Deprotonation of β,β-disubstituted α,β-unsaturated amides -Mechanism and stereochemical consequences

Canadian Journal of Chemistry

Volumn 84, Issue 10, 2006, Pages 1397-1410

  Green, James R ^a   Majewski, Marek ^b   Snieckus, Victor ^c,d  

^a UNIVERSITY OF WINDSOR   (Canada)

^b UNIVERSITY OF SASKATCHEWAN   (Canada)

^c UNIVERSITY OF WATERLOO   (Canada)

^d QUEEN S UNIVERSITY   (Canada)

Author keywords

Amide; Deprotonation mechanism; Dienolate; Enolization; Regioselectivity; Stereoselectivity; Transition state

Indexed keywords

DEPROTONATION MECHANISM; DIENOLATE; ENOLIZATION; TRANSITION STATE;

CARBON; DENSITY FUNCTIONAL THEORY; LITHIUM COMPOUNDS; REGIOSELECTIVITY; STEREOCHEMISTRY; STEREOSELECTIVITY;

AMIDES;

3 (1 BUTYL) 4 METHOXY N,N,2 TRIMETHYL 3 BUTENANIDE; 3 (1 BUTYL)N,N,2 TRIMETHYL 3 PENTENAMIDE; 3 (1,1 DIMETHYLETHYL)N,N,2 TRIMETHYL 3 PENTENAMIDE; 3 (2 BUTYL)N,N,2 TRIMETHYL 3 PENTENAMIDE; 3 (2 BUTYL)N,N,2,5 TETRAMETHYL 3 HEXENAMIDE; 3 DEUTERIOMETHYL N,N,2 TRIMETHYL 3 BUTENANIDE; 3 ETHYL 2 HEPTANOIC ACID; 3 ETHYL N,N DIMETHYL 2 HEPTENAMIDE; 3 ETHYL N,N DIMETHYL 2 PENTENAMIDE; 3 ETHYL N,N,3 TRIMETHYL 3 PENTENAMIDE; 4 DEUTERIO 3 [(DIETHYLPHOSPHORYL)OXY]N,N DIMETHYL 2 BUTENAMIDE; 4 DEUTERIO N,N DIMETHYL 3 OXOBUTENAMIDE; 4 DEUTERIO N,N TRIMETHYL 2 BUTENAMIDE; 4 DEUTERIO N,N,2,3 TETRAMETHYL 3 BUTENANIDE; 4 DEUTERIO N,N,3 TRIMETHYL 2 BUTENAMIDE; 6 DEUTERIO 5 (1,1 DIMETHYLETHYL) 1 CYCLOHEXENYL N,N DIMETHYLPROPANAMIDE; AMIDE; CARBON; CYCLOHEXYLIDENECARBOXAMIDE DERIVATIVE; DIMETHYL 2 [5 (1,1 DIMETHYLETHYL) 6 METHYL 1 CYCLOHEXENYL]PROPANAMIDE; ETHYL 2 PENTYNOIC ACID; ETHYL 3 ETHYL 2 HEPTENOIC ACID; ETHYL 3 OXO 2 TRIPHENYLPHOSPHORANYLIDENEPENTANOIC ACID; LITHIUM DIALKYLAMIDE; N,N 2 TRIMETHYL 3 HEXENAMIDE; N,N DIMETHYL 2 [3 (1,1 DIMETHYLETHYL) 6 METHYL 1 CYCLOHEXENYL]PROPANAMIDE; N,N DIMETHYL 3 HEXENAMIDE; N,N DIMETHYL 3 OXOBUTENAMIDE; N,N,2,3 TETRAMETHYL 4 TRIMETHYLSILYL 3 BUTENAMIDE; SENECIOAMIDE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; OUTCOME ASSESSMENT; PROTON TRANSPORT; STEREOCHEMISTRY;

EID: 33847616956     PISSN: 00084042     EISSN: None     Source Type: Journal    
DOI: 10.1139/V06-112     Document Type: Article

References (125)

