Luo Jian, Chen Guo-Shu, Chen Shu-Jie, Liu Yun-Lin
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China.
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China.
Sci Bull (Beijing). 2020 Apr 30;65(8):670-677. doi: 10.1016/j.scib.2019.12.023. Epub 2019 Dec 31.
An expedient and economic approach for constructing O,O,N-spiro compounds consisting of both a 1,3-oxazine and a furan ring through a catalyst-free formal [4+1]/[4+2] cycloaddition cascade sequence of isocyanides with two molecules of acylketene formed in situ through thermal-induced Wolff rearrangement of 2-diazo-1,3-diketones was developed. The reaction displayed good functional group tolerance and was compatible with different isocyanides and 2-diazo-1,3-diketones. Furthermore, preliminary asymmetric attempts of this reaction are made by utilizing optically pure isocyanides as inputs, and moderate diastereomeric induction was observed.
通过2-重氮-1,3-二酮热诱导的沃尔夫重排原位生成的两分子酰基乙烯酮与异腈进行无催化剂的形式[4+1]/[4+2]环加成串联反应，开发了一种便捷且经济的构建由1,3-恶嗪和呋喃环组成的O,O,N-螺环化合物的方法。该反应表现出良好的官能团耐受性，并且与不同的异腈和2-重氮-1,3-二酮兼容。此外，以光学纯异腈为原料对该反应进行了初步的不对称尝试，并观察到了适度的非对映体诱导。
