Pt(II)-Chiral diene-catalyzed enantioselective formal [4 + 2] cycloaddition initiated by C–C bond cleavage and elucidation of a Pt(II)/(IV) cycle by DFT calculations,Organic Chemistry Frontiers

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Pt(II)-Chiral diene-catalyzed enantioselective formal [4 + 2] cycloaddition initiated by C–C bond cleavage and elucidation of a Pt(II)/(IV) cycle by DFT calculations
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2021-10-28 , DOI: 10.1039/d1qo01467f
Takanori Shibata ₁ , Natsumi Shiozawa ₁ , Shun Nishibe ₁ , Hideaki Takano _{1,

2,

3} , Satoshi Maeda _{2,

3,

4}

Affiliation

A chiral Pt(II) complex was readily prepared from [PtCl₂(C₂H₄)]₂ and Hayashi's diene. Its dicationic derivative efficiently catalyzed a formal intramolecular [4 + 2] cycloaddition of biphenylenes possessing substituted arylalkynes tethered by an ortho-phenylene moiety at ambient temperature and axially chiral cycloadducts were obtained in excellent yields and ees. A study of the DFT calculations revealed a Pt(II)/(IV) cycle including oxidative addition of biphenylene along with C–C bond cleavage.

中文翻译：

Pt(II)-手性二烯催化的对映选择性形式 [4+2] 环加成由 C-C 键断裂引发，并通过 DFT 计算阐明 Pt(II)/(IV) 循环

从 [PtCl ₂ (C ₂ H ₄ )] ₂和林氏二烯很容易制备手性 Pt( II ) 配合物。其双阳离子衍生物有效地催化的分子内正式[4 + 2]具有取代arylalkynes亚联苯基环加成拴由邻位在环境温度下沿轴向以优良产率和EES获得手性cycloadducts亚苯基结构部分和。DFT 计算的研究揭示了 Pt( II )/( IV ) 循环，包括亚联苯的氧化加成以及 C-C 键断裂。

更新日期：2021-11-10

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