1. (a) R. Mahrwald (Editor). Modern aldol reactions. Wiley-VCH, Weinheim, Germany. 2004;
2. (b) C.H. Heathcock. In Asymmetric synthesis. Vol. 3. Edited by J.D. Morrison. Academic Press, New York. 1983. pp. 111-212.
3. (a) D.A. Evans. In Asymmetric synthesis. Vol. 3. Edited by J.D. Morrison. Academic Press, New York. 1983. pp. 1-110;
4. (b) see also: R.M. Pollack. Tetrahedron, 45, 4913 (1989);
5. (c) J.R. Green. In Science of synthesis. Vol. 8a. Edited by M. Majewski and V. Snieckus. Georg Thieme Verlag, Stuttgart, Germany. 2005. pp. 427-486.
6. R.E. Ireland, R.H. Mueller, and A.K. Willard. J. Am. Chem. Soc. 98, 2868 (1976).
7. R.R. Fraser and P.J. Champagne. J. Am. Chem. Soc. 100, 657 (1978).
8. (a) F. Johnson. Chem. Rev. 68, 375 (1968);
9. (b) G.J. Karabatsos and D.J. Fenoglio. Top. Stereochem. 5, 167 (1970).
10. (a) A.J. Kirby (Editor). Stereoelectronic effects. Oxford University, Oxford. 1996;
11. (b) P. Deslongchamps. Stereoelectronic effects in organic chemistry. Pergamon Press, Oxford, UK. 1983. p. 274;
12. (c) A.J. Kirby. Adv. Phys. Org. Chem. 29, 87 (1994).
13. For reviews, see: (a) M.C. Whisler, S. MacNeil, V. Snieckus, and P. Beak. Angew. Chem. Int. Ed. 43, 2206 (2004);
14. (b) P. Beak and A. I. Meyers. Acc. Chem. Res. 19, 356 (1986).
15. (a) A. Sun and D.B. Collum. J. Am. Chem. Soc. 122, 2452 (2000);
16. (b) D.J. Miller and W.H. Saunders, Jr. J. Org. Chem. 47, 5039 (1982).
17. (a) A. Sun and D.B. Collum. J. Am. Chem. Soc. 122, 2459 (2000);
18. (b) M. Al-Aseer, P. Beak, D. Hay, D.J. Kempf, S. Mills, and S.G. Smith. J. Am. Chem. Soc. 105, 2080 (1983);
19. (c) A.I. Meyers, W.F. Rieker, and L.M. Fuentes. J. Am. Chem. Soc. 105, 2082 (1983).
20. (a) For the modified Ireland-Narula model, see: H.P. Beutelman, L. Xie, and W.H. Saunders, Jr. J. Org. Chem. 54, 1703 (1989).
21. (a) F.E. Romesberg and D.B. Collum. J. Am. Chem. Soc. 117, 2166 (1995);
22. (b) J.M. Hayes, J.C. Greer, and F.S. Mair. New J. Chem. 25, 262 (2001).
23. (a) In the construction of the carbacyclic prostacyclic analogue isocicaprost, see: M. Lerm, H.-J. Gais, K. Cheng, and C. Vermeeren. J. Am. Chem. Soc. 125, 9653 (2003);
24. (b) in the stereoselective construction of oxetanes and ring fused tetrahydrofurans, see: P. Galatsis, S.D. Millan, and G. Ferguson. J. Org. Chem. 62, 5048 (1997).
25. (a) For reviews, see: S. Gil and M. Parra. Curr. Org. Chem. 6, 283 (2002);
26. (b) G. Casiraghi, F. Zanardi, G. Appendino, and G. Rassu. Chem. Rev. 100, 1929 (2000);
27. (c) J.R. Green. Ph.D. thesis, University of Waterloo, Waterloo, Ontario. 1987.
28. For studies concerning the site of deprotonation, see: (a) M. Iguchi and K. Tomioka. Org. Lett. 4, 4329 (2002);
29. (b) M.J. Aurell, L.R. Domingo, R. Mestres, E. Muñoz, and R.J. Zaragoza. Tetrahedron, 55, 815 (1999);
30. (c) D.W. Cameron, M.G. Looney, and J.A. Patterman. Tetrahedron Lett. 36, 7555 (1995);
