Computational, ReactIR-, and NMR-spectroscopic investigations on the chiral formyl anion equivalent N-(α-lithiomethylthiomethyl)-4-isopropyl-5,5-diphenyloxazolidin-2-one and related compounds

Chemistry - A European Journal

Volumn 7, Issue 19, 2001, Pages 4117-4125

  Gaul, Christoph ^a   Arvidsson, Per I ^a   Bauer, Walter ^b   Gawley, Robert E ^c   Seebach, Dieter ^a  

^a ETH ZURICH   (Switzerland)

^b UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^c Department of Biology   (United States)

Author keywords

Chiral formyl anion equivalent; Computational methods; IR spectroscopy; NMR spectroscopy; Structure elucidation

Indexed keywords

AGGLOMERATION; INFRARED SPECTROSCOPY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PROTONS;

REAGENTS;

LITHIUM;

ANION; CARBON; CARBONYL DERIVATIVE; LITHIUM DERIVATIVE; METHYL GROUP; N (ALPHA LITHIOMETHYLTHIOMETHYL) 4 ISOPROPYL 5,5 DIPHENYLOXAZOLIDIN 2 ONE; ORGANOLITHIUM COMPOUND; OXAZOLIDINONE DERIVATIVE; OXYGEN; PROTON; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL STRUCTURE; CHIRALITY; DIASTEREOISOMER; ENANTIOMER; ENERGY; INFRARED SPECTROMETRY; MEASUREMENT; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

EID: 0035476601     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20011001)7:19<4117::AID-CHEM4117>3.0.CO;2-I     Document Type: Article

References (91)

