Regio- and enantiospecific rhodium-catalyzed allylic etherification reactions using copper(I) alkoxides: Influence of the copper halide salt on selectivity
Regio- and enantiospecific rhodium-catalyzed allylic etherification reactions using copper(I) alkoxides: Influence of the copper halide salt on selectivity
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DOI：
10.1021/ja026337d
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发表时间：
2002-07-10
影响因子：
15
通讯作者：
Leahy, DK
中科院分区：
文献类型：
--
作者：
Evans, PA;Leahy, DK
过渡金属催化的烯丙基醚化反应是合成烯丙基醚的重要交叉偶联反应。我们以仲醇、仲醇和叔醇衍生的铜(I)醇类化合物为原料，发展了一种新的区域催化和对映异构体催化的环状不对称烯丙基醇衍生物的烯丙基醚化反应。本研究证明了卤化铜(I)盐的选择对于获得良好的区域专一性和对映体专一性是至关重要的，这为卤化物离子在不对称过渡金属催化反应中的作用提供了另一个例子。最后，以这种方式改变碱金属醇盐的反应性的能力可能为相关的金属催化的涉及杂原子的交叉偶联反应提供一种有用的方法。
The transition metal-catalyzed allylic etherification represents a fundamentally important cross-coupling reaction for the construction of allylic ethers. We have developed anewregio- and enantiospecific rhodium-catalyzed allylic etherification of acyclicunsymmetricalallylic alcohol derivatives using copper(I) alkoxides derived from primary, secondary and tertiary alcohols. This study demonstrates that the choice of copper(I) halide salt is crucial for obtaining excellent regio- and enantiospecificity, providing another example of the effect of halide ions in asymmetric transition metal-catalyzed reactions. Finally, the ability to alter the reactivity of the alkali metal alkoxides in this manner may provide a useful method for related metal-catalyzed cross-coupling reactions involving heteroatoms.