Tanaka Fujie
Chemistry and Chemical Bioengineering Unit, Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna, Okinawa 904-0495, Japan.
Chem Rec. 2023 Jul;23(7):e202200207. doi: 10.1002/tcr.202200207. Epub 2022 Oct 6.
Carbonyl transformations involving enolates and/or enamines have been used for various types of bond-forming reactions. In this account, catalysts and catalyst systems that have amino acids or primary, secondary, and/or tertiary amines as key catalytic functional groups that we have developed to accelerate chemical transformations, including regio-, diastereo- and enantioselective reactions, are discussed. Our chemical transformation strategies and methods that use amine derivatives as catalysts are also discussed. As amines can have different functions depending on protonation and on the species formed during the catalysis (such as enamines and iminium ions), dynamics and kinetic controls are the keys for understanding the catalysis. Further, strategies that harness dynamic steps and kinetic control in amine-catalyzed reactions have enabled the synthesis of complex molecules in stereocontrolled manners. Understanding the dynamic features and the kinetic controls of the catalysis will further the design of the catalysts and the development of chemical transformation strategies and methods.
涉及烯醇盐和/或烯胺的羰基转化已用于各种类型的成键反应。在本报告中，将讨论我们开发的以氨基酸或伯胺、仲胺和/或叔胺作为关键催化官能团的催化剂和催化剂体系，这些催化剂和体系可加速化学转化，包括区域选择性、非对映选择性和对映选择性反应。还将讨论我们使用胺衍生物作为催化剂的化学转化策略和方法。由于胺根据质子化情况以及催化过程中形成的物种（如烯胺和亚胺离子）可具有不同功能，动力学和动力学控制是理解催化作用的关键。此外，在胺催化反应中利用动态步骤和动力学控制的策略已能够以立体控制的方式合成复杂分子。理解催化作用的动态特征和动力学控制将推动催化剂的设计以及化学转化策略和方法的发展。