1. a) C. Gaul, D. Seebach, Org. Lett. 2000, 2, 1501;
2. b) C. Gaul, K. Schärer, D. Seebach, J. Org. Chem. 2001, 66, 3059.
3. H. W. Gschwend, H. R. Rodriguez, Org. React. 1979, 26, 1.
4. a) V. Snieckus, Chem. Rev. 1990, 90, 879;
5. b) V. Snieckus in Chemical Synthesis: Gnosis to Prognosis, Vol. 320 (Eds.: C. Chatgilialoglu, V. Snieckus), Kluwer, Dordrecht, 2000, p. 191.
6. a) P. Beak, D. B. Reitz, Chem. Rev. 1978, 78, 275;
7. b) P. Beak, W. J. Zajdel, D. B. Reitz, Chem. Rev. 1984, 84, 471.
8. P. Beak, A. I. Meyers, Acc. Chem. Res. 1986, 19, 356.
9. D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376;
10. Angew. Chem. Int. Ed. Engl. 1997, 36, 2283.
11. H. Gilman, F. J. Webb, J. Am. Chem. Soc. 1949, 71, 4092.
12. a) E. J. Corey, D. Seebach, J. Org. Chem. 1966, 31, 4097;
13. b) B. T. Gröbel, D. Seebach, Synthesis 1977, 357.
14. P. C. B. Page, M. B. van Niel, J. C. Prodger, Tetrahedron 1989, 45, 7643.
15. D. Seebach, J. Hansen, P. Seiler, J. M. Gromek, J. Organomet. Chem. 1985, 285, 1.
16. a) M. Marsch, K. Harms, O. Zschage, D. Hoppe, G. Boche, Angew. Chem. 1991, 103, 338;
17. Angew. Chem. Int. Ed. Engl. 1991, 30, 321;
18. b) G. Boche, M. Marsch, J. Harbach, K. Harms, B. Ledig, F. Schubert, J. C. W. Lohrenz, H. Ahlbrecht, Chem. Ber. 1993, 126, 1887;
19. c) D. J. Pippel, G. A. Weisenburger, S. R. Wilson, P. Beak, Angew. Chem. 1998, 110, 2600;
20. Angew. Chem. Int. Ed. Engl. 1998, 37, 2522.
21. For the X-ray crystal structure of a ortholithiated aromatic tertiary amide, see: J. Clayden, R. P. Davies, M. A. Hendy, R. Snaith, A. E. H. Wheatley, Angew. Chem. 2001, 113, 1282;
22. Angew. Chem. Int. Ed. 2001, 40, 1238.
23. a) R. Amstutz, D. Seebach, P. Seiler, B. Schweizer, J. D. Dunitz, Angew. Chem. 1980, 92, 59;
24. Angew. Chem. Int. Ed. Engl. 1980, 19, 54;
25. b) R. Amstutz, J. D. Dunitz, D. Seebach, Angew. Chem. 1981, 93, 487;
26. Angew. Chem. Int. Ed. Engl. 1981, 20, 465;
27. c) R. Amstutz, T. Laube, B. Schweizer, D. Seebach, J. D. Dunitz, Helv. Chim. Acta 1984, 67, 224;
28. d) D. Seebach, T. Maetzke, R. K. Haynes, M. N. Paddon-Row, S. S. Wong, Helv. Chim. Acta 1988, 71, 299.
29. W. Zarges, M. Marsch, K. Harms, W. Koch, G. Frenking, G. Boche, Chem. Ber. 1991, 124, 543.
30. F. Becke, F. W. Heinemann, D. Steinborn, Organometallics 1997, 16, 2736.
31. M. Al-Aseer, P. Beak, D. Hay, D. J. Kempf, S. Mills, S. G. Smith, J. Am. Chem. Soc. 1983, 105, 2080.
32. A. I. Meyers, W. F. Rieker, L. M. Fuentes, J. Am. Chem. Soc. 1983, 105, 2082.
33. J. J. P. Stewart, J. Comput. Chem. 1989, 10, 209.
34. E. Anders, R. Koch, P. Freunscht, J. Comput. Chem. 1993, 14, 1301.
35. a) A. Opitz, R. Koch, A. R. Katritzky, W.-Q. Fan, E. Anders, J. Org. Chem. 1995, 60, 3743;
36. b) E. U. Würthwein, K. Behrens, D. Hoppe, Chem. Eur. J. 1999, 5, 3459;
37. c) L. M. Pratt, S. Robbins, Theochem/J. Mol. Struct. 1999, 466, 95;
38. d) S. Nakamura, R. Nakagawa, Y. Watanabe, T. Toru, J. Am. Chem. Soc. 2000, 122, 11340;
39. e) H. Schulz, N. Nudelman, P. Viruela-Martin, R. Viruela-Martin, F. Tomas-Vert, J. Chem. Soc. Perkin Trans. 2 2000, 1619;
40. f) G. Hilmersson, Chem. Eur. J. 2000, 6, 3069.
41. G. Hilmersson, P. I. Arvidsson, Ö. Davidsson, M. Håkansson, J. Am. Chem. Soc. 1998, 120, 8143.
42. H. Weiss, A. V. Yakimansky, A. H. E. Müller, J. Am. Chem. Soc. 1996, 118, 8897.
