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Mn(III)‐Based Oxidative Cyclization of Alkenes Using Tricarbonyl System
Author(s) -
Huynh ThanhTruc,
Yamakawa Hiroyasu,
Nguyen VanHa,
Nishino Hiroshi
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201801443
Subject(s) - chemistry , carbocation , nucleophile , oxidative phosphorylation , medicinal chemistry , aryl , oxygen , redox , organic chemistry , catalysis , biochemistry , alkyl
The Mn(III)‐based oxidation of 1,1‐disubstituted ethenes with 2‐(2‐aryl‐2‐oxoethyl)malonates, 2‐acetyl‐4‐aryl‐4‐oxobutanoates, and 3‐acetyl‐1‐arylpentane‐1,4‐diones was evaluated. The reaction using the malonates mainly gave the 2,3‐dihydro‐4 H ‐pyran‐4,4‐dicarboxylates along with γ ‐lactones. A similar reaction using the acetyloxobutanoates and acetylpentanediones produced the 2,3,3a,6a‐tetrahydrofuro[2, 3‐ b ]furans and the corresponding dihydropyrans. The cyclization was strongly affected by the nucleophilicity of the carbonyl oxygen in the carbocation intermediate, and the kinetic and thermodynamic controls of the following reaction. The structure determination and the mechanisms are discussed.