31. (d) S.Y. Lee, Y.S. Kulkarni, B.W. Burbaum, M.L. Johnston, and B.B. Snider. J. Org. Chem. 53, 1848 (1988);
32. (e) C. Fehr and J. Galindo. J. Org. Chem. 53, 1828 (1988);
33. (f) V. Guay and P. Brassard. Synthesis, 294 (1987);
34. (g) S. Tsuboi, K. Muranaka, T. Sakai, and A. Takeda. J. Org. Chem. 51, 4944 (1986);
35. (h) F.L. Harris and L. Weiler. J. Chem. Soc. Chem. Commun. 1124 (1985);
36. (i) Y. Thebtaranonth and C. Yenjai. Tetrahedron Lett. 26, 4097 (1985);
37. (j) A.E. Greene, F. Coelho, J.-P. Deprés, and T.J. Brocksom. J. Org. Chem. 50, 1973 (1985);
38. (k) J.-P. Gesson, J.-C. Jacquesy, and B. Renoux. Tetrahedron, 40, 4743 (1984);
39. (l) E. Block, V. Eswarakrisknan, and K. Gebreyes. Tetrahedron Lett. 25, 5469 (1984);
40. (m) P. Brownbridge, P.G. Hunt, and S. Warren. Tetrahedron Lett. 24, 3391 (1983);
41. (n) F.L. Harris and E.-P. Krebs. Helv. Chim. Acta, 64, 1023 (1984);
42. (o) J.-P. Gesson, J.-C. Jacquesy, and M. Mondon. Tetrahedron Lett. 21, 2509 (1980);
43. (p) T.A. Hase and R. Kukkola. Synth. Commun. 10, 451 (1980);
44. (q) J.J. Eisch and J.E. Galle. J. Org. Chem. 44, 3279 (1979);
45. (r) W.G. Dauben, G.T. Rivers, and W.J. Zimmerman. J. Am. Chem. Soc. 99, 3414 (1977);
46. (s) J.A. Katzenellenbogen and A.L. Crumrine. J. Am. Chem. Soc. 98, 4925 (1976);
47. (t) J.D. White and W.L. Sung. J. Org. Chem. 39, 2323 (1974);
48. (u) M.S. Newman, V. De Vries, and R. Darlak. J. Org. Chem. 31, 2171 (1976).
49. For direct evidence of dienolate structure, see: (a) L.R. Domingo, S. Gil, and M. Parra. Tetrahedron: Asymmetry, 12, 915 (2001);
50. (b) L.R. Domingo, S. Gil, R. Mestres, and M.T. Picher. Tetrahedron, 52, 11105 (1996);
51. (c) P.G. Williard, J.R. Tata, R.H. Schlessinger, A.D. Adams, and E.J. Iwanowicz. J. Am. Chem. Soc. 110, 7901 (1988);
52. (d) A.D. Adams, R.H. Schlessinger, J.R. Tata, and J.J. Venit. J. Org. Chem. 51, 3068 (1986);
53. (e) A. Bongini, M. Orena, and S. Sandri. J. Chem. Soc. Chem. Commun. 50 (1986);
54. (f) R. Amstutz, J.D. Dunitz, J.P. Laube W.B. Schweizer, and D. Seebach. Chem. Ber. 119, 434 (1986);
55. (g) M.-E. Tran Huu Dau, M. Fétizon, and N.T. Anh. Tetrahedron Lett. 855 (1973);
56. (h) G.J. Heiszwolf and H. Kloosterziel. Recl. Trav. Chim. Pays-Bas, 86, 807 (1967);
57. (i) D. Ivanoff, B. Jordanov, and B. Blagoev. Naturwissenschaften, 51, 286 (1964);
58. (j) E.J. Corey and R.A. Sneen. J. Am. Chem. Soc. 78, 6269 (1956);
59. (k) M. Majewski. Ph.D. thesis, University of Waterloo, Waterloo, Ontario. 1982.
60. For evidence based on product analysis, see: (a) S.K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji, and K. Inomata. Bull. Chem. Soc. Jpn. 77, 2147 (2004);
61. (b) F. Bargiggia and O. Piva. Tetrahedron: Asymmetry, 14, 1819 (2003);
62. (c) M. Hiersemann, C. Lauterbach, and A. Pollex. Eur. J. Org. Chem. 2713 (1999);
