Direct Organocatalytic Enantioselective Mannich Reactions of Ketimines: An Approach to Optically Active Quaternary α-amino Acid Derivatives
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1 Direct rganocatalytic Enantioselective Mannich eactions of Ketimines: An Approach to ptically Active Quaternary α-amino Acid Derivatives Wei Zhang, Steen Saaby, and Karl Anker Jorgensen The Danish ational esearch Foundation: Center for Catalysis Department of Chemistry, Aarhus University Angew. Chem. Int. Ed. 2004, 43, Michael Wipf Group 1 9/13/2004
2 The Mannich eaction direct 4 X indirect preformed enol equivalent preformed imine List, B.; Pojarliev, P.; Biller, W. T.; Martin,. J.; J. Am. Chem. Soc. 2002, 124, Michael Wipf Group 2 9/13/2004
3 Iminoesters as Useful Electrophiles in Mannich eactions tosylisocyanate [AlCl 3 ] Et Ts Et p-methoxyaniline sieves Et PMP Et PhC 2 EtAc Et oxalyl chloride Et Cl α-haloglycine Taggi, A. E.; afez, A. M.; Leckta, T. Acc. Chem. es. 2003, 36, Michael Wipf Group 3 9/13/2004
4 Lewis Acid Catalyzed Mannich eactions of α-imino Esters X P M P X LG P M P -LG P P M X u X u Taggi, A. E.; afez, A. M.; Leckta, T. Acc. Chem. es. 2003, 36, Michael Wipf Group 4 9/13/2004
5 Chiral Lewis Acid Catalyzed Mannich eactions - 1 Et Ts TMS 2-10 mol% cat. TFor C 2 Cl 2-78 o C to 0 o C Ts Et 95%, 98%ee = Ar, Alk ' =p-me-ph ' ' P CuCl 4 P ' ' "cat" (a) Ferraris, D.; Young, B.; Dudding, T.; Lectka, T. J. Am. Chem. Soc. 1998, 120, (b) Ferraris, D.; Dudding, T.; Young, B.; Drury, W. J.; Lectka, T. J. rg. Chem. 1999, 64, (c) Ferraris, D.; Young, B.; Cox, C.; Dudding, T.; Drury, W. J.; yzhkov, Lev.; Lectka, T. J. Am. Chem. Soc. 2002, 124, Michael Wipf Group 5 9/13/2004
6 Chiral Lewis Acid Catalyzed Mannich eactions - 2 PMP TMS 5 mol% cat. DMF, 25 o C PMP 80-95%, 71-90%ee = Ar ' =Tol ' ' ' ' P P Pd Pd P P ' ' ' ' "cat" 2 2Tf - (a) agiwara, E.; Fujii, A.; Sodeoka, M. J. Am. Chem. Soc. 1998, 120, (b) Fujii, A.; Sodeoka, M.; 1999, 40, Michael Wipf Group 6 9/13/2004
7 Chiral Lewis Acid Catalyzed Mannich eactions - 3 Et 1 TMS 10 mol% cat. C 2 Cl 2, 25 o C 1 Et 77-97%, 90-97%%ee = Ar, Me, SEt ' = Ar, Alk Ph Ph Cu Tf Tf "cat" (a) Kobayashi, S.; Matsubara,.; Kitagawa,. rg. Lett. 2002, 4, (b) Kobayashi, S.; amada, T.; Manabe, K. J. Am. Chem. Soc. 2002, 124, Michael Wipf Group 7 9/13/2004
8 Chiral Lewis Acid Catalyzed Mannich eactions - 4 Ar PPh 2 Me Et 2 Zn, 4eq 1-5 mol% cat. TF, MS 3A, Ph 2 P Ar Me -20 o C, 2-24 h 93-98%, 88/12-96/4 de, 95-98% ee "cat" Matsunaga, S.; Kumagai,.; arada, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, Michael Wipf Group 8 9/13/2004
9 Mannich eactions by rganocatalysis Proposed Transition States PMP mol% DMS, 25 o C 2-20 h PMP %, 11-99%ee, 19:1 dr PMP 2 C 2 Et 1 2 1C 2Et PMP (a) List, B. J. Am. Chem. Soc. 2000, 122, (b) Cordova, A.; otz, W.; Zhong, G.; Betancort, J. M.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, Me PMP 20 mol% DMS, 25 o C 2-20 h PMP 44-78%, 74-92%ee, 5:1-19:1 dr Me PMP C 2 Et Me PMP C 2 E (a) Cordova, A.; Barbas, C. F. Tetrahedron Lett. 2002, 43, (b) otz, W.; Tanaka, F.; Barbas, C. F., III. Acc. Chem. es. 2004, 37, Michael Wipf Group 9 9/13/2004
10 The Scoop: Mannich eactions Largely estricted to Imines Derived From Aldehydes PG LA* PG LA* LA* PG Et Et Et Saaby, S.; akama, K.; Lie, M. A.; azell,. G.; Jorgensen, K. A. Chem. Eur. J. 2003, 9, Imines bearing α-protons are susceptible to form enamines in the presence of Bronstead or Lewis acids. The equilibrium of the flexible imine double bond is often shifted towards the Z isomer and thereby render difficult a constrained and rigid bidentate coordination to a Lewis acid complex A characteristic and fundamental problem related to the use of ketimine substrates is steric hindrance. The disubstituted carbon atom of a prochiral ketimine double bond is much less reactive than the analagous monosubstituted prochiral aldimine, owing to unfavorable steric interactions during the C C bond forming step. Michael Wipf Group 10 9/13/2004
