Copper(I)-Catalyzed Regio- and Stereoselective Intramolecular Alkylboration of Propargyl Ethers and Amines
Copper(I)-Catalyzed Regio- and Stereoselective Intramolecular Alkylboration of Propargyl Ethers and Amines
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DOI：
10.1021/acs.joc.7b02071
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发表时间：
2017-10-06
影响因子：
3.6
通讯作者：
Ito, Hajime
中科院分区：
文献类型：
--
作者：
Iwamoto, Hiroaki;Ozawa, Yu;Ito, Hajime
研究了铜催化的炔丙基醚和含烷基亲电基团的胺的区域和立体选择性分子内烷基化。该反应显示出高的官能团耐受性，并得到高度官能化的含杂环的烯基硼酸酯，它们是有机化学中的通用合成中间体。硼化产物可以通过立体定向转化转化为多取代烯烃。机理研究表明，铜（I）催化硼基化反应的化学和立体选择性取决于离去基团的类型。密度泛函理论计算表明，炔硼铜化反应的区域选择性是由炔丙基醚中氧原子的电子效应和炔丙基位置上取代基与硼原子之间的空间拥挤效应共同控制的.
The copper(I)-catalyzed regio- and stereoselective intramolecular alkylation of propargyl ethers and amines bearing an alkyl electrophilic moiety has been developed. The reaction showed high functional group tolerance and gave highly functionalized alkenylboronates bearing heterocyclic rings, which are versatile synthetic intermediates in organic chemistry. The borylation products can be transformed into multisubstituted alkenes through stereospecific transformations. Mechanistic studies showed that the chemo- and stereoselectivity of copper(I)-catalyzed borylation depends on the type of leaving group. Density functional theory calculations suggested that the regioselectivity of the borylcupration of the alkyne is controlled by the electronic effect of the oxygen atom of the propargyl ether in combination with the steric congestion between the boryl group and the substituent at the propargylic position.