Rhodium-Catalyzed Pauson鈥揔hand Reaction Using a Small-Bite-Angle P-Stereogenic C1-Diphosphine Ligand
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- 作者：Edgar Crist贸bal-Lecina ; Andrea R. Costantino ; Arnald Grabulosa ; Antoni Riera ; Xavier Verdaguer
- 刊名：Organometallics
- 出版年：2015
- 出版时间：October 26, 2015
- 年：2015
- 卷：34
- 期：20
- 页码：4989-4993
- 全文大小：309K
- ISSN：1520-6041
文摘
The asymmetric Pauson鈥揔hand reaction catalyzed by [Rh(COD)(MaxPHOS)]BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observed results. The intermediate rhodium dicarbonyl complex 6 was synthesized, and its solid-state structure was elucidated by X-ray crystallography.