Enamides and enecarbamates as nucleophiles in stereoselective C-C and C-N bond-forming reactions

Accounts of Chemical Research

Volumn 41, Issue 2, 2008, Pages 292-301

  Matsubara, Ryosuke ^a   Kobayashi, Shu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; AMIDE; BIOLOGICAL PRODUCT; CARBAMIC ACID DERIVATIVE; CARBON; GLYOXYLIC ACID; GLYOXYLIC ACID DERIVATIVE; NITROGEN;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; STEREOISOMERISM;

ALDEHYDES; AMIDES; BIOLOGICAL PRODUCTS; CARBAMATES; CARBON; GLYOXYLATES; MOLECULAR STRUCTURE; NITROGEN; STEREOISOMERISM;

EID: 40549137094     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar700098d     Document Type: Article

References (61)

1. Stork, G.; Terrell, R.; Szmuszkovicz, J. A New Synthesis of 2-Alkyl and 2-Acyl Ketones. J. Am. Chem. Soc. 1954, 76, 2029-2030.
2. There have been a few reports on the use of enamides and enecarbamates as nucleophiles. (a) Eberson, L.; Malmberg, M.; Nyberg, K. Enamides as Nucleophilic-Reagents - Reactions with Cyclic N-Formylimmonium and Acylium Ions. Acta Chem. Scand. 1984, 38, 391-396.
3. (b) Meth-Cohn, O.; Westwood, K. T. A Versatile New Synthesis of Quinolines and Related Fused Pyridines. Part 12. A General Synthesis of 2-Chloropyridines and 2-Pyridones. J. Chem. Soc., Perkin Trans. 1 1984, 1173-1182.
4. (c) Shono, T.; Matsumura, Y.; Tsubata, K.; Sugihara, Y.; Yamane, S. -I.; Kanazawa, T.; Aoki, T. Electroorganic Chemistry. 60. Electroorganic Synthesis of Enamides and Enecarbamates and Their Utilization in Organic Synthesis. J. Am. Chem. Soc. 1982, 104, 6697-6703.
5. 3-N-Aryl-aldimine. J. Org. Chem. 2000, 65, 5009-5013.
6. Diels-Alder reaction with amino dienes is known. (e) Wipf, P.; Wang, X. Diels-Alder Approaches to Ring-Functionalized Cyclic β-Amino Acids. Tetrahedron Lett. 2000, 41, 8747-8751.
7. (f) Chigr, M.; Fillion, H.; Rougny, A. An Efficient Route to Aminoanthraquinones and Derivatives via a Diels-Alder Reaction. Tetrahedron Lett. 1987, 28, 4529-4532, and references cited therein.
8. Gridnev, I. D.; Imamoto, T. On the Mechanism of Stereoselection in Rh-Catalyzed Asymmetric Hydrogenation: A General Approach for Predicting the Sense of Enantioselectivity. Acc. Chem. Res. 2004, 37, 633-644, and references cited therein.
9. PCP = p-chlorophenyl; PMP = p-MeO-phenyl; OMeP = o-Me-phenyl; MMeP = m-Me-phenyl; PMeP = p-Me-phenyl; α-Nap = α-Naphthyl; β-Nap = β-Naphthyl; Alloc = allyloxycarbonyl; L = liquid.
10. Some enamides and enecarbamates decompose on silica gel chromatography. It is suggested to use neutral silica gel to be safe.
11. Some N-H enamines are known to be stable. For example, see (a) Christoffers, J.; Mann, A. New Auxiliaries for Copper-Catalyzed Asymmtric Michael Reactions: Generation of Quaternary Stereocenters at Room Temperature. Chem. - Eur. J. 2001, 7, 1014-1027.
12. (b) Hervouet, K.; Guingant, A. Highly Diastereoselective Addition of Cyclic β-Enamino Esters to N-Acryloyl-(S)-Proline Derivatives. Tetrahedron: Asymmetry 1996, 7, 421-424.
13. (c) Cavé, C.; Desmaële, D.; d'Angelo, J. Stereochemical Aspects in the Asymmetric Michael Addition of Chiral Imines to Substituted Electrophilic Alkenes. J. Org. Chem. 1996, 61, 4361-4368.
