Highly Conjugated π-Systems Arising from Cannibalistic Hexadehydro-Diels-Alder Couplings: Cleavage of C-C Single and Triple Bonds.,Chemistry - A European Journal

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Highly Conjugated π-Systems Arising from Cannibalistic Hexadehydro-Diels-Alder Couplings: Cleavage of C-C Single and Triple Bonds.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-07-03 , DOI: 10.1002/chem.202002511
Jan Maier ₁ , Marian Deutsch ₂ , Julia Merz ₁ , Qing Ye _{1,

3} , Oliver Diamond ₁ , Maja-Tessa Schilling ₁ , Alexandra Friedrich ₁ , Bernd Engels ₂ , Todd B Marder ₁

Affiliation

We have investigated the cannibalistic self‐trapping reaction of an ortho‐benzyne derivative generated from 1,11‐bis(p‐tolyl)undeca‐1,3,8,10‐tetrayne in an HDDA reaction. Without adding any specific trapping agent, the highly reactive benzyne is trapped by another bisdiyne molecule in at least three different modes. We have isolated and characterized the resulting products and performed high‐level calculations concerning the reaction mechanism. During the cannibalistic self‐trapping process, either a C≡C triple bond or an sp–sp³ C−C single bond is cleaved. Up to seven rings and nine C−C bonds are formed starting from two 1,11‐bis(p‐tolyl)undeca‐1,3,8,10‐tetrayne molecules. Our experiments and calculations provide considerable insight into the variety of reaction pathways which the ortho‐benzyne derivative, generated from a bisdiyne, can take when reacting with another bisdiyne molecule.

中文翻译：

由同类相食的六氢-Diels-Alder 偶联产生的高度共轭 π-系统：CC 单键和三键的断裂。

我们研究了 HDDA 反应中由 1,11-双(对甲苯基)十一碳二炔-1,3,8,10-四炔生成的邻苯衍生物的同类相食自捕获反应。在不添加任何特定捕获剂的情况下，高反应性苯炔以至少三种不同的模式被另一个双二炔分子捕获。我们对所得产物进行了分离和表征，并对反应机理进行了高级计算。在同类自陷过程中，C−C 三键或 sp–sp ³ C−C 单键被裂解。从两个 1,11-双(对甲苯基)十一碳-1,3,8,10-四炔分子开始，可形成多达七个环和九个 C−C 键。我们的实验和计算为由双二炔生成的邻苯衍生物与另一个双二炔分子反应时可以采取的各种反应途径提供了相当多的见解。

更新日期：2020-07-03

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