CpRuII-chiral bisamidine complex catalyzed asymmetric Caroll-type decarboxylative allylation of β-keto allyl esters

TETRAHEDRON

卷:76

Article

Ogawa, Shintarou¹  Miyata, Kengo¹  Kawakami, Sho¹  Tanaka, Shinji¹  Kitamura, Masato¹ 

[1] Nagoya Univ, Res Ctr Mat Sci, Grad Sch Sci, Grad Sch Pharmaceut Sci, Nagoya, Aichi 4648601, Japan

关键词: Decarboxylative allylation;    Ruthenium;    sp(2)-bidentate ligand;    Homogeneous catalysis;   

DOI  :  10.1016/j.tet.2019.130888

来源: Elsevier

【 摘 要 】

Carroll-rearrangement-type intramolecular decarboxylative allylation of beta-keto allyl esters with a cationic CpRu complex bearing a chiral bisamidine-type bidentate ligand is reported. The catalytic system allows the efficient transformation of the mono substituted, 3-arylallyl esters of beta-keto acids to the corresponding gamma,delta-enones. Notably, the catalytic turnover is more than an order higher than that of the previously reported examples. The developed reaction system displays improved regioselectivity and enantioselectivity and a broad substrate scope. Mechanistic studies using NMR experiments, substratestructure/reactivity relationship studies, and crossover experiment reveal a possible reaction pathway involving the enolate of the beta-keto acid. (C) 2019 Published by Elsevier Ltd.

【 授权许可】

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