Nickel-catalyzed hydroalkylation of 1, 3-dienes with malonates using a homoallyl carbonate as the 1, 3-diene and hydride source. (30th March 2021)

• Record Type: Journal Article
• Authors: Tsuji, Hiroaki; Takahashi, Yoshiyuki; Kawatsura, Motoi
• Is Part Of: Tetrahedron letters. Volume 68(2021)
• Publication Date: 2021-03-30
• Subjects: Nickel Catalysis -- Hydroalkylation -- 1, 3-Dienes -- Malonates -- Homoallyl carbonates; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2021.152916
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Nickel-catalyzed hydroalkylation of 1, 3-dienes. A homoallyl carbonate as a surrogate for the 1, 3-diene and hydride source. Malonates were used as a carbon pronucleophile. Abstract: The use of a malonate nucleophile in the transition metal-catalyzed hydroalkylation of 1, 3-dienes remains immature. Herein, we report the nickel-catalyzed hydroalkylation of 1, 3-dienes with malonates using a homoallyl carbonate as the 1, 3-diene and hydride source. A broad range of homoally carbonates and malonate derivatives were well tolerated under a Ni/DPEphos catalyst system, providing the corresponding 1, 2-hydroalkylation products in 40–94% yields with excellent regioselectivity (32 examples). We also suggested the possible reaction mechanism for the nickel-catalyzed hydroalkylation of in situ generated 1, 3-dienes with malonates.