14. Suen, Y. H.; Horeau, A.; Kagan, H. B. Iminomagnesium Compounds. I. Reaction with Acid Chlorides. Bull. Soc. Chim. Fr. 1965, 5, 1454-1457.
15. Machida, S.; Tanaka, I. Preparation and Properties of Poly(vinylamine) Derivatives. Kyoto Kogei Sen'i Daigaku Sen'igakubu Gakujutsu Hokoku 1975, 7, 423-431.
16. (b) Sato, M. Studies on 1-Alkenyl Isocyanates and Their Derivatives. J. Org. Chem. 1961, 26, 770-779.
17. Mecozzi, T.; Petrini, M. A Stereoselective Synthesis of Primary (Z)-Enecarbamates from α-Amidoalkylphenyl Sulfones. Synlett 2000, 73-74, and references cited therein.
18. For the other synthetic methods for N-H enamides and enecarbamates, see (a) Fürstner, A.; Brehm, C.; Cancho-Grande, Y. Stereoselective Synthesis of Enamides by a Peterson Reaction Manifold. Org. Lett. 2001, 3, 3955-3957.
19. (b) Han, C.; Shen, R.; Su, S.; Porco, J. A., Jr. Copper-Mediated Synthesis of N-Acyl Vinylogous Carbamic Acids and Derivatives: Synthesis of the Antibiotic CJ-15,801. Org. Lett. 2004, 6, 27-30.
20. (c) Willis, M. C.; Brace, G. N.; Holmes, I. P. Efficient Palladium-Catalyzed Enamide Synthesis from Enol Triflates and Enol Tosylates. Synthesis 2005, 3229-3234.
21. (d) Burk, M. J.; Casy, G.; Johnson, N. B. A Three-Step Procedure for Asymmetric Catalytic Reductive Amidation of Ketones. J. Org. Chem. 1998, 63, 6084-6085.
22. (e) Wallace, D. J.; Klauber, D. J.; Chen, C.-Y.; Volante, R. P. Palladium-Catalyzed Amidation of Enol Triflates: A New Synthesis of Enamides. Org. Lett. 2003, 5, 4749-4752.
23. (f) Jiang, L.; Job, G. E.; Klapars, A.; Buchwald, S. L. Copper-Catalyzed Coupling of Amides and Carbamates with Vinyl Halides. Org. Lett. 2003, 5, 3667-3669.
24. (g) Cherney, R. J.; Wang, L. Efficient Mitsunobu Reactions with N-Phenylfluorenyl or N-Trityl Serine Esters. J. Org. Chem. 1996, 61, 2544-2546.
25. (h) Boar, R. B.; McGhie, J. F.; Robinson, M.; Barton, D. H.; Horwell, D. C.; Stick, R. V. A Simple Synthesis of Enamides from Ketoximes. J. Chem. Soc., Perkin Trans. 1 1975, 1237-1241.
26. See also (i) Lenz, G. R. The Photochemistry of Enamides, Synthesis 1978, 489-518.
27. (a) Matsubara, R.; Nakamura, Y.; Kobayashi, S. Copper(II)-Catalyzed Highly Enantioselective Addition of Enamides to Imines: The Use of Enamides as Nucleophiles in Asymmetric Catalysis. Angew. Chem., Int. Ed. 2004, 43, 1679-1681.
28. (b) Terada, M.; Machioka, K.; Sorimachi, K. High Substrate/Catalyst Organocatalysis by a Chiral Bronsted Acid for an Enantioselective Aza-Ene-Type Reaction. Angew. Chem., Int. Ed. 2006, 45, 2254-2257.
29. For example, (a) Hagiwara, E.; Fujii, A.; Sodeoka, M. Enantioselective Addition of Enol Silyl Ethers to lmines Catalyzed by Palladium Complexes: A Novel Way to Optically Active Acylalanine Derivatives. J. Am. Chem. Soc. 1998, 120, 2474-2475.
30. (b) Knudsen, K. R.; Risgaard, T.; Nishiwaki, N.; Gothlef, K. V.; Jørgensen, K. A. The First Catalytic Asymmetric Aza-Henry Reaction of Nitronates with Imines: A Novel Approach to Optically Active β-Nitro-α-Amino Acid and α,β-Diamino Acid Derivatives. J. Am. Chem. Soc. 2001, 123, 5843-5844.
