Patil Nitin T, Lutete Léopold Mpaka, Wu Huanyou, Pahadi Nirmal K, Gridnev Ilya D, Yamamoto Yoshinori
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
J Org Chem. 2006 May 26;71(11):4270-9. doi: 10.1021/jo0603835.
A conceptually novel approach for asymmetric intramolecular hydroamination, hydroalkoxylation and hydrocarbonation of alkynes using chiral palladium catalysts are described. The reactions of the aminoalkynes 5, alkynols 7, and alkynylmethines 9 in the presence of Pd2(dba)3 x CHCl3/PhCOOH/renorphos 4 in benzene (or benzene-hexane) at 100 degrees C gave the corresponding cyclization products (nitrogen heterocycles 6, oxygen heterocycles 8, and carbocycles 10) in good yields with good enantioselectivities. The origins of enantioselectivities in the hydroamination reaction are discussed based on DFT computations.
描述了一种使用手性钯催化剂对炔烃进行不对称分子内氢胺化、氢烷氧基化和烃化的概念新颖的方法。在100℃下，氨基炔烃5、炔醇7和炔基次甲基9在Pd2(dba)3·CHCl3/PhCOOH/renorphos 4存在下于苯（或苯-己烷）中反应，以良好的对映选择性得到了相应的环化产物（氮杂环6、氧杂环8和碳环10），产率良好。基于密度泛函理论计算讨论了氢胺化反应中对映选择性的来源。
