Direct and Asymmetric Aldol Reactions of N-Azidoacetyl-1,3-thiazolidine-2-thione Catalyzed by Chiral Nickel(II) Complexes. A New Approach to the Synthesis of -Hydroxy--Amino Acids

Teloxa, Saul F.Mellado Hidalgo, MiguelKennington, Stuart C. D.Romea, PedroUrpí Tubella, FèlixAullón López, GabrielFont Bardia, Ma. Mercedes2022-12-142022-12-142022-12-010947-6539https://hdl.handle.net/2445/191586A direct and asymmetric triisopropylsilyltrifluoromethanesulfonate (TIPSOTf) mediated aldol reaction of N-azidoacetyl-1,3-thiazolidine-2-thione with aromatic aldehydes catalyzed by a chiral nickel(II)-Tol-BINAP complex has been developed (BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl). The catalytic protocol gives the corresponding anti α-azido-β-silyloxy adducts with outstanding stereocontrol and in high yields. Theoretical calculations account for the stereochemical outcome of the reaction and lay the foundations for a mechanistic model. In turn, the easy removal of the thiazolidinethione yields a wide array of enantiomerically pure derivatives in a straightforward and efficient manner. Such a noteworthy character of the heterocyclic scaffold together with the appropriate manipulation of the azido group open a new route to the synthesis of di- and tripeptide blocks containing a β-aryl-β-hydroxy-α-amino acid.10 p.application/pdfengcc-by-nc-nd (c) Teloxa, Saul F., et al, 2022http://creativecommons.org/licenses/by-nc-nd/3.0/es/Síntesi asimètricaNíquelReacció aldòlicaAsymmetric synthesisNickelAldol reactionDirect and Asymmetric Aldol Reactions of N-Azidoacetyl-1,3-thiazolidine-2-thione Catalyzed by Chiral Nickel(II) Complexes. A New Approach to the Synthesis of -Hydroxy--Amino Acidsinfo:eu-repo/semantics/article7241272022-12-14info:eu-repo/semantics/openAccess