Enantioselective intramolecular [2 + 2 + 2] cycloaddition of enediynes for the synthesis of chiral cyclohexa-1,3-dienes.
Enantioselective intramolecular [2 + 2 + 2] cycloaddition of enediynes for the synthesis of chiral cyclohexa-1,3-dienes.
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DOI：
10.1021/jo070762d
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发表时间：
2007-07
期刊：
影响因子：
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通讯作者：
T. Shibata;H. Kurokawa;Kazumasa Kanda
中科院分区：
文献类型：
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作者：
T. Shibata;H. Kurokawa;Kazumasa Kanda
各种烯二炔的对映选择性分子内 [2 + 2 + 2] 环加成（其中两个乙炔部分通过反式烯烃部分连接）使用 Rh-H8-BINAP 催化剂得到手性三环环己-1,3-二烯。对于碳原子束缚的烯二炔，无论其炔末端的取代基如何，对映选择性通常从良好到高。相反，对于杂原子束缚的烯二炔，需要适当的取代基在两个炔部分之前诱导炔和烯烃部分的氧化偶联，这对于高度对映选择性的分子内环加成非常重要。
The enantioselective intramolecular [2 + 2 + 2] cycloaddition of various enediynes, where two acetylenic moieties are connected by a trans-olefinic moiety, gave chiral tricyclic cyclohexa-1,3-dienes using Rh-H8-BINAP catalyst. In the case of carbon-atom-tethered enediynes, enantioselectivity was generally good-to-high regardless of the substituents on their alkyne termini. In contrast, with heteroatom-tethered enediynes, appropriate substituents were required to induce the oxidative coupling of alkyne and alkene moieties before that of two alkyne moieties, which would be important for highly enantioselective intramolecular cycloaddition.