Enzymes in Functional Group Transformation: Enantioselectivity and Asymmetric Bioreduction, Slides of Biochemistry

Download Enzymes in Functional Group Transformation: Enantioselectivity and Asymmetric Bioreduction and more Slides Biochemistry in PDF only on Docsity! Module 9: Enzymes in Functional G T f tiroup rans orma on Lecture16: Enzymes in Functional Group Transformation 1 Docsity.com Use of enantiocontrolling group OOH OH Cl CO2RCl CO2R Cl CO2R R = Me, Et, nPr, nBu ee = 50-60% R = nPent to n-decyl ee = >90% S L O S L O O O Both "S" and "L" similar in size "S" and "L" differ in size R1 OR2R1 O O OR2 L S L S Docsity.com Diff t diff i l ti it OH eren enzymes er n se ec v y O F C F3CYeast R 3 R OH F3C R = H, Br, OMe, OH G. candidum R Docsity.com A t i bi d ti f th th i f f l d O OH M symme r c ore uc on or e syn es s o use u compoun s CO Me CO Me O e G. candidum ATCC 34614 2 2 O O 92 % yield ee = 99% S CF3 S CF3 OH CF3 OBn G. candidum KHMDS, BnBr Raney Ni ee = 99% Docsity.com E i d di l i d i f hl k OH CO Et O NHCOR nant o an astereo se ecet ve re uct on o a c oro etone O Ph CO2Et Ph Cl 2 Ph CO2Et OH CO2HPh M. racemosus R Ph Cl OHR. glutinis = side chain of taxol or Dilitazem R = OtBu; side chain of taxotere Ph Cl CO2Et O Ph CO2Et Docsity.com Yeast mediated synthesis of DMAP analogue and related amines N Cl O R N Cl OH R OPG R NMe2 Baker's yeast 30oC 14-43h MeNH2 Protection N , (S); 73-79% yield ee = > 98% Chiral 4-DMAP analogueR = Me, Et, nPr, nBu, Ph N N OH N NH2 Baker's yeast 37oC 8 days DPPA, DBU Ph3P, H2O O , 76% yield; ee = > 99% Docsity.com Enantiocomplementary reduction of biaryl ketones S OH R. glutinis ( ) O N Ph MUCL 30607 subs conc: 0.1 g/L 27oC, 2d 96% yield; 91% ee N S Ph OH S. montanus N S Ph (CBS 6772) subs conc: 1.5 g/L 27oC, 7d 79% yield; 99% ee Docsity.com Reduction of prochiral aminoketones O OH S OH Tropinone reductase from D. stramonium N N O OpH = 7.5, 37oC, 12h 88.4 % yield; 96% ee N Squalene synthase inhibitor Docsity.com