NMR investigations on the proline-catalyzed aldehyde self-condensation: Mannich mechanism, dienamine detection, and erosion of the aldol addition selectivity

Journal of Organic Chemistry

Volumn 76, Issue 9, 2011, Pages 3005-3015

  Schmid, Markus B ^a   Zeitler, Kirsten ^a   Gschwind, Ruth M ^a  

^a UNIVERSITY OF REGENSBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALDOL ADDITION; ALDOL CONDENSATION; ALDOLIZATION; ALIPHATIC ALDEHYDES; C-C BOND FORMATION; CATALYST MOLECULE; DEUTERATIONS; DIASTEREO-SELECTIVITY; IN-SITU; NMR SPECTROSCOPY; RATE DETERMINING STEP; REACTION OPTIMIZATION; REACTION PATHWAYS; REACTION PROFILE; SELF-CONDENSATION; TIME-DEPENDENT;

ADDITION REACTIONS; ALDEHYDES; AMINO ACIDS; CATALYSIS; CATALYSTS; CONDENSATION; DEUTERIUM; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLIGOMERIZATION; OLIGOMERS; ORGANIC COMPOUNDS; REACTION INTERMEDIATES;

CONDENSATION REACTIONS;

ALDEHYDE; CARBON; PROLINE;

ADDITION REACTION; ALDOL REACTION; ARTICLE; CHEMICAL BOND; HYDROLYSIS; MANNICH REACTION; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLIGOMERIZATION; POLYMERIZATION; STEREOCHEMISTRY;

ACETALDEHYDE; ALDEHYDES; ALKENES; AMINES; CATALYSIS; DEUTERIUM; KINETICS; MAGNETIC RESONANCE SPECTROSCOPY; PROLINE; STEREOISOMERISM; SUBSTRATE SPECIFICITY;

EID: 79955555770     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo200431v     Document Type: Article

References (62)

