Transition states and origins of 1,4-asymmetric induction in alkylations of 2,2,6-trialkylpiperidine enamines

Chemistry - A European Journal

Volumn 16, Issue 21, 2010, Pages 6310-6316

  Um, Joann M ^a   Kaka, Naeem S ^b   Hodgson, David M ^b   Houk, K N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

Aldehydes; Alkylation; Asymmetric synthesis; Density functional calculations; Transition states

Indexed keywords

ALKYL SUBSTITUENT; ASYMMETRIC INDUCTION; ASYMMETRIC SYNTHESIS; AXIAL POSITIONS; B3LYP/6-31G; C-ALKYLATION; COMPUTATIONAL MODELING; COMPUTATIONAL STUDIES; DENSITY-FUNCTIONAL CALCULATIONS; ENAMINES; EXPERIMENTAL OBSERVATION; NUCLEOPHILIC SUBSTITUTIONS; PIPERIDINE RINGS; STERIC REASONS; TERMINAL EPOXIDE; TRANSITION STATE; TRANSITION STATES;

ALDEHYDES; ALKYLATION; AMINES; ELECTRON TRANSITIONS; HYDROCARBONS; LITHIUM; SYNTHESIS (CHEMICAL);

DENSITY FUNCTIONAL THEORY;

ALDEHYDE; BIPHENYL DERIVATIVE; ENAMINE; IMIDAZOLE DERIVATIVE; PIPERIDINE; PIPERIDINE DERIVATIVE;

ALKYLATION; ARTICLE; CHEMISTRY; CONFORMATION;

ALDEHYDES; ALKYLATION; BIPHENYL COMPOUNDS; IMIDAZOLES; MOLECULAR CONFORMATION; PIPERIDINES;

EID: 77952684472     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201000046     Document Type: Article

References (56)