31. (c) Hamada, T.; Manabe, K.; Kobayashi, S. Enantio- and Diastereoselective, Stereospecific Mannich-Type Reactions in Water. J. Am. Chem. Soc. 2004, 126, 7768-7769.
32. (d) Taggi, A. E.; Hafez, A. M.; Lectka, T. α-Imino Esters: Versatile Substrates for the Catalytic, Asymmetric Synthesis of α- and β-Amino Acids and β-Lactams. Acc. Chem. Res. 2003, 36, 10-19, and references cited therein.
33. (a) Kobayashi, S.; Kitagawa, H.; Matsubara, R. Direct Formation of N-Acylated Amino Acid Derivatives via Nucleophilic Addition to N-Acylimino Esters Using a Polymer-Supported Amine and Scandium Triflate. J. Comb. Chem. 2001, 3, 401-403.
34. (b) Kobayashi, S.; Matsubara, R.; Kigatawa, H. Catalytic Asymmetric Mannich-Type Reactions of N-Acylimino Esters for Direct Formation of N-Acylated Amino Acid Derivatives. Efficient Synthesis of a Novel Inhibitor of Ceramide Trafficking, HPA-12. Org. Lett. 2002, 4, 143-145.
35. (c) Kobayashi, S.; Matsubara, R.; Nakamura, Y.; Kitagawa, H.; Sugiura, M. Catalytic, Asymmetric Mannich-type Reactions of N-Acylimino Esters: Reactivity, Diastereo- and Enantioselectivity, and Application to Synthesis of N-Acylated Amino Acid Derivatives. J. Am. Chem. Soc. 2003, 125, 2507-2515.
36. (a) Yasuda, S.; Kitagawa, H.; Ueno, M.; Ishitani, H.; Fukasawa, M.; Nishijima, M.; Kobayashi, S.; Hanada, K. A Novel Inhibitor of Ceramide Trafficking from the Endoplasmic Reticulum to the Site of Sphingomyelin Synthesis, J. Biol. Chem. 2001, 276, 43994-44002.
37. (b) Ueno, M.; Kitagawa, H.; Ishitani, H.; Ysuda, S.; Hanada, K.; Kobayashi, S. Catalytic Enantioselective Synthesis of a Novel Inhibitor of Ceramide Trafficking, (1R/,3R)-N-(3-Hydroxy-1- hydroxymethyl-3-phenylpropyl)-dodecanamide (HPA-12). Tetrahedron Lett. 2001, 42, 7863-7865.
38. (c) Nakamura, Y.; Matsubara, R.; Kitagawa, H.; Kobayashi, S.; Kumagai, K.; Yasuda, S.; Hanada, K. Stereoselective Synthesis and Structure-Activity Relationship of Novel Ceramide Trafficking Inhibitors. (1R,3R)- N-(3-Hydroxy-1-hydroxymethyl-3-phenylpropyl)dodecanamide and Its Analogues. J. Med. Chem. 2003, 46, 3688-3695.
39. (a) Matsubara, R.; Nakamura, Y.; Kobayashi, S. Highly Diastereo- and Enantioselective Reactions of Enecarbamates with Ethyl Glyoxylate to Give Optically Active syn and anti α-Alkyl-β-Hydroxy Imines and Ketones. Angew. Chem., Int. Ed. 2004, 43, 3258-3260.
40. (b) Matsubara, R.; Vital, P.; Nakamura, Y.; Kiyohara, H.; Kobayashi, S. Highly Diastereo- and Enantioselective Reactions of Enecarbamates with an Aldehyde. Tetrahedron 2004, 60, 9769-9784.
41. A concerted aza-ene-type reaction was proposed in the Michael reaction using a chiral enamine: (a) Ambroise, L.; Desmaéle, D.; Mahuteau, J.; d'Angelo, J. The Asymmetric Michael Reaction Using Chiral Imines under Neutral Conditions: Stereochemical Evidences in Support of a Cyclic Transition State. Tetrahedron Lett. 1994, 35, 9705-9708.
42. (b) Lucero, M. J.; Houk, K. N. Conformational Transmission of Chirality: The Origin of 1,4-Asymmetric Induction in Michael Reactions of Chiral lmines. J. Am. Chem. Soc. 1997, 119, 826-827.
43. The importance of hydrogen on nitrogen of enamine in aldol reactions has been described: (c) Bahmanyar, S.; Houk, K. N. Transition States of Amine-Catalyzed Aldol Reactions Involving Enamine Intermediates: Theoretical Studies of Mechanism, Reactivity, and Stereoselectivity. J. Am. Chem. Soc. 2001, 123, 11273-11283.
