Ning Yongquan, Song Qingmin, Sivaguru Paramasivam, Wu Lizuo, Anderson Edward A, Bi Xihe
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, China.
Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, U.K.
Org Lett. 2022 Jan 21;24(2):631-636. doi: 10.1021/acs.orglett.1c04081. Epub 2022 Jan 5.
Here we report a silver-catalyzed alkynyl carbene insertion into β-ketocarbonyls using alkynyl -nosylhydrazones as alkynyl carbene precursors, which provides access to trisubstituted allenyl ketones. This reaction represents the first example of an alkynyl carbene insertion into a C-C σ bond, affording products homologated with an sp carbon center. The products are useful substrates for further transformations. Experimental investigations and theoretical calculations suggest the reaction proceeds through a stepwise enol cyclopropanation/retro-aldol pathway.
在此，我们报道了一种以炔基 - 亚磺酰腙作为炔基卡宾前体的银催化炔基卡宾插入β - 羰基化合物的反应，该反应可用于合成三取代联烯酮。此反应是炔基卡宾插入C - C σ键的首例，得到的产物在sp碳中心上实现了同系化。这些产物是用于进一步转化的有用底物。实验研究和理论计算表明，该反应通过逐步的烯醇环丙烷化/逆羟醛途径进行。
