The use of Chiral Ketones /Aldehydes in the Asymmetric Epoxidation of Olefins. Somnath Bhattacharjee Michigan State University 12th January, 2005
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1 The use of Chiral Ketones /Aldehydes in the Asymmetric Epoxidation of lefins Somnath Bhattacharjee Michigan State University 12th January, 2005
2 Introduction
3 Sharpless Asymmetric Epoxidation 3 C C 2 (-)-diethyl tartrate Ti(-i-Pr) 4, t Bu (+)-diethyl tartrate Ti(-i-Pr) 4, t Bu 3 C Gao, Y.; anson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune,.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, Rossiter, B. E.; Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 464. (2R, 3R) 58% yield, 95% ee 3 C (2S, 3S) 70% yield, 92% ee
4 Jacobsen Asymmetric Epoxidation C C Catalyst, 3 mol % C C NaCl 81% yield, 87% ee. N + Mn PF 6 - N Chang, S.; Lee, N..; Jacobsen, E. N. J. rg. Chem. 1993, 58, 6939.
5 Dioxirane Catalyzed Epoxidation C 2 Cl 2-2 KS Bu 4 NS 4 R 3 R 2 R 4 R 2 1 S 5 R 3 R 2 R 4 4 R 2 S 3 2 R 2 S 4 2 S 3 R 2 3 Schulz, M.; Liebsch, S.; Kluge, R.; Adam, W. J. rg. Chem. 1997, 62, 188. Curci, R.; Fiorentino, M.; Troisi, L.; Edwards, J..; Pater, R.. J. rg. Chem. 1980, 45, 4758.
6 Activities of Various ketones in Catalyzing in situ Epoxidation of trans-stilbene Catalyst xone/nac 3 C 3 CN/ 2 rt, p R 2 catalyst 1 Catalyst Entry R 2 reaction time (min) 1. C 3 C C 3 CF 3 < 4 3. C 3 C 2 F CF 3 70 Yang, D.; Yip, Y. C.; Tang, M. W.; Wong, M.; Zheng, J.; Cheung, K. J. Am. Chem. Soc. 1996, 118,
7 First Example of Ketone-Catalyzed Asymmetric Epoxidation Catalyst xone/nac 3 C 3 CN/ 2 rt, p Me Entry ketone yield ee config. (equiv) (%) (%) F 3 C C (2.0) (+)-(1R,2R) 2. 2 (1.0) (+)-(1R,2R) 3. 3 (1.0) (+)-(1R,2R) 4. 4 (1.0) (+)-(1R,2R) CF Catalyst Curci, R.; D' Accolti, L.; Fiorention, M.; Rosa, A. Tetrahedron Lett. 1995, 36, Adam, W.; Curci, R.; Edwards, J. Acc. Chem. Res. 1989,22, 205. Curci, R.; Fiorentino, M.; Serio, M. R. J. Chem. Soc., Chem. Commun. 1984, 155.
8 Chiral Ketones with C 2 Symmetry for Asymmetric Epoxidation
9 Asymmetric Epoxidation of Unfunctionalized lefins Catalyzed by Ketone 1 47% ee (-)-(S,S) 87% ee (-)-(S,S) 50% ee (+)-(S) Yang, D.; Yip, Y. C.; Tang, M. W.; Wong, M. K.; Zeng, J..; Cheung, K. K. J. Am. Chem. Soc. 1996, 118,
10 The Spiro and Planar Transition States for the Dioxirane Epoxidation of lefins R' R R' R R' R xygen non-bonding orbital R' R xygen non-bonding orbital lefin π * orbital lefin π * orbital Spiro T.S Planar T.S Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997,119,
11 Proposed Spiro Transition State for the epoxidation of trans olefins (S, S) A (R, R) B Spiro 1 Favored Spiro 2 disfavored Yang, D.; Wong, M.; Yip, Y.; Wang, X. Tang, M.; Zheng, J.; Cheung, K. J. Am. Chem. Soc. 1998, 120,
