Journal
ADVANCED SYNTHESIS & CATALYSIS
Volume 364, Issue 14, Pages 2333-2339Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.202200327
Keywords
silver catalysis; asymmetric aldol reaction; oxazolines; DFT calculation; noncovalent interactions
Categories
Funding
- JSPS KAKENHI [JP18H03906, JP21H04680, JP20H04797, JP20H02729, JP20K15268]
Ask authors/readers for more resources
The silver-catalyzed asymmetric aldol reaction of isocyanoacetic acid derivatives with aldehydes has been developed using a chiral prolinol-phosphine ligand as a hydrogen-bond-donating P,N,O ligand. DFT calculations revealed a stepwise reaction mechanism, involving C-C bond formation and subsequent enantioselectivity-determining ring formation. The prolinol moiety of the ligand activates the aldehyde through a two-point hydrogen bond, facilitating the stereocontrolled cyclization. Additional nonclassical hydrogen bonds and London dispersion interactions may also contribute to stereocontrol.
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 center dot center dot center dot O/sp(3) -C-H center dot center dot center dot 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 center dot center dot center dot O hydrogen bonds as well as London dispersion interactions may also participate synergistically in the stereocontrol.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available