Synthesis, Resolution, and Absolute Configuration of Chiral Tris(2-pyridylmethyl)amine-Based Hemicryptophane Molecular Cages

Dawei Zhang (1) , Benjamin Bousquet (1) , Jean-Christophe Jean (1) , Delphine Pitrat (1) , Marion Jean (2) , Nicolas Vanthuyne (1) , Laure Guy (1) , Jean-Pierre Dutasta (1) , Alexandre Martinez (2)

1 LC - Laboratoire de Chimie - UMR5182
2 ISM2 - Institut des Sciences Moléculaires de Marseille

The synthesis, characterization, and chiroptical properties of a new class of hemicryptophane cages combining a cyclotriveratrylene unit and a tris(2-pyridylmethyl)amine (TPA) moiety are reported. Changing the linkers between these two units allows for the modification of the size and shape of the cavity. The synthesis is straightforward and efficient, providing gram-scale of cage compounds. The racemic mixture of each hemicryptophane host can be readily resolved by chiral HPLC, giving an easy access to the enantiopure molecular cages of which absolute configurations have been assigned by ECD spectroscopy. These new hemicryptophanes are available chemical platforms ready to use for various purposes due to the versatile metal complexation properties of the TPA unit. A Zn(II)@hemicryptophane complex has been obtained and used as a heteroditopic host for the selective recognition of zwitterionic guests.

Domaines: Chimie organique; Chimie de coordination

Dawei Zhang, Benjamin Bousquet, Jean-Christophe Jean, Delphine Pitrat, Marion Jean, et al.. Synthesis, Resolution, and Absolute Configuration of Chiral Tris(2-pyridylmethyl)amine-Based Hemicryptophane Molecular Cages. Journal of Organic Chemistry, 2017, 82 (12), pp.6082-6088. ⟨10.1021/acs.joc.7b00559⟩. ⟨hal-01682759⟩