| Title | Mechanistic Study on the Cleavage and Reorganization of C(sp(3))H and CN Bonds in Carbodiimides: Synthesis of 1,2-Dihydrothiopyrimidines and 2,3-Dihydropyrimidinthiones through Four-Component Coupling |
| Authors | Wang, Yang Zhao, Fei Zhou, Yi Chi, Yue Wang, Zitao Zhang, Wen-Xiong Xi, Zhenfeng |
| Affiliation | Peking Univ, Coll Chem, Key Lab Bioorgan Chem & Mol Engn, BNLMS,Minist Educ, Beijing 100871, Peoples R China. Nankai Univ, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China. |
| Keywords | CH activation multicomponent reactions reaction intermediates reaction mechanisms synthetic methods EARTH-METAL COMPLEXES EFFICIENT MULTICOMPONENT REACTIONS ONE-POT SYNTHESIS AMINE N-H HIGHLY EFFICIENT TERMINAL ALKYNES COORDINATION CHEMISTRY CATALYTIC ADDITION SUBSTITUTED GUANIDINES ORGANIC-SYNTHESIS |
| Issue Date | 2013 |
| Publisher | chemistry a european journal |
| Citation | CHEMISTRY-A EUROPEAN JOURNAL.2013,19,(32),10643-10654. |
| Abstract | This study sheds light on the cleavage and reorganization of C(sp(3))-H and C= N bonds of carbodiimides in a three-component reaction of terminal alkynes, sulfur, and carbodiimides by a combination of methods including 1) isolation and X-ray analysis of sixmembered- ring lithium species 2-S, 2) trapping of the oxygen-analogues (B-O and D-O) of both four-membered- ring intermediate B-S and ringopening intermediate D-S, 3) deuterium labeling studies, and 4) theoretical studies. These results show that 1) the reaction rate-determining step is [2+ 2] cycloaddition, 2) the C= N bond cleavage takes place before C(sp(3))-H bond cleavage, 3) the hydrogen attached to C6 in 2-S originates from the carbodiimide, and 4) three types of new azaheterocycles, such as 1,2-dihydrothiopyrimidines, N-acyl 2,3-dihydropyrimidinthiones, and 1,2-dihydropyrimidinamino acids are constructed efficiently based on 2-S. All results strongly support the idea that the reaction proceeds through [2+ 2] cycloaddition/4p electrocyclic ring-opening/1,5-H shift/6p electrocyclic ring-closing as key steps. The research strategy on the synthesis, isolation, and reactivity investigation of important intermediates in metal-mediated reactions not only helps achieve an in-depth understanding of reaction mechanisms but also leads to the discovery of new synthetically useful reactions based on the important intermediates. |
| URI | http://hdl.handle.net/20.500.11897/342835 |
| ISSN | 0947-6539 |
| DOI | 10.1002/chem.201301633 |
| Indexed | SCI(E) PubMed |
| Appears in Collections: | å å¦ä¸ å å å·¥ç¨ å¦é ¢ 生物有机与分子工程教育部重点实验室 |
