Le Tam Minh, Csámpai Antal, Fülöp Ferenc, Szakonyi Zsolt
Institute of Pharmaceutical Chemistry, University of Szeged, H-6720, Szeged Eötvös utca 6, Hungary.
Institute of Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518, Budapest-112, Hungary.
Chemistry. 2018 Sep 12;24(51):13607-13615. doi: 10.1002/chem.201802484. Epub 2018 Aug 17.
A library of monoterpene-based aminodiols was synthesized and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The reduction of a bicyclic α-methylene ketone, derived from natural (-)-limonene followed by epoxidation, gave the key epoxy alcohol intermediate. Ring opening of the oxirane ring with primary amines induced by lithium perchlorate afforded the required aminodiols. Substituent-dependent ring closure of the secondary aminodiols with formaldehyde resulted in both spirooxazolidines and a fused 1,3-oxazine. Cyclization reactions of the studied aminodiols, resulting in spirocyclic oxazolidines and an isomeric perhydro-1,3-oxazine-fused compound along with the possible iminium intermediates, were analyzed by a systematic series of comparative DFT models performed at the B3LYP/6-31+G(d,p) level of theory.
合成了一个基于单萜的氨基二醇库，并将其用作二乙基锌与苯甲醛加成反应的手性催化剂。由天然（-）-柠檬烯衍生的双环α-亚甲基酮经还原后进行环氧化反应，得到关键的环氧醇中间体。用高氯酸锂引发的伯胺使环氧乙烷环开环，得到所需的氨基二醇。仲氨基二醇与甲醛的取代基依赖性环化反应生成了螺恶唑烷和稠合的1,3-恶嗪。通过在B3LYP/6-31+G(d,p)理论水平上进行的一系列系统的比较密度泛函理论（DFT）模型，分析了所研究的氨基二醇的环化反应，该反应生成了螺环恶唑烷和一种异构的全氢-1,3-恶嗪稠合化合物以及可能的亚胺中间体。