12 Proposed Planar Transition State for the epoxidation of trans olefins (S, S) A (R, R) B Planar 1 favored Planar 2 disfavored Yang, D.; Wong, M.; Yip, Y.; Wang, X. Tang, M.; Zheng, J.; Cheung, K. J. Am. Chem. Soc. 1998, 120,
13 Asymmetric Epoxidation of Unfunctionalized lefins Catalyzed by Ketones Catalyst xone/nac 3 C 3 CN/ 2 rt, p (S, S) A 3 3' (R)-1 X X 1. X= 2. X= Cl 3. X= Br 4. X= I 5. X= C 2 C 3 Entry Catalyst yield (ee) (%) Config. 1. (R)-1 91 (47) (-)-(S,S) 2. (R)-2 95 (76) (-)-(S,S) 3. (R)-3 92 (75) (-)-(S,S) 4. (R)-4 90 (32) (-)-(S,S) 5. (R)-6 92 (66) (-)-(S,S) Yang, D.; Wang, X.; Wong, M., Yip, Y.; Tang, M. J. Am. Chem. Soc. 1996, 118,
14 New Approaches for Asymmetric Epoxidation of trans lefin 10 mole % (S)-6 xone, K 2 C 3 DME- 2 C F F 1 Song 2 Denmark Catalyst Mol (%) Time (h) Temp ( o C) Yield (%) ee (%) Song, C. E.; Lee, K. C.; Lee, S; Jin, B. W. Tetrahedron: Asymmetry. 1997, 8, Denmark, S. E.; Wu, Z. Synlett 1999,
15 ypothetical Transition Structures for Approach of Alkenes to Dioxirane of (-)-2 R b R' a R R' Me Me F F Denmark, S. E.; Matsuhashi,. J. rg. Chem. 2002, 67,
16 Behar s Approach to Improve the Enantioselectivity for Asymmetric Epoxidation F F R 2R1 3 Denmark Behar 4., R 2, R 3, R 4 = 5., R 3, R 4 =, R 2 = F 6., R 3 =, R 2, R 4 = F 7., R 2, R 3 = F, R 4 = 8., R 2, R 3, R 4 = F R 4 R 3 Catalyst Mol (%) Time (h) Temp ( o C) Yield (%) ee (%) Stearman, J. C.; Behar, V. Tetrahedron. Lett. 2002, 43,
17 Summary F R 3 F 1 Song Behar 3 Cl F F (R)-3 3' Cl 2 Denmark
18 Fructose-derived Chiral Ketones for Epoxidation
19 Fructose-derived Ketone Catalyst for the Asymmetric Epoxidation of trans Stilbene xone, 2 -C 3 CN p d entry Time (h) Isolated Yield (%) ee (%) > > Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997,119,
20 Possible Reaction Pathway of Ketone 1 R 3 R 2 S 5 R 2 R Baeyer-Villiger Reaction S S 4 S ydrolysis Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997,119,
21 Baeyer-Villiger Reaction R 2 2 R ' R R ' Mechanism 2 R R ' R R' G 2 R R ' Example 2 2 F + F F 71% E 29% F Renz, M.; Meunier, B.; Eur. J. rg. Chem. 1999, 737 Crudden, C. M.; Chen, A. C.; Calhoun, L. A.Angew. Chem., Int. Ed. 2000, 39, 2852
22 Effect of p in Ketone Catalyzed Epoxidation xone, 2 -C 3 CN p R 3 R 2 S 5 Catalyst 1 R 3 R Baeyer-Villiger Reaction S S 4 p p entry Time (h) Yield (ee) (%) Yield (ee)(%) (85) 86 (>95) S ydrolysis Frohn, M.; Wang, Z.; Shi, Y. J. rg. Chem. 1998, 63,
23 Approaches to Circumvent Baeyer-Villiger Reaction 4 2 mcpba major Ac Ac 4 5 Epoxidation by catalyst 5 Entry Substrate Yield (%) ee (%) config Et C 2 Et C 2 Et C 2 Et C 2 Et C 2 Et (+)-(2S,3R) (+) (+) (+) (+) 6. C 2 Et (-)-(2S,3S) Wu, X.; She, X.; Shi, Y. J. Am. Chem. Soc. 2002, 124,
24 Comparison Between Ketones 1 and 5 Ac Ac 1 5 Ketone 1 Ketone 5 Entry Substrate Yield (ee) (%) Yield (ee) (%) config (95.5) 81 (83) (R, R) (97.9) 67 (96) (R, R) 3. TBS 87 (94) 73 (94) (R, R) Me (93) (R, R) 89 (95.5) (98) 93 (92) (R, R) Tian,.; She, X.; Shi, Y. rganic Lett. 2001, 3,
