CATALYTIC INTERMOLECULAR HYDROACYLATION USING RHODIUM COMPLEX

我们在2004年报道了水杨醛与1，4-五或1，5-六二烯在铑催化剂作用下的分子间氢酰化反应，在温和的反应条件下得到了异和正氢酰化产物的混合物。上述发现促使我们对该反应进行研究，以开发一种实用的立体选择性和区域选择性的合成反应. Rh催化的顺丁烯二烯的π-面选择性分子间氢酰化反应研究了Rh催化的顺丁烯二烯与水杨醛的π-面选择性分子间氢酰化反应。在与异戊烯的反应中，由于空间位阻的作用，选择性地产生外氢化酰化产物。在降冰片二烯的情况下，由于螯合作用，立体选择性地获得内产物。此外，由于螯合作用和远取代基效应，7-叔丁氧基降冰片二烯反应生成的产物为内、顺式产物。因此，可以避免立体选择性的氢酰化反应.腈促进的铑催化的烯烃与水杨醛的分子间氢酰化反应铑催化的水杨醛和烯腈的分子间氢酰化反应已被发现在室温下进行，并优先得到正氢酰化产物。乙腈和乙酸钠的加入加速了铑催化的单烯烃氢酰化反应，在温和的反应条件下，只生成正构氢酰化产物。还提出了区域选择性的可能反应机理。因此，该反应的一般性可被广泛开发。

We reported in 2004 that an intermolecular hydroacylation between salicylaldehydes and 1,4-penta-or 1,5-hexa-dienes by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso-and normal-hydroacylated products. The above findings prompted us to study this reaction to develop a practical synthetic reaction in connection with stereoselectivity and regioselectivity.1. Rh-catalyzed π-facial selective intermolecular hydroacylation of norbornenesRh-catalyzed π-facial selective intermolecular hydroacylation of norbornenes with salicylaldehydes have been attained. In the reaction with norbornylene, the exo-hydroacylated product was produced selectively because of steric hindrance. In the case of norbornadiene, the endo-product was obtained stereoselectively because of chelation effect. Additionally, because of chelation effect and remote substituent effects, the product formed in the reaction of 7-tert-butoxynorbornadiene was the endo, syn-product. Thus, the stereoselective hydroacylation could be achieved.2. Nitrile-promoted Rh-catalyzed intermolecular hydroacylation of olefins with salicylaldehydeRh-catalyzed intermolecular hydroacylation of salicylaldehyde and alkenylnitriles has been found to proceed at room temperature and to preferentially give normal-hydroacylated products. Addition of acetonitrile and sodium acetate accelerated the Rh-catalyzed hydroacylationof monoolefines to exclusively produce the normal-hydroacylated products under miled reaction conditions. Plausible reaction mechanisms for the regioselections are also proposed. Thus, the generality of this reaction could be widely developed.