The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles via an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(I) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.

中文翻译：

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烯丙基连接的环己酮的双催化对映选择性脱对称

对映体富集氮杂双环[3.3.1]壬烷-6-酮杂环的结构通过丙二烯联环己酮的对映选择性desymmetrization，启用通过双催化体系，其提供与手性脯氨酰胺和丙二烯与铜的环己酮的激活同步描述了（I）递送立体定义的双环核的助催化剂。还成功地应用于氧类似物，从而为结构复杂的双环醚构架提供了新的对映选择性合成入口。使用密度泛函理论（DFT）计算发现了机械途径以及对映和非对映选择性的起源。