44. Matsubara, R.; Kawai, N.; Kobayashi, S. Catalytic Enantioselective and Diastereoselective Addition of Aldehyde-Derived Enecarbamates to α-Oxo Aldehydes. Angew. Chem., Int. Ed. 2006, 45, 3814-3816.
45. (a) Denmark, S. E.; Ghosh, S. K. The First Catalytic, Diastereoselctive, and Enantioselective Crossed-Aldol Reactions of Aldehydes. Angew. Chem., Int. Ed. 2001, 40, 4759-4762.
46. (b) Northrup, A. B.; MacMillan, D. W. C. Two-Step Synthesis of Carbohydrates by Selective Aldol Reactions. Science 2004, 305, 1752-1755.
47. (c) Córdova, A.; Ibrahem, I.; Casas, J.; Sundén, H.; Engqvist, M.; Reyes, E. Amino Acid Catalyzed Neogenesis of Carbohydrates: A Plausible Ancient Transformation. Chem. - Eur. J. 2005, 11, 4772-4784, references cited therein.
48. Wolfram, M. L.; Mc.Fadden, G. H.; Chaney, A. Synthesis of Benzyl Vinylcarbamate and 3-O-Vinylcarbamoyl-D-mannitol Pentanitrate. J. Org. Chem. 1961, 26, 2597-2599.
49. See the references cited in ref 17.
50. Reviews for direct-type catalytic asymmetric reactions: (a) Alcaide, B.; Almendros, P. The Direct Catalytic Asymmetric Aldol Reaction. Eur. J. Org. Chem. 2002, 1595-1601.
51. (b) List, B. Enamine Catalysis Is a Powerful Strategy for the Catalytic Generation and Use of Carbanion Equivalents. Acc. Chem. Res 2004, 37, 548-557.
52. (c) Notz, W.; Tanaka, F.; Barbas, C. F., III. Enamine-Based Organocatalysis with Proline and Diamines: The Development of Direct Catalytic Asymmetric Aldol, Mannich, Michael, and Diels-Alder Reactions. Acc. Chem. Res 2004, 37, 580-591.
53. (d) Shibasaki, M.; Kanai, M.; Funabashi, K. Recent Progress in Asymmetric Two-center Catalysis. Chem. Commum. 2002, 1989-1999.
54. (e) Shibasaki, M.; Yoshikawa, N. Lanthanide Complexes in Multifunctional Asymmetric Catalysis. Chem. Rev. 2002, 102, 2187-2209.
55. 2-Symmetric Bis(oxazoline) Copper(II) Complexes in the Synthesis of Chiral, Differentiated Glutarate Esters. J. Am. Chem. Soc. 2000, 122, 9134-9142.
56. (b) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.; Willis, M. C. Enantioselective and Diastereoselective Mukaiyama-Michael Reactions Catalyzed by Bis(oxazoline) Copper(II) Complexes. J. Am. Chem. Soc. 2001, 123, 4480-4491.
57. Kobayashi, S.; Kiyohara, H.; Nakamura, Y.; Matsubara, R. Catalytic Asymmetric Synthesis of α-Amino Phophonates Using Enantioselective carbon-carbon Bond-Forming Reactions. J. Am. Chem. Soc. 2004, 126, 6558-6559.
58. Kitajima, H.; Ito, K.; Katsuki, T. A New Methodogy for the Stereoselctive Snthesis of 4-Substituted Butenolides: Asymmetric Michael Addition Reaction of 2-(Trimethylsilyloxy)furans to Oxazolidinone Enoates. Tetrahedron 1997, 53, 17015-17028.
59. A compound similar to compound 34 is known to inhibit the Lewis Acid Catalyst, see ref 22b
60. 2-symmetric Nickel Diamine Complex as an Asymmetric Catalyst for Enecarbamate Additions to Butane-2,3-dione. Org. Biomol. Chem. 2005, 3, 2910-2913.
61. Matsubara, R.; Kobayashi, S. Catalytic Asymmetric Amination of Enecarbamates. Angew. Chem., Int. Ed. 2006, 45, 7993-7995.