1. For reviews, see: a) R. Göttlich in Science of Synthesis: Houben-Weyl Methods of Molecular Transformations, Vol. 2 (Ed.: R. Brückner), Thieme, Stuttgart, 2006, pp. 355-366;
2. P. Melchiorre, Angew. Chem. 2009, 121, 1386;
3. Angew. Chem. Int. Ed. 2009, 48, 1360-1363.
4. N. Vignola, B. List, J. Am. Chem. Soc. 2004, 126, 450-451;
5. A. Fu, B. List, W. Thiel, J. Org. Chem. 2006, 71, 320-326;
6. See also: P. G. Cozzi, F. Benfatti, L. Zoli, Angew. Chem. 2009, 121, 1339-1342;
7. Angew. Chem. Int. Ed. 2009, 48, 1313-1316.
8. D. A. Nicewicz, D. W. C. MacMillan, Science 2008, 322, 77-80.
9. D. M. Hodgson, N. S. Kaka, Angew. Chem. 2008, 120, 10106-10108;
10. Angew. Chem. Int. Ed. 2008, 47, 9958-9960.
11. D. M. Hodgson, C. D. Bray, N. D. Kindon, J. Am. Chem. Soc. 2004, 126, 6780-6781;
12. D. M. Hodgson, C. D. Bray, N. D. Kindon, N. J. Reynolds, S. J. Coote, J. M. Um, K. N. Houk, J. Org. Chem. 2009, 74, 1019-1028.
13. G. Stork, A. Brizzolara, H. Landesman, J. Szmuszkovicz, R. Terrell, J. Am. Chem. Soc. 1963, 85, 207-222;
14. P. W. Hickmott, Tetrahedron 1982, 38, 1975-2050;
15. Enamines: Synthesis Structure and Reactions, 2nd ed. (Ed.: A.G. Cook), Marcel Dekker, New York, 1988;
16. The Chemistry of Enamines (Ed.: Z. Rappoport), Wiley, New York, 1994;
17. T. Sammakia, J. A. Abramite, M. F. Sammons in Science of Synthesis, Vol.33 (Eds.: B. M. Trost, G. A. Molander), Thieme, Stuttgart, 2006, pp. 405-441.
18. N2) reactions of enamines: a) reference [2b];
19. A. Arrieta, F. P. Cossio, B. Lecea, J. Org. Chem. 1999, 64, 1831-1842. Reference [2b] describes the reactivity of pyrrolidine-based enamines, which are known to give different stereochemical outcomes than the six-membered analogues:
20. P. H.-Y. Cheong, H. Zhang, R. Thayumanavan, F. Tanaka, K. N. Houk, C. F. Barbas III, Org. Lett. 2006, 8, 811-814. Reference [7b] describes acyclic enamines. For DFT studies of aldol and Mannich reactions by proline-type catalysts, see:
21. A. Armstrong, Y. Bhonoah, A. J. P. White, J. Org. Chem. 2009, 74, 5041-5048;
22. D. Seebach, U. Groselj, D. M. Badine, W.B. Schweizer, A. K. Beck, Helv. Chim. Acta 2008, 91, 1999-2034;
23. A. Fu, H. Li, H. Si, S. Yuan, Y. Duan, Tetrahedron: Asymmetry 2008, 19, 2285-2292;
24. A. Fu, H. Li, S. Yuan, H. Si, Y. Duan, J. Org. Chem. 2008, 73, 5264-5271;
25. C. B. Shinisha, R. B. Sunoj, Org. Biomol. Chem. 2007, 5, 1287-1294;
26. F. R. Clemente, K.N. Houk, J. Am. Chem. Soc. 2005, 127, 11294-11302.
27. See the Supporting Information for a full analysis of the gas-phase and solution-phase geometries.
28. J.-J. Delpuech in Cyclic Organonitrogen Stereodynamics (Eds.: J. B. Lambert, Y. Takeuchi), Wiley-VCH, Weinheim, 1992, pp. 169-252;
29. K. L. Brown, L. Damm, J. D. Dunitz, A. Eschenmoser, R. Hobi, C. Kretky, Helv. Chim. Acta 1978, 61, 3108-3135.
30. See the Supporting Information for all conformers.
31. J.B. Lambert, R.J. Nienhuis, J. Am. Chem. Soc. 1980, 102, 6659-6665.
32. K. Tani, T. Yamagata, S. Akutagawa, H. Kumobayashi, T. Taketomi, H. Takaya, A. Miyashita, R. Noyori, S. Otsuka, J. Am. Chem. Soc. 1984, 106, 5208-5217.
33. V. Barone, M. Cossi, J. Phys. Chem. A 1998, 102, 1995-2001;
34. M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 2003, 24, 669-681.
35. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652;
36. A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377;
37. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789.
38. Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burent, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.
39. O. Acevedo, W. L. Jorgensen, Acc. Chem. Res. 2009, 42, 724-733;
40. O. Acevedo, W. L. Jorgensen, J. Chem. Theory Comput. 2007, 3, 1412-1419;
41. O. Acevedo, W. L. Jorgensen, J. Am. Chem. Soc. 2006, 128, 6141-6146;
42. O. Acevedo, W. L. Jorgensen, Org. Lett. 2004, 6, 2881-2884;
43. A. Warshel in Computer Modeling of Chemical Reactions in Enzymes and Solutions, Wiley, New York, 1991.
44. R. Ditchfield, W. J. Hehre, J. A. Pople, J. Chem. Phys. 1971, 54, 724-728;
45. W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, 2257-2261;
46. P.C. Hariharan, J.A. Pople, Theor. Chim. Acta 1973, 28, 213-222.
47. W. R. Wadt, P. J. Hay, J. Chem. Phys. 1985, 82, 284-298;
48. M.W. Wong, P. M, W. Gill, R. H. Nobes, L. Radom, J. Phys. Chem. 1988, 92, 4875-4880;
49. P.J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283.
50. B3LYP with the LANL2DZ basis set has been shown to effectively model the geometries and energies of iodo compounds.
51. See: M. Tredwell, J. A. R. Luft, M. Schuler, K. Tenza, K. N. Houk, V. Gouverneur, Angew. Chem. 2007, 120, 363-366;
52. Angew. Chem. Int. Ed. 2007, 46, 357-360, and references therein.
53. A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72, 5639-5648;
54. K. Raghavachari, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650-654;
55. M. J. Frisch, J. A. Pople, J. S. Binkley, J. Chem. Phys. 1984, 80, 3265-3269.
56. K. Wolinski, J. F. Hilton, P. Pulay, J. Am. Chem. Soc. 1990, 112, 8251-8260.