手性轴烯的 Rh(I)催化环羰化反应构建 5,7-双环体系的对映选择性合成。
Enantioselective synthesis of 5,7-bicyclic ring systems from axially chiral allenes using a Rh(I)-catalyzed cyclocarbonylation reaction.
机构信息
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
出版信息
J Org Chem. 2013 Apr 19;78(8):3737-54. doi: 10.1021/jo4002432. Epub 2013 Mar 29.
Abstract
A transfer of chirality in an intramolecular Rh(I)-catalyzed allenic Pauson-Khand reaction (APKR) to access tetrahydroazulenones, tetrahydrocyclopenta[c]azepinones and dihydrocyclopenta[c]oxepinones enantioselectively (22-99% ee) is described. The substitution pattern of the allene affected the transfer of chiral information. Complete transfer of chirality was obtained for all trisubstituted allenes, but loss of chiral information was observed for disubstituted allenes. This work constitutes the first demonstration of a transfer of chiral information from an allene to the 5-position of a cyclopentenone using a cyclocarbonylation reaction. The absolute configuration of the corresponding cyclocarbonylation product was also established, something that is rarely done.
摘要
在手性铑（I）催化的烯丙基 Pauson-Khand 反应（APKR）中，通过分子内转移手性，可以立体选择性地获得四氢吖嗪酮、四氢环戊[c]氮杂卓酮和二氢环戊[c]氧杂卓酮（22-99%ee）。烯丙基的取代模式影响手性信息的转移。对于所有三取代的烯丙基，都可以完全转移手性，但对于二取代的烯丙基，则观察到手性信息的损失。这项工作首次证明了在手性环丙羰化反应中，通过环加成反应从烯丙基向环戊烯酮的 5-位转移手性信息。相应的环羰化产物的绝对构型也得到了确定，这是很少做的事情。
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