State Key Laboratory for Conservation and Utilization of Bio-Resources in Yunnan, Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming, 650091, China.
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12697-12701. doi: 10.1002/anie.201706304. Epub 2017 Aug 30.
The application potential of primary amine catalysts in the context of Mannich reactions of aldehydes with ketimines is exemplified by isatin-derived ketimines and cyclic trifluoromethyl ketimines. Primary amine catalysts exhibit either unusual stereoselectivity or reactivity, which is not observable with secondary amine catalysts. Moreover, reversal of diastereofacial selectivity between primary and secondary amine catalysts is disclosed. These new reactions provide useful methods for the syntheses of chiral 3-substituted 3-amino-2-oxindoles and dihydroquinazolinones bearing a trifluoromethylated quaternary stereocenter. The synthetic utility of the reactions is demonstrated through the formal synthesis of AG-041R and DPC 083 and the total synthesis of (-)-psychotriasine.
本文以色胺酮和环状三氟甲基亚胺为例，阐述了伯胺催化剂在醛与亚胺的曼尼希反应中的应用潜力。伯胺催化剂表现出非寻常的立体选择性或反应性，这在仲胺催化剂中是观察不到的。此外，本文还揭示了伯胺催化剂和仲胺催化剂之间的非对映选择性的反转。这些新反应为合成具有手性 3-取代 3-氨基-2-氧代吲哚和含有三氟甲基化季立体中心的二氢喹唑啉酮提供了有用的方法。通过 AG-041R 和 DPC 083 的形式合成以及 (-)-psychotriasine 的全合成，证明了这些反应的合成实用性。