25 Transition State Analysis for the Epoxidation of trans lefin by Ketone 1 Catalyst xone/nac 3 C 3 CN/ 2 rt (R, R) (R, R) Spiro 1 Favored 1 Planar 1 disfavored Spiro 2 disfavored (S, S) 2 Planar 2 Favored Tu, Y.; Wang, Z.' Shi, Y. J. Am. Chem. Soc. 1996, 118,
26 Asymmetric Epoxidation of Trisubstituted lefin by Ketone 1 xone, R R C 3 CN R 1 R 2 R 2 p 11, catalyst 1 (catalyst) Entry Substrate Yield (%) ee (%) Config (R,R) (+)-(R) (+)-(R,R) Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997, 119,
27 Transition State Analysis for the Epoxidation of Trisubstituted lefins xone, R R C 3 CN R 1 R 2 R 2 p 11, catalyst 1 (catalyst) R 3 R 2 Spiro 1 Favored R 2 R3 Spiro 2 disfavored R 3 R 2 R 1 Major 1 R 3 R 2 Planar 1 disfavored R 1 R 2 R 3 Planar 2 disfavored Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997, 119,
28 Transition State Analysis for the Epoxidation of Trisubstituted lefin by Ketone 1 xone, R R C 3 CN R 1 R 2 R 2 p 11, catalyst 1 (catalyst) R 3 R 2 R 3 Spiro 4 disfavored R 2 R 3 Spiro 3 disfavored R 3 R 2 Planar 3 disfavored minor R 2 R 3 Planar 4 Favored R2 Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997, 119,
29 Effects of the Size of Substituents on Enantioslectivity R 3 R 3 R 2 R R 2 1 Major R 3 R 2 minor R 3 R2 Spiro 1 Effect of the size of Planar 4 26% ee 79% ee 81% ee Effect of the size of R 3 ee increases as the size of decreases C % ee 91% ee ee increases as the size of R 3 increase Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997, 119,
30 Epoxidation of cis and Terminal lefins by Ketone 1 Entry Subtrate Yield (%) ee (%) Config. 1 (catalyst) (-)-(1S,2R) (+)-(R,R) (+)-(R) 4. C (+)-(R) (-)-(S) Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997,119,
31 Transition State Analysis for cis and Terminal lefins cis lefin Terminal lefins R 2 R 3 1 spiro 1 Spiro 3 Planar 3 R 3 R 2 2 spiro 2 Spiro 4 Planar 4 Wang, Z.; Tu, Y.; Frohn, M.; Zhang, J.; Shi, Y. J. Am. Chem. Soc. 1997, 119,
32 Summary Advantages: Enantioselctivity is high for trans and tri substitued olefins. Disadvantages: Enantioselectivity is very low for cis and terminal olefins. 1 Ac Ac Effective catalyst for elctron deficient olefins. 5
33 Transition State Analysis to Design new Catalyst for cis lefins Me Me Spiro 1 Spiro 2 X Y Me X Y Me Spiro 3 Spiro 4 Tian,.; She, X.; Shu, L.; Yu,.; Shi, Y. J. Am. Chem. Soc. 2000, 122,
34 6, xone Fructose-derive new Catalyst for the Epoxidation of cis lefins Up to 97% ee Entry Substrate Yield (%) ee (%) Config (-)-(1R,2S) Boc N (-)-(1R,2S) (-)-(5R,6S) (-)-(2S,3R) (+) Tian,.; She, X.; Yu,.; Shu, L.; Shi, Y. J. rg. Chem. 2002, 67,
35 Transition State Analysis for the Epoxidation of cis lefins NBoc Ar R NBoc R Ar Spiro 1 Spiro 2 NBoc NBoc R Ar Ar R Planar 1 Planar 2 Tian,.; She, X.; Yu,.; Shu, L.; Shi, Y. J. rg. Chem. 2002, 67,