63. (d) K. Tomooka, A. Nagasawa, and T. Nakai. Chem. Lett. 1049 (1998);
64. (e) K. Tomooka, A. Nagasawa, S.-Y. Wei, and T. Nakai. Tetrahedon Lett. 37, 8895 (1996);
65. (f) P. Galatsis, J.J. Manwell, and S.C. Millan. Tetrahedron Lett. 37, 5261 (1996);
66. (g) Y. Yamamoto, S. Hatsuya, and J.-i. Yamada. J. Org. Chem. 55, 3118 (1990);
67. (h) S. Fier, R.W. Sullivan, and B. Rickborn. J. Org. Chem. 53, 2353 (1988);
68. (i) A. Bongini, M. Orena, and S. Sandri. J. Chem. Soc. Chem. Commun. 50 (1986);
69. (j) S.G. Alcock, J.E. Baldwin, R. Bohlmann, L.M. Harwood, and J.I. Seeman. J. Org. Chem. 50, 3526 (1985);
70. (k) S.H. Bell, D.W. Cameron, and G.I. Feutrill. Tetrahedron Lett. 26, 6519 (1985);
71. (l) E. Piers and A.V. Gavai. J. Org. Chem. 56, 2374 (1990);
72. (m) Y. Ikeda and H. Yamamoto. Tetrahedron Lett. 25, 5181 (1984);
73. (n) W. Oppolzer, R. Pitteloud, G. Bernardinelli, and K. Baetlig. Tetrahedron Lett. 24, 4975 (1983);
74. (o) A.I. Meyers, W.F. Rieker, and L.M. Fuentes. J. Am. Chem. Soc. 105, 2082 (1983);
75. (p) A.S. Kende and B.H. Toder. J. Org. Chem. 47, 163 (1982);
76. (q) M. Majewski, G.B. Mpango, M.T. Thomas, A. Wuand, and V. Snieckus. J. Org. Chem. 46, 2029 (1981), and refs. cited therein;
77. (r) E.-P. Krebs. Helv. Chim. Acta, 64, 1023 (1981);
78. (s) M. Hayashi, Y. Arai, H. Wakatsuka, M. Kawamura, Y. Konishi, T. Tsuda, and K. Matsumoto. J. Med. Chem. 23, 525 (1980);
79. (t) H. Koyama, K. Kogure, K. Mori, and M.P. Zimmerman. Synth. Commun. 7, 189 (1977);
80. (u) P.E. Pfeffer and L.S. Silbert. J. Org. Chem. 36, 3290 (1971);
81. (v) P.v.R. Schleyer, J.D. Pill, and J.A. Pople. Tetrahedron, 33, 2497 (1977);
82. (w) S.R. Wilson and R.S. Myers. J. Org. Chem. 40, 3309 (1975);
83. (x) A.S. Kende, D. Constantinides, SJ. Lee, and L. Liebeskind. Tetrahedron Lett. 405 (1975);
84. (y) M. Matsui. Agr. Biol. Chem. 36, 792 (1972).
85. P. Beak, D.J. Kempf, and K.D. Wilson. J. Am. Chem. Soc. 107, 4745 (1985).
86. To avoid overlap, we exclude presentation of our results on 3b, which are in complete agreement with those reported by Harris and Weiler (ref. 19). For a preliminary communication, see: M. Majewski, J. R. Green, and V. Snieckus. Tetrahedron Lett. 27, 531 (1986).
87. Weiler and Harris have reported an analogous investigation of α,β-unsaturated acids and esters: (a) F.L. Harris and L. Weiler. Tetrahedron Lett. 25, 1333 (1984);
88. (b) F.L. Harris and L. Weiler. Tetrahedron Lett. 26, 1939 (1985).
89. For a review, see: A.R. Katritzky, M. Piffl, H. Lang, and E. Anders. Chem. Rev. 99, 665 (1999).
90. J.R. Green, M. Majewski, B.I. Alo, and V. Snieckus. Tetrahedron Lett. 27, 535 (1986).
91. F.-W. Sum and L. Weiler. Can. J. Chem. 57, 1431 (1979).
92. (a) E. Corey and J.A. Katzenellenbogen. J. Am. Chem. Soc. 91, 1851 (1969);
93. (b) J.B. Siddall, M. Biskup, and J.H. Fried. J. Am. Chem. Soc. 91, 1854 (1969).
