1246953-38-7Relevant academic research and scientific papers
Enantioselective Formal α-Methylation and α-Benzylation of Aldehydes by Means of Photo-organocatalysis
Filippini, Giacomo,Silvi, Mattia,Melchiorre, Paolo
, p. 4447 - 4451 (2017)
Detailed herein is the photochemical organocatalytic enantioselective α-alkylation of aldehydes with (phenylsulfonyl)alkyl iodides. The chemistry relies on the direct photoexcitation of enamines to trigger the formation of reactive carbon-centered radicals from iodosulfones, while the ground-state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl and benzyl groups.
Optically active N- and C-terminal building blocks for the synthesis of peptidyl olefin peptidomimetics
Mirilashvili, Sima,Chasid-Rubinstein, Naama,Albeck, Amnon
experimental part, p. 4671 - 4686 (2010/10/19)
Peptidyl olefin peptidomimetics serve as biologically active compounds or as intermediates for other peptidyl isosteres. The N-terminal side of the C=C bond could be easily prepared in an optically pure form from α-amino acids. Synthesis of C-terminal building blocks in an optically pure form is more challenging. We developed a chemoenzymatic stereoselective approach to such optically active C-terminal building blocks to be assembled into peptidyl olefins by a variety of reactions. They include an electrophilic aldehyde and nucleophilic sulfone, phosphonium salt, phosphonate, and diselenide. Key enzymatic hydrolysis of prochiral diesters to the corresponding hydroxy esters introduces optical activity. The sequence of the subsequent chemical reactions, either protection- hydrolysis-functionalization or functionalization-hydrolysis- protection, determines the absolute stereochemistry of the final building blocks.
