Experimental Observation of β-Carbon Elimination from Alkenylrhodium Complexes through Exchange Reactions of the Alkenyl Unit
Experimental Observation of β-Carbon Elimination from Alkenylrhodium Complexes through Exchange Reactions of the Alkenyl Unit
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DOI：
10.1021/acs.organomet.1c00695
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发表时间：
2022-02-14
期刊：
影响因子：
2.8
通讯作者：
Ishii, Youichi
中科院分区：
文献类型：
--
作者：
Iwamoto, Takahiro;Shibuya, Koushi;Ishii, Youichi
通过研究无张力金属环烯基铑配合物中烯烃单元的交换反应，研究了烯基金属配合物的β-碳消除反应，得到相应的炔，这是一种罕见的β-碳消除反应。当用另一种内炔处理衍生自1-萘基膦和二苯基乙炔的烯基铑络合物1时，即使在0 ℃下也形成1和烯基交换的络合物2的平衡混合物。使用PPh 3的原位捕集实验表明，交换反应是由1的β-碳消除介导的，以提供作为中间体的二苯基乙炔络合物。一项理论研究也支持β-碳消除的参与。还描述了炔取代基的影响。
We have investigated beta-carbon elimination of an alkenylmetal complex to give the corresponding alkyne, a rare type of beta-carbon elimination, through the study of the exchange reaction of the alkene unit in an unstrained metallacyclic alkenylrhodium complex. When alkenylrhodium complex 1 derived from 1-naphthylphosphine and diphenylacetylene was treated with another internal alkyne, an equilibrium mixture of 1 and alkenylgroup-exchanged complex 2 was formed even at 0 degrees C. An in situ trapping experiment using PPh3 revealed that the exchange reaction was mediated by beta-carbon elimination of 1 to afford a diphenylacetylene complex as an intermediate. A theoretical study also supported the involvement of the beta-carbon elimination. The effects of alkyne substituents are also described.