94. M. Hanack, C.J. Collins, H. Stutz, and B.M. Benjamin. J. Am. Chem. Soc. 103, 2356 (1981).
95. G. Markl. Chem. Ber. 94, 3005 (1961).
96. C.J. Timmons. J. Chem. Soc. Chem. Commun. 576 (1965).
97. (a) B.B. Snider, M. Karras, and R.S.E. Conn. J. Am. Chem. Soc. 100, 4264 (1978);
98. (b) B.B. Snider, R.S.E. Conn, and M. Karras. Tetrahedron Lett. 1679 (1979).
99. W. Kitching, H.A. Olszowy, G.M. Drew, and W. Adcock. J. Org. Chem. 47, 5153 (1982).
100. R. Amstutz, J.D. Dunitz, J.P. Laube, W.G. Schweizer, and D. Seebach. Chem. Ber. 119, 434 (1986).
101. (a) D. Seebach, R. Amstutz, and J.D. Dunitz. Helv. Chim. Acta, 64, 2622 (1981);
102. (b) H.D. Zook and J.A. Miller. J. Org. Chem. 36, 1112 (1976).
103. T.I. Moder, C.C.K. Hsu, and F.R. Jensen. J. Org. Chem. 45, 1008 (1980).
104. W. Kitching, H.A. Olszowy, and K. Harvey. J. Org. Chem. 47, 893 (1982).
105. J. Sicher, J. Jonáš, and M. Tichý. Tetrahedron Lett. 825 (1963). A value of A = 1.53 in a different solvent system has been cited; see: H. Booth and M.L. Jozefowicz. J. Chem. Soc. Perkin Trans. 2, 895 (1976).
106. (a) S. Hanessian, A. Gomtsyan, and N. Malek. J. Org. Chem. 65, 5623 (2000);
107. (b) S.E. Denmark and J.E. Marlin. J. Org. Chem. 56, 1003 (1991).
108. (a) T.G. Back and K. Nakajima. J. Org. Chem. 65, 4543 (2000);
109. (b) T.G. Back, M.V. Krishna, and K.R. Muralidharan. J. Org. Chem. 54, 4146 (1989).
110. (a) K. Dawes, N.J. Turro, and J.M. Conia. Tetrahedron Lett. 1377 (1971);
111. (b) B.J.L. Huff, T.N. Tuller, and D. Caine. J. Org. Chem. 34, 3070 (1969).
112. 2NH-enolate complexes; see: T. Laube, J.D. Dunitz, and D. Seebach. Helv. Chim. Acta, 68, 1373 (1985).
113. (a) J. Toullec. In Advances in physical organic chemistry. Vol. 18. Edited by V. Gold and L. Bethell. Academic Press, London. 1982. pp. 1-77;
114. (b) G. Lamaty. In Isotopes in organic chemistry. Vol. 2. Edited by E. Buncel and C.C. Lee. Elsevier. Amsterdam. 1976. pp. 33-88.
115. (a) D.M. Hodgson and M.A.H. Stent. Top. Organometal. Chem. 5, 1 (2003);
116. (b) J. Eames. Eur. J. Org. Chem. 393 (2002);
117. (c) M. Majewski. In Advances in asymmetric synthesis. Vol. 3. Edited by A. Hassner. JAI, Stamford. 1998. pp. 39-76;
118. (d) N.S. Simpkins. In Advanced asymmetric synthesis. Edited by G.R. Stephenson. Chapman and Hall, London, UK. 1996. pp. 111-125.
119. W.C Still, M. Kahn, and A. Mitra. J. Org. Chem. 43, 2923 (1978).
120. D.D. Perrin, W.L. Amarego, and A. Mitra. Purification of laboratory chemicals. 2nd ed. Pergamon, Oxford, UK. 1980.
121. M.R. Winkle, J.M. Lansinger, and R.C. Ronald. J. Chem. Soc. Chem. Commun. 87 (1980).
122. G.B.W. Mpango. Ph.D. dissertation, University of Waterloo, Waterloo, Ontario. 1980.
123. H. Brederick, R. Gompper, and K. Klemm. Chem. Ber. 92, 1456 (1959).
124. E. Schzanberg. Z. Phys. Chem. A181, 430 (1938).
125. G. Cahiez, D. Bernard, and J.F. Normant. Synthesis, 247 (1976).