Institute of Research in Biomedicine (IRB Barcelona), The Barcelona Institute of Science and Technology (BIST), Baldiri Reixach 10, 08028, Barcelona, Spain.
Departament de Química Inorgànica i Orgànica, Secció Química, Orgànica, Universitat de Barcelona, Martí i Franquès 1, 08028, Barcelona, Spain.
Angew Chem Int Ed Engl. 2022 Jul 18;61(29):e202204300. doi: 10.1002/anie.202204300. Epub 2022 May 31.
Chiral compounds containing nitrogen heteroatoms are fundamental substances for the chemical, pharmaceutical and agrochemical industries. However, the preparation of some of these interesting scaffolds is still underdeveloped. Herein we present the synthesis of a family of P-stereogenic phosphinooxazoline iridium catalysts from L-threonine methyl ester and their use in the asymmetric hydrogenation of N-Boc-2,3-diarylallyl amines, achieving very high enantioselectivity. Furthermore, the synthetic utility of the 2,3-diarylpropyl amines obtained is demonstrated by their transformation to 3-aryl-tetrahydroquinolines and 4-benzyl-tetrahydroisoquinolines, which have not yet been obtained in an enantioselective manner by direct reduction of the corresponding aromatic heterocycles. This strategy allows the preparation of these types of alkaloids with the highest enantioselectivity reported up to date.
手性含氮杂原子化合物是化学、制药和农化工业的基础物质。然而，其中一些有趣的结构的制备仍不够完善。在此，我们介绍了一类由 L-苏氨酸甲酯合成的 P 手性膦氧氮杂环戊烯铱催化剂，并将其用于 N-Boc-2,3-二芳基烯丙基胺的不对称氢化反应，获得了非常高的对映选择性。此外，通过将获得的 2,3-二芳基丙胺转化为 3-芳基-四氢喹啉和 4-苄基-四氢异喹啉，证明了它们的合成实用性，而这些化合物尚未通过相应的芳香杂环的直接还原以对映选择性的方式获得。该策略允许以迄今为止报道的最高对映选择性制备这些类型的生物碱。
