Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies
Kai Yang, Qun Dang, Pei-Jun Cai, Yang Gao, Zhi-Xiang Yu* and Xu Bai*
*College of Chemistry, Peking University, Beijing 100871; Jilin University, 1266 Fujin Rd., Changchun, Jilin 130021, P. R. China, Email: yuzxpku.edu.cn, xbaijlu.edu.cn
K. Yang, Q. Dang, P.-J. Cai, Y. Gao, Z.-X. Yu, X. Bai, J. Org. Chem., 2017, 82, 2336-2344.
DOI: 10.1021/acs.joc.6b02570 (free Supporting Information)
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TFA-catalyzed inverse electron demand Diels-Alder (IEDDA) reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones provide highly functionalized pyrimidines as products in good yields. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid is required for both ihDA and rDA reactions.
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Energy profiles of the IEDDA reaction between H-A and acetone calculated at the MP2/6-311+G(d,p)-SMD(EtOH)//B3LYP/6-31G(d)-SMD(EtOH) level of theory.