Co-catalysis in the way of synergetic catalysis and sequential catalysis has emerged as a powerful tool to achieve one-pot tandem reaction. Herein, a tri-functional catalytic system containing phosphino-phosphonium bi-functional ligand (L2) based Rh-catalyst and aniline was developed for three-step tandem hydroformylation-aldol condensation-hydrogenation to produce ketones from olefins. It was found that the intramolecular bi-functionalities of phosphino-fragment and phosphonium [P(V)⁺] in L2 greatly facilitated hydroformylation due to their synergetic effect on activation of carbonyl (CO) in Rh-acyl intermediate. In addition, the phosphonium in L2 also served as a Lewis acid to catalyse condensation of acetone with aniline to form enamine catalyst. The latter with more nucleophilicity was able to attack the aldehydes (formed from the preceding hydroformylation) to accomplish the subsequent aldol condensation along with the release of aniline. Finally, the obtained α,β-unsaturated ketones were hydrogenated to yield ketones over L2-based Rh-catalyst under the hydroformylation conditions. Such tri-functional catalytic system in combination of transition-metal catalysis, Lewis acid catalysis and enamine catalysis also exhibited good generality for the tandem hydroformylation-aldol condensation-hydrogenation of the different olefins to produce ketones.

以协同催化和顺序催化的方式进行的共催化已经成为实现一锅串联反应的有力工具。在此，开发了一种基于膦-膦双功能配体（L2）的Rh催化剂和苯胺的三功能催化体系，用于三步串联加氢甲酰化-醛醇缩合加氢以从烯烃生产酮。发现L2中的膦片段和ino [P（V）⁺ ]的分子内双功能极大地促进了加氢甲酰化，因为它们对Rh-酰基中间体中的羰基（C O）具有协同作用。此外，L2中的the也用作路易斯酸，以催化丙酮与苯胺的缩合反应，形成烯胺催化剂。具有亲核性的后者能够攻击醛（由先前的加氢甲酰化形成），以完成随后的羟醛缩合以及苯胺的释放。最后，将所获得的α，β-不饱和酮在加氢甲酰化条件下在基于L 2的Rh催化剂上氢化以产生酮。结合过渡金属催化，路易斯酸催化和烯胺催化的这种三官能催化体系对于不同的烯烃的串联加氢甲酰化-醛醇缩合加氢生成酮也显示出良好的通用性。