Catalytic Asymmetric Enyne Addition to Aldehdyes and Rh(I)-Catalyzed Stereoselective Domino Pauson-Khand/[4+2] Cycloaddition
Catalytic Asymmetric Enyne Addition to Aldehdyes and Rh(I)-Catalyzed Stereoselective Domino Pauson-Khand/[4+2] Cycloaddition
复制标题
DOI：
10.1021/jo3026065
复制
发表时间：
2013-03-15
影响因子：
3.6
通讯作者：
Pu, Lin
中科院分区：
文献类型：
--
作者：
Chen, Wei;Tay, Jia-Hui;Pu, Lin
在室温下，1，1‘-双-2-萘酚ZnEt2-Ti((OPR)-Pr-I)(4)-Cy2NH体系催化1，3-烯炔与脂肪醛和其他醛的加成反应，产率为75-96%，ee为82-97%。该体系也广泛适用于其他烷基、芳基和硅基炔烃与结构不同的醛的高度对映选择性反应。通过催化不对称烯炔与脂肪醛的加成反应，制备了一系列具有光学活性的三烯丙醇。在催化量的[RhCl(CO)(2)](2)和1atm的CO存在下，光学活性的三苯炔发生高度立体选择性的多米诺骨牌Pauson-Khandd/[4+2]环加成反应生成光学活性的多环产物。Rh(I)催化剂还可以催化二炔与CO的偶联反应，然后进行[4+2]环加成反应，生成光学活性的多环产物。这些转化对含四元手性碳中心的聚喹烷的不对称合成具有潜在的应用价值。
The 1,1'-bi-2-naphthol ZnEt2-Ti((OPr)-Pr-i)(4)-Cy2NH system is found to catalyze the 1,3-enyne addition to aliphatic aldehydes as well as other aldehydes at room temperature with 75-96% yield and 82-97% ee. This system is also broadly applicable for the highly enantioselective reaction of other alkyl-, aryl-, and silylalkynes with structurally diverse aldehydes. The propargylic alcohols prepared from the catalytic asymmetric enyne addition to aliphatic aldehydes are used to prepare a series of optically active trienynes. In the presence of a catalytic amount of [RhCl(CO)(2)](2) and 1 atm of CO, the optically active trienynes undergo highly stereoselective domino Pauson-Khand/[4 + 2] cycloaddition to generate optically active multicyclic products. The Rh(I) catalyst is also found to catalyze the coupling of a diyne with CO followed by [4 + 2] cycloaddition to generate an optically active multicyclic product. These transformations are potentially useful for the asymmetric synthesis of polyquinanes containing a quaternary chiral carbon center.