64299-63-4Relevant academic research and scientific papers
Tailoring Reaction Selectivity by Modulating a Catalytic Diad on a Foldamer Scaffold
Andrews, Mary Katherine,Gellman, Samuel H.,Liu, Xinyu
supporting information, (2022/02/10)
Use of a tunable molecular scaffold to align a reactive diad for bifunctional catalysis can reveal relationships between functional group identity and reactivity that might otherwise be impossible to identify. Here we use an α/β-peptide helix to show that an aligned pair of primary amine groups is uniquely competent to catalyze crossed aldol condensations with an aryl aldehyde as the electrophile. Geometrically similar diads in which one amine group is secondary, or both are secondary, are good catalysts for other types of aldol condensations but not those involving an aryl aldehyde. Catalytic efficacy requires β-amino acid residues that are preorganized for helix formation via cyclic constraint. Conventional peptides (exclusively α-amino acid residues) that display the primary amine diad are poor catalysts, which highlights the critical role of the foldamer scaffold.
REACTION OF ENOLATES OF ACYLTRIMETHYLSILANES WITH ALDEHYDES. CANNIZZARO TYPE OXIDATION-REDUCTION REACTION WITH A TRIMETHYLSILYLCARBONYL GROUP
Kuwajima, Isao,Matsumoto, Kazuhisa,Sugahara, Shuichi
, p. 525 - 528 (2007/10/02)
The reaction of an acyltrimethylsilane enolate with 2 eq of an aldehyde gives a 1:2 adduct, while that with the enolate of an α-chloroacyltrimethylsilane affords an α,β-unsaturated aldehyde as a 1:1 adduct accompanied by the carboxylic acid derived from the starting aldehyde.An oxidation-reduction reaction mechanism on the trimethylsilylcarbonyl group has been proposed.
