HYDROARYLATION
C-H
ASYMMETRIC HYDROVINYLATION
UNACTIVATED ALKENES
HYDRIDE
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Summary:Upon exposure to a cationic Ir­(I)-complex modified with the chiral diphosphine DuanPhos, hydroalkylations of styrenes and α-olefins with diverse heteroaryl tert-butyl acetates occur with complete branched selectivity and very high enantioselectivity. The initial adducts undergo acid promoted decarboxylation in situ to provide alkylated heteroarenes possessing defined β-stereocenters. The processes are postulated to proceed via a stereodefined chiral Ir-enolate, which arises upon heteroarene directed enolization of the heteroaryl acetate precursor. The method can be classified as an enantioselective decarboxylative C­(sp3)–C­(sp3) cross-coupling.
Bibliography:European Research Council (ERC)
ObjectType-Article-1
SourceType-Scholarly Journals-1
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content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.3c10163