文献类型：期刊文献

英文题名：Thermally-induced intramolecular [2+2] cycloaddition of allene-methylenecyclopropanes: expedient access to two separable spiropolycyclic heterocycles

作者：Li, Min[1,2];Wei, Yin[3];Shi, Min[1,2,3]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, 130 Mei Long Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, 130 Mei Long Rd, Shanghai 200237, Peoples R China;[3]Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Chinese Acad Sci, Ctr Excellence Mol Synth,State Key Lab Organometal, 345 Lingling Rd, Shanghai 200032, Peoples R China

年份：2023

卷号：10

期号：2

起止页码：440

外文期刊名：ORGANIC CHEMISTRY FRONTIERS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000893752800001)】；

基金：We are grateful for the financial support from the National Key R & D Program of China (2022YFC2303101), the National Natural Science Foundation of China (21372250, 21121062, 21302203, 20732008, 21772037, 21772226, 21861132014, 91956115, and 22171078), and the Fundamental Research Funds for the Central Universities 222201717003.

语种：英文

摘要：In this paper, a thermally-induced intramolecular [2 + 2] cycloaddition of allene-methylenecyclopropanes has been developed for the rapid construction of nitrogen-containing spiro[bicyclo[3.2.0]heptane-6,1 '-cyclopropane] and spiroheptane-2,1 '-cyclopropane polycyclic heterocycles in excellent total yields with good functional group compatibility under relatively mild conditions. These two heterocycles are separable and formed at the same time in the absence of any catalyst or additive. The reaction mechanism is clarified by control experiments and DFT calculations, and it was found that the reaction proceeded through a stepwise process via a key intermediate containing a seven-membered ring rather than a concerted pathway.