Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
College of Chemistry, Beijing Normal University, Beijing, 100875, China.
Nat Commun. 2023 May 22;14(1):2911. doi: 10.1038/s41467-023-38488-4.
We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization of 1,3-enynes as atom-economic and achiral allene precursors. The synergistic catalysis enables the construction of all-carbon quaternary centers-tethered allenes bearing non-adjacent 1,3-axial central stereogenic centers in high level of diastereo- and enantio-selectivity. By switching the configurations of ligands and aminocatalysts, diastereodivergence can be achieved and any of the four diastereoisomers can be accessed in high diastereo- and enantio- selectivity.
我们在此描述了β-酮羰基和醛与 1,3-烯炔的不对称α-烯丙基allenylation。已鉴定出协同手性伯胺/Pd 催化剂，以促进 1,3-烯炔作为原子经济性和非手性烯丙基前体的利用。协同催化使构建全碳季碳中心键合的烯丙基成为可能，这些烯丙基带有非相邻的 1,3-轴向中心立体中心，具有高水平的非对映选择性和对映选择性。通过切换配体和氨基催化剂的构型，可以实现非对映选择性发散，并且可以以高的非对映选择性和对映选择性获得四种非对映异构体中的任何一种。
