Metal-free gem selective dimerization of terminal alkynes catalyzed by a pyridonate borane complex†,Catalysis Science & Technology

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Metal-free gem selective dimerization of terminal alkynes catalyzed by a pyridonate borane complex†
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2019-04-16 00:00:00 , DOI: 10.1039/c9cy00253g
Max Hasenbeck _{1,

2,

3,

4} , Tizian Müller _{1,

2,

3,

4} , Urs Gellrich _{1,

2,

3,

4}

Affiliation

A metal free gem selective dimerization of terminal alkynes catalyzed by a pyridonate borane complex is described. Each individual step of the catalytic cycle was verified experimentally and a protocol for the catalytic reaction was developed. The mechanism of the reaction was further investigated by DFT and DLPNO-CCSD(T) computations. The catalytic transformation commences with C–H cleavage by a boroxypyridine that displays frustrated Lewis pair reactivity. The pyridone borane complex that forms upon C–H cleavage dissociates into a pyridone and an alkynylborane. An unprecedented 1,2-carboboration and a protodeborylation effected by the pyridone yield the 1,3-enyne and complete the catalytic cycle. The change in the coordination mode of the boroxypyridine upon C–H cleavage, described by the term boron-ligand cooperation, enables the dissociation of the formed pyridone borane complex and the 1,2-carboboration and is thus vital for the catalytic reaction.

中文翻译：

吡啶酸酯硼烷配合物催化的末端炔烃的无金属宝石选择性二聚†

无金属的宝石描述了由吡啶酸硼烷络合物催化的末端炔的选择性二聚。实验验证了催化循环的每个步骤，并开发了催化反应方案。通过DFT和DLPNO-CCSD（T）计算进一步研究了反应机理。催化转化开始于硼氢化吡啶对CH的裂解，显示出沮丧的路易斯对反应性。经C H裂解形成的吡啶酮硼烷络合物解离为吡啶酮和炔基硼烷。吡啶酮前所未有的1,2-碳硼化和原脱硼化作用可生成1,3-烯炔并完成催化循环。硼原子-配位体配合作用描述了硼氢化吡啶在C–H裂解后的配位模式的变化，

更新日期：2019-04-16

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