Chiral Lewis acids play an important role in the precise construction of various types of chiral molecules. Here, a cage-shaped borate 2 was designed and synthesized as a chiral Lewis acid that possesses a unique C -symmetric structure composed of three homochiral binaphthyl moieties. The highly symmetrical structure of 2 with homochirality was clearly elucidated by X-ray crystallographic analysis. The peculiar chiral environment of 2⋅THF exhibited chiral recognition of some simple amines and a sulfoxide. Moreover, the application of 2⋅THF to hetero-Diels-Alder reactions as a chiral Lewis-acid catalyst afforded the enantioselective products, which were obtained through an entropy-controlled pathway according to the analysis of the relationship between optical yield and reaction temperature. In particular, the robust chiral reaction field of 2⋅THF allowed the first example of an asymmetric hetero-Diels-Alder reaction with a simple diene despite the requirement of high temperature.

Monomeric cage-shaped aluminum aryl oxides 1Al were synthesized using tripodal triphenolic ligands. The Lewis acidity and catalytic activity of the obtained 1Al•py were investigated. The Lewis acidity of 1Al•py originates from the flexible change in the coordination number of the aluminum center, allowing the catalytic O-glycosylation to occur with a high efficiency and an unusual stereoselectivity.

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