1. Berkessel, A.; Gröger, H. Asymmetric Organocatalysis-From Biomimetic Concepts to Applications in Asymmetric Synthesis; Wiley-VCH: Weinheim, 2005.
2. Dalko, P. I., Ed. Enantioselective Organocatalysis: Reactions and Experimental Procedures; Wiley-VCH: Weinheim, 2007.
3. Chem. Rev. 2007, 107, 12: special issue on organocatalysis.
4. Reetz, M. T.; List, B.; Jaroch, S.; Weinmann, H.; Eds.; Ernst Schering Foundation Symposium Proceedings "Organocatalysis" Springer: Berlin, 2008.
5. List, B., Ed. Top. Curr. Chem. 2010, 291: Asymmetric Organocatalysis.
6. List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396
7. List, B. Chem. Commun. 2006, 819-824
8. Mukherjee, S.; Yang, J. W.; Hoffmann, S.; List, B. Chem. Rev. 2007, 107, 5471-5569
9. Melchiorre, P.; Marigo, M.; Carlone, A.; Bartoli, G. Angew. Chem., Int. Ed. 2008, 47, 6138-6171
10. Bertelsen, S.; Jørgensen, K. A. Chem. Soc. Rev. 2009, 38, 2178-2189
11. Pihko, P. M.; Majander, I.; Erkkilä, A. Top. Curr. Chem. 2010, 291, 29-75
12. Nielsen, M.; Worgull, D.; Zweifel, T.; Gschwend, B.; Bertelsen, S.; Jørgensen, K. A. Chem. Commun. 2011, 47, 632-649
13. Bahmanyar, S.; Houk, K. N. J. Am. Chem. Soc. 2001, 123, 11273-11283
14. Bahmanyar, S.; Houk, K. N.; Martin, H. J.; List, B. J. Am. Chem. Soc. 2003, 125, 2475-2479
15. Hoang, L.; Bahmanyar, S.; Houk, K. N.; List, B. J. Am. Chem. Soc. 2003, 125, 16-17
16. Sharma, A.; Sunoj, R. Angew. Chem., Int. Ed. 2010, 49, 6373-6377
17. List, B.; Hoang, L.; Martin, H. J. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5839-5842
18. Seebach, D.; Beck, A. K.; Badine, D. M.; Limbach, M.; Eschenmoser, A.; Treasurywala, A. M.; Hobi, R.; Prikoszovich, W.; Linder, B. Helv. Chim. Acta 2007, 90, 425-471
19. Zotova, N.; Broadbelt, L. J.; Armstrong, A.; Blackmond, D. G. Bioorg. Med. Chem. Lett. 2009, 19, 3934-3937
20. Schmid, M. B.; Zeitler, K.; Gschwind, R. M. Angew. Chem., Int. Ed. 2010, 49, 4997-5003
21. Bock, D. A.; Lehmann, C. W.; List, B. Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 20636-20641
22. Kanzian, T.; Lakhdar, S.; Mayr, H. Angew. Chem., Int. Ed. 2010, 49, 9526-9529
23. Blackmond, D. G.; Moran, A.; Hughes, M.; Armstrong, A. J. Am. Chem. Soc. 2010, 132, 7598-7599
24. For a recent GC-based investigation of aldol/Mannich ratios in the condensation of isobutyraldehyde with acetone, see: Domínguez de María, P.; Bracco, P.; Castelhano, L. F.; Bargeman, G. ACS Catal. 2011, 1, 70-75
25. Trost, B. M.; Brindle, C. S. Chem. Soc. Rev. 2010, 39, 1600-1632
26. Recently, the organocatalytic asymmetric Knoevenagel condensation has been introduced: Lee, A.; Michrowska, A.; Sulzer-Mosse, S.; List, B. Angew. Chem., Int. Ed. 2011, 50, 1707-1710
27. Erkkilä, A.; Pihko, P. M. Eur. J. Org. Chem. 2007, 4205-4216
28. Zumbansen, K.; Döhring, A.; List, B. Adv. Synth. Catal. 2010, 352, 1135-1138
29. List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573-575
30. Nozière, B.; Córdova, A. J. Phys. Chem. A 2008, 112, 2827-2837
31. Arend, M.; Westermann, B.; Risch, N. Angew. Chem., Int. Ed. 1998, 37, 1044-1070
32. Ishikawa, T.; Uedo, E.; Okada, S.; Saito, S. Synlett 1999, 450-452
33. Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301-303
34. Casas, J.; Sundén, H.; Córdova, A. Tetrahedron Lett. 2004, 45, 6117-6119
35. Smith, M. B.; March, J. March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 6th ed.; John Wiley & Sons, Inc.: Hoboken, 2006.
36. Hong, B.-C.; Wu, M.-F.; Tseng, H.-C.; Liao, J.-H. Org. Lett. 2006, 8, 2217-2220
37. Erkkilä, A.; Pihko, P. M. J. Org. Chem. 2006, 71, 2538-2541
38. A similar dual activation of carbonyl species by proline has recently been proposed for the organocatalytic homodimerization of enones: Guidi, V.; Sandoval, S.; McGregor, M. A.; Rosen, W. Tetrahedron Lett. 2010, 51, 5086-5090
39. Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798-6799
40. Miyano, M. J. Org. Chem. 1981, 46, 1854-1857
41. Zotova, N.; Franzke, A.; Armstrong, A.; Blackmond, D. G. J. Am. Chem. Soc. 2007, 129, 15100-15101
42. Zotova, N.; Moran, A.; Armstrong, A.; Blackmond, D. Adv. Synth. Catal. 2009, 351, 27652769
43. Interestingly, the rate-limiting step of the proline-catalyzed intramolecular Hajos-Parrish-Eder-Sauer-Wiechert (44, 45) aldol reaction has been shown to precede the C-C bond formation. (46) However, this may be attributed to the acceleration of the C-C bond formation by the "apparent concentration effect in the intramolecular case". (19)
44. Eder, U.; Sauer, G.; Wiechert, R. Angew. Chem., Int. Ed. 1971, 10, 496-497
45. Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621
46. Zhu, H.; Clemente, F. R.; Houk, K. N.; Meyer, M. P. J. Am. Chem. Soc. 2009, 131, 1632-1633
47. This type of graphical representation is used to show the clear trend of a strongly increasing formation rate for the condensation product 3 upon higher catalyst loadings in contrast to the nearly unchanging formation rates of the aldol products 2a, b which are by far less affected by increasing catalyst amounts and only exceed the formation rate of the condensation product at the lowest catalyst loading (approximately 0.7% enamine concentration ≈ 10 mol% of proline). Because of the limited solubility of proline in DMSO at amounts exceeding 30 mol % of catalyst loading and the influence of water on the reaction rates (enamine formation) as noticed by us and others, (19) we found the relation of the formation rates against the actual present catalyst amount represented by the enamine concentration to be more accurate, especially in case of short reaction times. (Note: enamine formation is fast and reversible according to our earlier EXSY analyses. (20))
48. Alcaide, B.; Almendros, P. Angew. Chem., Int. Ed. 2008, 47, 4632-4634
49. García-García, P.; Ladépêche, A.; Halder, R.; List, B. Angew. Chem., Int. Ed. 2008, 47, 4719-4721
50. Hayashi, Y.; Itoh, T.; Aratake, S.; Ishikawa, H. Angew. Chem., Int. Ed. 2008, 47, 2082-2084
51. Hayashi, Y.; Itoh, T.; Ohkubo, M.; Ishikawa, H. Angew. Chem., Int. Ed. 2008, 47, 4722-4724
52. Hayashi, Y.; Okano, T.; Itoh, T.; Urushima, T.; Ishikawa, H.; Uchimaru, T. Angew. Chem., Int. Ed. 2008, 47, 9053-9058
53. Hayashi, Y.; Samanta, S.; Itoh, T.; Ishikawa, H. Org. Lett. 2008, 10, 5581-5583
54. http://riodb01.ibase.aist.go.jp/sdbs/, accessed March 11, 2011.
55. Bertelsen, S.; Marigo, M.; Brandes, S.; Diner, P.; Jørgensen, K. A. J. Am. Chem. Soc. 2006, 128, 12973-12980
56. Hong, B.-C.; Wu, M.-F.; Tseng, H.-C.; Huang, G.-F.; Su, C.-F.; Liao, J.-H. J. Org. Chem. 2007, 72, 8459-8471
57. Utsumi, N.; Zhang, H.; Tanaka, F.; Barbas, C. F., III. Angew. Chem., Int. Ed. 2007, 46, 1878-1880
58. de Figueiredo, R. M.; Fröhlich, R.; Christmann, M. Angew. Chem., Int. Ed. 2008, 47, 1450-1453
59. Liu, K.; Chougnet, A.; Woggon, W.-D. Angew. Chem., Int. Ed. 2008, 47, 5827-5829
60. Han, B.; Xiao, Y.-C.; He, Z.-Q.; Chen, Y.-C. Org. Lett. 2009, 11, 4660-4663
61. Marqués-López, E.; Herrera, R. P.; Marks, T.; Jacobs, W. C.; Könning, D.; de Figueiredo, R. M.; Christmann, M. Org. Lett. 2009, 11, 4116-4119
62. Bencivenni, G.; Galzerano, P.; Mazzanti, A.; Bartoli, G.; Melchiorre, P. Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 20642-20647