Silver‐Catalyzed Asymmetric Aldol Reaction of Isocyanoacetic Acid Derivatives Enabled by Cooperative Participation of Classical and Nonclassical Hydrogen Bonds. Issue 14 (21st June 2022)

• Record Type: Journal Article
• Authors: Sakai, Satoshi; Fujioka, Akane; Imai, Koji; Uchiyama, Kei; Shimizu, Yohei; Higashida, Kosuke; Sawamura, Masaya
• Is Part Of: Advanced synthesis & catalysis. Volume 364:Issue 14(2022)
• Page Start: 2333
• Page End: 2339
• Publication Date: 2022-06-21
• Subjects: silver catalysis -- asymmetric aldol reaction -- oxazolines -- DFT calculation -- noncovalent interactions; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.202200327
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: 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/ sp 3 ‐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. Abstract :