Highly enantioselective and regioselective nickel-catalyzed coupling of allenes, aldehydes, and silanes
Highly enantioselective and regioselective nickel-catalyzed coupling of allenes, aldehydes, and silanes
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DOI：
10.1021/ja0521831
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发表时间：
2005-05-25
影响因子：
15
通讯作者：
Jamison, TF
中科院分区：
文献类型：
--
作者：
Ng, SS;Jamison, TF
由Ni(CoD)2和NHC−IPR衍生的络合物催化了涉及烯、醛和有机硅烷的三组分偶联反应，并将烯的轴向手性转移到产物中的立体中心，具有很高的保真度。观察到了一种意想不到的区域选择性；人们青睐的是烯丙基而不是高烯丙基的醇类化合物，对应于两个亲电原子耦合的不寻常过程： ，烯原子和醛碳原子。在所有的情况下，都观察到了高的对映体选择性，高的Z/E选择性，以及对于不同取代的联烯，高的位置选择性。这一转化代表了第一个多组分对映体选择性偶联过程。
A complex derived from Ni(cod)2and NHC−IPr catalyzes a three-component coupling reaction involving allenes, aldehydes, and organosilanes and transfers the axial chirality of the allene to a stereogenic center in the product with very high fidelity. An unexpected regioselectivity is observed; favored are allylic rather than homoallylic alcohol derivatives, corresponding to the unusual process of coupling two electrophilic atoms: the allene sp and aldehyde carbon atoms. In all cases, high enantioselectivity, highZ/Eselectivity, and, with differentially substituted allenes, high site selectivity are observed. This transformation represents the first enantioselective multicomponent coupling process of allenes.