Zhang Lin, Yamazaki Ken, Leitch Jamie A, Manzano Ruben, Atkinson Victoria A M, Hamlin Trevor A, Dixon Darren J
Department of Chemistry, Chemistry Research Laboratory, University of Oxford 12 Mansfield Road Oxford UK.
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Chem Sci. 2020 Jun 24;11(28):7444-7450. doi: 10.1039/d0sc02878a.
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles 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.
描述了对映体富集的氮杂双环[3.3.1]壬-6-酮杂环的构建，即通过双催化体系实现的联烯连接的环己酮的对映选择性去对称化，该体系能使环己酮与手性脯氨酰胺以及联烯与铜（I）共催化剂同步活化，以构建立体定义的双环核心。还成功应用于氧类似物，从而为构建结构复杂的双环醚骨架提供了一种新的对映选择性合成方法。利用密度泛函理论（DFT）计算揭示了对映选择性和非对映选择性的机理途径及起源。
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