碳化物
环加成
叶立德
化学
钴
立体选择性
催化作用
对映选择合成
密度泛函理论
产量(工程)
组合化学
计算化学
药物化学
有机化学
材料科学
铑
冶金
作者
Xiaobin Lin,Maoping Pu,Xinpeng Sang,Shiyang Li,Xiaohua Liu,Yun‐Dong Wu,Xiaoming Feng
标识
DOI:10.1002/anie.202201151
摘要
Herein, we report the first example of enantioselective (2+1) cycloaddition of thioketones with α-diazo pyrazoleamides for the direct synthesis of tetrasubstituted thiiranes. In the presence of chiral N,N'-dioxide/cobalt(ΙΙ) complexes (2-5 mol%), excellent efficiency (up to 99 % yield within 15 mins) and high stereoselectivity (up to >19 : 1 dr and 97 % ee) are available. Elaborations of thiiranes via desulfuration have also been conducted to deliver tetrasubstituted olefins. Density functional theory calculations reveal that the reaction initiates from a doublet state cobalt(ΙΙ) carbenoid, which is followed by a quartet cobalt(ΙΙ)-bound thiocarbonyl ylide pathway. This work provides a route for the selective construction of tetrasubstituted thiiranes and olefins that are otherwise difficult to access.
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