ISCHIA ADVANCED SCHOOL OF ORGANIC CHEMISTRY
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1 ewis acid activation ewis base activation ISCIA ADVACED SC F GAIC CEMISTY Dual in Enantioselective Synthesis of Cyanohydrins Me A A Me UM ewis base catalysis is the process by which an electronpair donor increases the rate of a given reaction by interacting with an acceptor atom in one of the reagents or substrates. The binding event may enhance either the electrophilic or nucleophilic character of the bound species. Furthermore, the ewis base should not be consumed or altered during the course of the reaction - a hallmark of any catalytic process. S.E. Denmark and G.. Beutner, Angew. Chem. Int. Ed. 2008, 47, Christina Moberg M Si Si Enhanced electrophilicity at Si Biocatalysis Synthetic systems ewis or Brønsted base B 2 2 Asp i i ys B Asp i ys 2 2 i C 2 3 ewis acid rate enhancement: Shibasaki, M.; Kanai, M. Chem. arm. Bull. 2001, 49, Kanemasa, S.; Ito, K. Eur. J. rg. Chem. 2004, Ma, J.-A.; Cahard, D. Angew. Chem. Int. Ed. 2004, 43, Kanai, M.; Kato,.; Ichikawa, E.; Shibasaki, M. Synlett 2005,
2 Early examples Enzyme catalysis rganocatalysis Corey s oxazaborolidine oyori s dialkylzinc P 2- is 3 is Zn 2 is F 3 C CF 3 S Chiral Scaffold Base u 2 B B Me Me 2 Zn Zn C 2 "M" C F Carbohydrate elongation C (C) n C 2 C 1. C 2. (C) n C 2 The adiponitrile process C C C
3 TMS as cyanide source ther sources first prepared in 1782 by C. W. Scheele Versatile synthetic route to cyanohydrins known for more than 100 years First asymmetric cyanation made by osenthaler in 1908 Metal catalysts affording highly enantioenriched products known today Mowry, D. T., Chem. ev. 1948, 42, 189 osenthaler,., Biochem. Z. 1908, 14, 238 orth, M., Tetrahedron: Asymmetry, 2003, 14, 147 Brunel, J.-M.; olmes, I. P. Angew. Chem. Int. Ed. 2004, 43, 2752 Carl Wilhelm Scheele ( ) Easy to handle in lab TMS-protected cyanohydrins prepared directly, prevents racemization: - abile - Expensive - Volatile, highly toxic and flammable TMS Et 4 - Me P Me Me P Me Me Me ewis acid catalysis--salen catalyst Base Catalysed Additons to Ketones Et 2 equiv. 1 mol% catalyst -40 C 18 h 100% conv. 95% ee Et atural and modified cinchona alkaloids Several days reaction times Belokon, Y. ; Blacker, A. J.; Clutterbuck,. A.; orth, M. rg. ett., 2003, 5, 4505 S.-K. an,. Deng, J. Am. Chem. Soc. 2001, 123,
4 Dual P EWIS BASE Et 2 Al Cl Cl Al EWIS ACID P Et 2 Et 5 mol% catalyst -40 C 18 h Et Si Et Will ewis Acid - ewis Base Catalysis increase the reactivity? Y. amashima, D. Sawada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 1999, 121, 2641 J. Casas, A. Baeza, J. M. Sansano, C. ájera, J. M. Saá, Tetrahedron: Asymmetry 2003, 14, 197 Et 5 mol% catalyst -40 C Et Et 5 mol% catalyst -40 C Base time (h) yield ee (%) Et 3, 10% Et Base time(h) yield ee(%) DMAP DABC Et Et i Pr Cinchonidine Quinine Sparteine
5 Aldehyde time yield ee (h) isolated (%) Benzaldehyde Pivalaldehyde Valeraldehyde p-me-benzaldehyde p-cl-benzaldehyde t-cinnemaldehyde (,)-Salen- Et 3-40 C Me ()-tembamide Me red C 2 2 Me ()-aegeline traditional indian medicines with hypoglycemic activity? Aegle marmelos. Veum, S.. M. Pereira, J. C. van der Waal, U. anefeld, Eur. J. rg. Chem. 2006, ewis base nucleophile activation ewis Base Dual ewis base electrophile activation ewis Acid * time (h) yield ee (%) 10% DABC Et Sparteine Cinchonidine Sparteine (ent-complex) Cinchonidine (ent-complex) S. undgren, E. Wingstrand, M. Penhoat, C. Moberg, J. Am. Chem. Soc. 2005, 127
6 ewis Base ewis Acid * ewis Base Aldehyde time yield ee (h) isolated (%) (%) Benzaldehyde Pivalaldehyde Valeraldehyde p-me-benzaldehyde p-me-benzaldehyde p-cl-benzaldehyde (E)-cinnemaldehyde % -40 C, 8h yield ee (%) DABC <1 - Et Sparteine 23 0 Cinchonidine 9 40 S. undgren, E. Wingstrand, M. Penhoat, C. Moberg, J. Am. Chem. Soc. 2005, 127, Dual Cl fenvalerate A Duel Amongst ivals Cl Cl cypermethrin A E A E Br Br deltamethrin F 3 C B u B u CF 3 acrinathrin
7 ' esults "", Et 3 ' ' Dual ' * ' Me 75-96% ee, except Cl Increase reactivity of the system Increase selectivty of the system ewis Base ewis Acid igh Throughput Screening ewis Acids ewis Bases Enzymatic method for determining enantiomeric excess A: 50µl B: 50µl ewis Acid ewis Base Absorbance Principle: Selectively process one of the enantiomers of a product mixture from a catalytic reaction A B C: 20 µl S aswell, ull C Channel dimensions of 100*50 µm Flow: 1 µl/ min Pressure driven flow eaction mixture a. Analysis of unreacted benzaldehyde AD AD, AD b. Analysis of (S)--acetylated cyanohydrin ' CAB AD AD, AD c. Analysis of ()--acetylated cyanohydrin ' PE AD AD, AD A S Up to 92% conversion and 80% ee A. amberg, S. undgren, M. Penhoat, C. Moberg, K. ult, J. Am. Chem. Soc. 2006, 128,
8 Additons to Ketones Conclusion Et 3 racemic nonracemic ewis acid-ewis base activation is efficient in cyanations of aldehydes with acetyl cyanide and cyanoformate, providing -functionalized highly enantioenriched cyanohydrins in high yields with perfect atom economy. The conversions and enantioselectivities can be idetermined by an enzymatic high throughput method. ewis Base ' * ewis Acid Activated by Me - racemic Dynamic kinetic resolution '
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