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Silver-Catalyzed Asymmetric Aldol Reaction of Isocyanoacetic Acid Derivatives Enabled by Cooperative Participation of Classical and Nonclassical Hydrogen Bonds
Advanced Synthesis & Catalysis ( IF 5.4 ) Pub Date : 2022-06-03 , DOI: 10.1002/adsc.202200327
Satoshi Sakai 1 , Akane Fujioka 1 , Koji Imai 1 , Kei Uchiyama 1 , Yohei Shimizu 1, 2 , Kosuke Higashida 1, 2 , Masaya Sawamura 1, 2
Affiliation  

The silver-catalyzed asymmetric aldol reaction of isocyanoacetic acid derivatives with aldehydes has been developed by employing a chiral prolinol-phosphine as a hydrogen-bond-donating P,N,O ligand. DFT calculations indicated that the reaction proceeds in a stepwise manner, involving C−C bond forming carbonyl addition and subsequent enantioselectivity-determining oxazoline ring formation. An O−H⋅⋅⋅O/sp3-C−H⋅⋅⋅O two-point hydrogen bond donated by the prolinol moiety of the ligand activates the aldehyde in the C−C bond formation step and facilitates the subsequent cyclization under stereocontrol by the catalyst. The calculations further suggest that additional nonclassical C−H⋅⋅⋅O hydrogen bonds as well as London dispersion interactions may also participate synergistically in the stereocontrol.

中文翻译:

通过经典和非经典氢键的协同参与实现异氰基乙酸衍生物的银催化不对称羟醛反应

通过使用手性脯氨醇-膦作为供氢键的 P,N,O 配体,开发了异氰基乙酸衍生物与醛的银催化不对称羟醛反应。DFT 计算表明反应以逐步方式进行,包括形成 C-C 键的羰基加成和随后的对映选择性决定恶唑啉环的形成。由配体的脯氨醇部分提供的 O−H⋅⋅⋅O/ sp 3 -C−H⋅⋅⋅O 两点氢键在 C−C 键形成步骤中激活醛,并促进随后在立体控制下的环化由催化剂。计算进一步表明,额外的非经典 C−H···O 氢键以及伦敦色散相互作用也可能协同参与立体控制。
更新日期:2022-06-03
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