N-Phosphino-p-tolylsulfinamide Ligands: Synthesis, Stability, and Application to the Intermolecular Pauson−Khand Reaction

详细信息    查看全文

• 作者：Marc Revé ; s ; Thierry Achard ; Jordi Solà ; Antoni Riera ; Xavier Verdaguer
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：September 19, 2008
• 年：2008
• 卷：73
• 期：18
• 页码：7080-7087
• 全文大小：299K
• 年卷期：v.73,no.18(September 19, 2008)
• ISSN：1520-6904

文摘

Here we synthesized a family of racemic and optically pure N-phosphino-p-tolylsulfinamide (PNSO) ligands. Their stability and coordination behavior toward dicobalt−alkyne complexes was evaluated. Selectivities of up to 3:1 were achieved in the ligand exchange process with (μ-TMSC₂H)Co₂(CO)₆. The resulting optically pure major complexes were tested in the asymmetric intermolecular Pauson−Khand reaction and yielded up to 94% ee. X-ray studies of the major complex 18a indicated that the presence of an aryl group on the sulfinamide reduces the hemilabile character of the PNSO ligands.