Liu Li-Xia, Huang Wen-Jun, Yu Chang-Bin, Zhou Yong-Gui
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
Org Biomol Chem. 2023 Nov 1;21(42):8516-8520. doi: 10.1039/d3ob01315d.
It is challenging to enantioselectively construct molecules bearing multiple nonadjacent stereocenters, in contrast to those bearing a single stereocenter or adjacent stereocenters. Herein, we report an enantio- and diastereoselective synthesis of substituted chiral allenes with nonadjacent axial and two central chiral centers through a combination of retro-oxa-Michael addition and palladium-catalyzed asymmetric allenylic alkylation. This methodology exhibits good functional-group compatibility, and the corresponding allenylic alkylated compounds, including flavonoid frameworks, are obtained with good yields and diastereoselectivities and excellent enantioselectivities (all >95% ee). Furthermore, the scalability of the current synthetic protocol was proven by performing a gram-scale reaction.
与构建具有单个立体中心或相邻立体中心的分子相比，对映选择性地构建具有多个不相邻立体中心的分子具有挑战性。在此，我们报道了一种通过逆氧杂-Michael加成和钯催化的不对称烯丙基烷基化相结合的方法，对映选择性和非对映选择性合成具有不相邻轴向和两个中心手性中心的取代手性丙二烯。该方法具有良好的官能团兼容性，并且以良好的产率、非对映选择性和优异的对映选择性（均>95% ee）获得了相应的烯丙基烷基化化合物，包括黄酮类骨架。此外，通过进行克级反应证明了当前合成方案的可扩展性。
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