期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 19, 期 32, 页码 10643-10654出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201301633
关键词
CH activation; multicomponent reactions; reaction intermediates; reaction mechanisms; synthetic methods
资金
- Natural Science Foundation of China
- 973 Program [2011CB808600]
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.
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