36 Catalyst 6 for the Epoxidation of Terminal lefins R 6, xone R Up to 85 % ee Entry Substrate Yield (%) ee (%) Config (-)-(R) (-)-(R) Boc N (-) NBoc NBoc NBoc Spiro 1 Spiro 2 Planar 1 Tian,.; She, X.; Shi, Y. rg. lett. 2001, 5,
37 Comparison Between Ketone Catalysts 1 and 6 Entry Substrate ketone Yield (ee) (%) [85] Boc N [81] [61] 6 97 [61] [24] 6 81 [92] [98] [68] [98] 6 80 [55] [85] 6 96 [67] [95.5] [88]
38 N-aryl Substituted xazolidinone for the Epoxidation of lefins 7 N X Entry Ketone yield (ee) (%) yield (ee) (%) 1. 7a 71 (83) (2R,3S) 56 (80) (R) 2. 7b 60 (84) (2R,3S) 60 (80) (R) 3. 7c 72 (90) (2R,3S) 61 (80) (R) 7a, X = p-me 7b, X = p-me 7c, X = p-mes 2 7d, X= p-n 2 7e, X = o-n d 55 (90) (2R,3S) 30 (79) (R) 5. 7e 59 (78) (2R,3S) 55 (62) (R) X N X X N N Spiro 1 Favored Spiro 2 Planar 1 Shu, L.; Wang, P.; Gan, Y.; Shi, Y. rg. lett. 2003, 3,
39 N-aryl Eubstituted xazolidinone for the Epoxidation of cis lefins Ketone 3a Ketone 3b Entry Substrate Conv. (ee) (%) Conv. (ee) (%) (84) 100 (90) N Catalyst X Me Me 86 (88) 80 (92) 94 (91) 100 (93) 3a, X= Me 3b, X= S 2 Me X X= Me 100 (88) 96 (92) X=F 99 (87) 100 (91) X=N 2 86 (98) 91 (97) Me Me 72 (92) 100 (97) 6. Me 75 (91) 97 (96) 7. Me Me Me 97 (91) 100 (94) Shu, L.; Shi, Y. Tetrahedron Lett. 2004, 45,
40 Possible Transition State N Me Y X N Me Y X Spiro 1 Favored Spiro 2 Edge-tilted-T Shu, L.; Wang, P.; Gan, Y.; Shi, Y. Tetrahedron. lett. 2004, 3,
41 Summary R N 6 Effective catalyst for cis and Terminal olefins R= Boc, X
42 ydrogen Peroxide as Primary xidant Instead of Potassium Peroxomonosulfate (KS 5 ) R 2 R C 3 CN-K 2 C 3 R 2 R 3 1, catalyst R 2 R 3 R 3 R C N N 4 2 C 3 C 3 CN N 3 C 5 3 C N 2 N 3 C 3 Shu, L.; Shi, Y. Tetrahedron, 2001, 57,
43 Comparison Between 2 2 and KS 5 as xidant R 2 R C 3 CN-K 2 C 3 R 2 R KS 5 Entry Substrate Yield (ee) (%) Yield (ee) (%) (92) 90 (98) 94 (96) 85 (98) (95) 89 (96) (98) 94 (98) (89) 98 (95) Shu, L.; Shi, Y. Tetrahedron, 2001, 57,
44 First Reported Chiral Aldehydes for the Epoxidation of lefins Entry Substrate Catalyst yield (ee) (%) Config. 2 C Bn 1 C Bn, KS 5 C 3 CN, 0 o C, 2h p 10.5 C (63.5) (R,R) (93.5) (R,R) (39) (R,R) (81) 8 (92) (R) (R) (36) (R) (70) (R,R) (48) (R,R) (67) (R,R) (18) (S) (18) (S) Bez, G.; Zhao, C. Tetrahedron Letter, 2003, 44,
45 Transition State Analysis 2 C Bn C 3 4 Favored (R,R) Disfavored (S,S) Bez, G.; Zhao, C. Tetrahedron Letter, 2003, 44,
46 Conclusion Advantages 1. igh catalytic activity of ketone catalyst was achieved. 2. igh level of enantioselectivity was achieved. Disadvantages 1. Broad generality of substrates couldn t be achieved.
47 Acknowledgement Prof. Babak Borhan Prof. W.. Reusch Prof. J. E. Jackson Prof. W. D. Wulff Chrysoula, Courtney, Dan, Jennifer, Jun, Marina, Montserrat, Stewart, Tao, Shang Vijay, Keith
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