11 Intrinsic Protecting Groups: Their ole in Modulating Ketimine eactivity PG Ar Et Et vs. Me Et By anchoring the nitrogen protecting group by means of an aryl substituent, the degree of rotational freedom, as well as possible imine double bond isomerization, is minimized, rendering a beneficial preorganized structure for bidentate Lewis acid activation. Moreover, the problem of enamine formation is also circumvented Et Et PMB-isocyanate unig's base TFA (cat) Dean-Stark PMB Saaby, S.; akama, K.; Lie, M. A.; azell,. G.; Jorgensen, K. A. Chem. Eur. J. 2003, 9, Et Et formic acid Michael Wipf Group 11 9/13/2004
12 Lewis Acid Catalyzed Ketimine Alkylation Et 2 TMS mol% cat. C 2 Cl 2, -78 o C mol% C 2 Et C 2 2 Boc 2, DMAP MeC, T, 17 h Boc C 2 E Cs 2 C 3 2 Me, T, 2h Ph Zn cat. Ph 2 2 Tf - Saaby, S.; akama, K.; Lie, M. A.; azell,. G.; Jorgensen, K. A. Chem. Eur. J. 2003, 9, Michael Wipf Group 12 9/13/2004
13 Et chiral amine C 2 Et C 2 Et i Pr C C i Pr i Pr 1a 2a Table 1: Direct organocatalytic asymetric Mannich reaction of ketimine 1a with 2a. Entry Catalyst (mol%) T [ºC] 2a [equiv] Solvent Yield [a] [%] 3a/4a [b] ee [c] [%] 1 5a (30) 0 5 C 2 Cl : b (30) 0 5 C 2 Cl 2 11 >20: c (30) 0 5 C 2 Cl 2 trace >20:1 4 5d (30) 0 5 C 2 Cl 2 39 >20: e (5) 0 5 C 2 Cl : e (5) 0 5 C 2 Cl : e (5) 0 5 Et : e (5) 0 2 Et 2 99 >20: e (5) Et : e (2) 0 2 Et :1 91 [a] Combined yield of the two isolated diastereomeric products. [b] The diastereomeric ratio was determined by 1 M spectroscopic analysis of the crude product mixture. [c] The ee of the major product was determined by PLC on a Daicel Chiralpak AS column. 3a 4a C 2 C 2 Me Ph Ar Ph Ar Ar = 3,5 xylyl 5a 5b 5c 5d 5e Zhang, W.; Saaby, S.; Jorgensen, K. A. Angew. Chem. Int. Ed. 2004, 43, Michael Wipf Group 13 9/13/2004
14 1 2 3 Et 4 5e (5 mol%) 0 o C, 20 h C 2 Et C 4 1a-f 2a 4 = ipr 2b 4 = Me 2c 4 = allyl 3a-h Table 2. eaction of ketimines 1a-f with aldehydes 2a-c under the optimized reaction conditions 3/4 [b] Entry Imine Solvent Product Yield ee[%] [c] [%] [a] 1 1a Et 2 ipr 3a 99 >20: b Et 2 Me ipr 3b 98 6: c Et 2 Me ipr 3c 95 9: d Et 2 F ipr 3d 97 19: e Et 2 Me ipr 3e 90 >20: f Et 2 C 4 4 ipr 3f 93 >20: a C 2 Cl 2 Me 3g 72 5: a C 2 Cl 2 allyl 3h 82 4:1 98 [a] Combined yield of the two isolated diastereomeric products. [b] The diastereomeric ratio was determined by 1 M spectroscopic analysis of the crude product. [c] The ee value of the major product (with configuration at the quaternary center) was determined by PLC on a Chiral stationary phase (see Supporting Information for details). Zhang, W.; Saaby, S.; Jorgensen, K. A. Angew. Chem. Int. Ed. 2004, 43, Michael Wipf Group 14 9/13/2004
15 Conclusions The first organocatalytic, enantioselective Mannich reaction of ketimines and unmodified aldehydes based on the concept of intrinsic protecting group anchoring has been reported. Catalysis is achieved by the addition of simple chiral amines (2-5 mol%) providing optically active quaternary α-amino acid derivatives in high yields (72-99%) and good optical purities (83-98% ee). Through careful selection of the amine catalyst, the diastereoselectivity of the reaction can be controlled. Michael Wipf Group 15 9/13/2004
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