磷叶立德活化手性（Salen）TiCl配合物用于硝基烯烃的高对映选择性氰化反应
Activation of Chiral (Salen)TiCl Complex by Phosphorane for the Highly Enantioselective Cyanation of Nitroolefins.
作者信息
Chen Chen, Wu Wen-Biao, Li Yan-Hong, Zhao Qiu-Hua, Yu Jin-Sheng, Zhou Jian
机构信息
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, China.
出版信息
Org Lett. 2020 Mar 6;22(5):2099-2104. doi: 10.1021/acs.orglett.0c00612. Epub 2020 Feb 27.
We report that phosphorane can activate (salen)TiCl complex to achieve unprecedented excellent enantioselectivity and a broad substrate scope in the cyanation of nitroolefins. Our cyanating reagent Me(CHCl)SiCN proves to be more active than TMSCN in this reaction, allowing 11 β-aliphatic nitrolefins and 12 β-CF nitroolefins (either β-aryl or aliphatic) to work well to give the corresponding tertiary or quaternary β-nitronitriles with high to excellent enantioselectivity.
我们报道，磷叶立德可以活化（水杨醛）钛络合物，从而在硝基烯烃的氰化反应中实现前所未有的优异对映选择性和广泛的底物范围。我们的氰化试剂Me(CHCl)SiCN在该反应中被证明比TMSCN更具活性，使得11种β-脂肪族硝基烯烃和12种β-CF硝基烯烃（β-芳基或脂肪族）都能顺利反应，以高至优异的对映选择性得到相应的叔或季β-硝基腈。
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