110270-49-0Relevant articles and documents
Chemo- and Enzyme-Catalyzed Reactions Revealing a Common Temperature-Dependent Dynamic Solvent Effect on Enantioselectivity
Cainelli, Gianfranco,Galletti, Paola,Giacomini, Daria,Gualandi, Andrea,Quintavalla, Arianna
, p. 3548 - 3559 (2003)
The enantiomeric ratio E of enzyme-catalyzed (Candida antarctica lipase and lipase PS) and chemocatalyzed (L-proline-based diamines) acylation reactions of 1-(naphthalen-2-yl)ethanol, 2-phenylpropanol, and 2-benzylpropane-1,3-diol is dependent on solvent and temperature. Plots of In E vs. 1/T showed the presence of inversion temperatures (Tinv). The Tinv values for the bio-catalyzed and the chemo-catalyzed reactions are fairly in agreement, and correspond as well to the TNMR values obtained by variable-temperature 13C-NMR experiments on the substrates in the same solvent of the resolution. This result demonstrates that clustering effects in the substrate solvation manage the chemical and the enzymatic enantioselectivity, and, moreover, that the solute-solvent cluster is always the real reacting species in solution for chemical as well as for enzymatic reactions.
Optically active N- and C-terminal building blocks for the synthesis of peptidyl olefin peptidomimetics
Mirilashvili, Sima,Chasid-Rubinstein, Naama,Albeck, Amnon
body text, 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.
Asymmetric synthesis of homoisoflavanone using lipase-catalyzed reaction
Kawasaki, Masashi,Toyooka, Naoki,Matsui, Yoshinori,Tanaka, Akira,Goto, Michimasa,Kakuda, Hiroko,Kawabata, Shigeki,Kometani, Tadashi
, p. 761 - 765 (2007/10/03)
The (R)- and (S)-enantiomers of 3-benzyl-4-chromanone (homoisoflavanone) were synthesized starting with the optically active 2-benzyl-1,3-propanediol monoacetates, which were obtained via the lipase-catalyzed enantioselective reaction.
