β,γ-Vicinal Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Directed Nucleopalladation

A palladium­(II)-catalyzed 1,2-dicarbofunctionalization reaction of unactivated alkenes has been developed, wherein a cleavable bidentate directing group is used to control the regioselectivity and stabilize the putative alkylpalladium­(II) intermediate. Under the optimized reaction conditions, a br...

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Veröffentlicht in:Journal of the American Chemical Society 2016-11, Vol.138 (46), p.15122-15125
Hauptverfasser: Liu, Zhen, Zeng, Tian, Yang, Kin S, Engle, Keary M
Format: Artikel
Sprache:eng
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Zusammenfassung:A palladium­(II)-catalyzed 1,2-dicarbofunctionalization reaction of unactivated alkenes has been developed, wherein a cleavable bidentate directing group is used to control the regioselectivity and stabilize the putative alkylpalladium­(II) intermediate. Under the optimized reaction conditions, a broad range of nucleophiles and electrophiles were found to participate in this transformation, providing moderate to high yields. 3-Butenoic acid derivatives containing internal alkenes and α-substituents were reactive substrates, offering a powerful platform for preparing β,γ-substituted carbonyl compounds with multiple stereocenters.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b09170