43. A. Abbotto, A. Streitwieser, P. v. R. Schleyer, J. Am. Chem. Soc. 1997, 119, 11255.
44. In an attempt to incorporate a third dimethyl ether molecule geometry optimization resulted in a structure in which one of the three ligands lost the coordination to lithium.
45. L. J. Bartolotti, R. E. Gawley, J. Org. Chem. 1989, 54, 2980.
46. T. Hintermann, D. Seebach, Helv. Chim. Acta 1998, 81, 2093.
47. S. D. Bull, S. G. Davies, M. S. Key, R. L. Nicholson, E. D. Savory, Chem. Commun. 2000, 1721.
48. a) N. D. Epiotis, R. L. Yates, F. Bernardi, S. Wolfe, J. Am. Chem. Soc. 1976, 98, 5435;
49. b) J. R. Larson, N. D. Epiotis, J. Am. Chem. Soc. 1981, 103, 410.
50. a) J.-M. Lehn, G. Wipff, J. Am. Chem. Soc. 1976, 98, 7498;
51. b) J.-M. Lehn, G. Wipff, J. Demunynck, Helv. Chim. Acta 1977, 60, 1239.
52. a) P. v. R. Schleyer, A. J. Kos, Tetrahedron 1983, 39, 1141;
53. b) P. v. R. Schleyer, T. Clark, A. J. Kos, G. W. Spitznagel, C. Rohde, D. Arad, K. N. Houk, N. G. Rondan, J. Am. Chem. Soc. 1984, 106, 6467.
54. K. B. Wiberg, H. Castejon, J. Am. Chem. Soc. 1994, 116, 10489.
55. G. Cuevas, E. Juaristi, J. Am. Chem. Soc. 1997, 119, 7545.
56. R. K. Dress, T. Rölle, R. W. Hoffmann, Chem. Ber. 1995, 128, 673.
57. Cambridge Structural Database 5.2 (Oct. 2000).
58. a) H. Günther in Encyclopedia of Nuclear Magnetic Resonance (Eds.: D. M. Grant, R. K. Harris), Wiley, Chichester, 1996, p. 2807;
59. b) W. Bauer in Lithium Chemistry: A Theoretical and Experimental Overview (Eds.: A.-M. Sapse, P. v. R. Schleyer), Wiley, Chichester, 1995, p. 125;
60. c) W. Bauer, P. v. R. Schleyer, Adv. Carbanion Cliem. 1992, 1, 89;
61. d) R. D. Thomas in Isotopes in the Physical and Biomedical Sciences: Isotope Applications in NMR Studies (Eds.: E. Buncel, J. R. Jones), Elsevier, Amsterdam, 1991, p. 367;
62. e) G. Fraenkel, H. Hsu, B. M. Su in Lithium: Current Applications in Science, Medicine, and Technology (Ed.: R. O. Bach), Wiley, New York, 1985, p. 273;
63. f) G. Fraenkel, A. M. Fraenkel, M. J. Geckle, F. J. Schloss, J. Am. Chem. Soc. 1979, 101, 4745.
64. P. Laszlo in The Multinuclear Approach to NMR-Spectroscopy (Eds.: J. B. Lambert, F. G. Riddell), Reidel, Dordrecht, 1983, p. 261.
65. For selected references on mixed aggregates of lithium compounds, see: a) D. Seebach, R. Hässig, J. Gabriel, Helv. Chim. Acta 1983, 66, 308;
66. b) W. Bauer, L. Lochmann, J. Am. Chem. Soc. 1992, 114, 7482;
67. c) R. F. Schmitz, F. J. J. Dekanter, M. Schakel, G. W. Klumpp, Tetrahedron 1994, 50, 5933;
68. d) G. Hilmersson, Ö. Davidsson, J. Organomet. Chem. 1995, 489, 175;
69. e) P. I. Arvidsson, P. Ahlberg, G. Hilmersson, Chem. Eur. J. 1999, 5, 1348;
70. f) K. B. Aubrecht, B. L. Lucht, D. B. Collum, Organometallics 1999, 18, 2981.
71. gNMR Version 3.65, Cherwell Scientific Limited, The Magdalen Centre Oxford Science Park, Oxford (UK), 1996.
72. Line-shape broadening due to exchange is calculated on a method based on: a) G. Binsch, J. Am. Chem. Soc. 1969, 91, 1304;
73. b) D. S. Stephenson, G. Binsch, J. Magn. Res. 1978, 30, 625.
74. ‡ values correspond to the coalescence temperature.
75. The activation parameters measured for compound 7 are similar to those reported for simple α-thio-, α-seleno-, and α-telluro-substituted alkyllithiums: a) T. Ruhland, R. K. Dress, R. W. Hoffmann, Angew. Chem. 1993, 105, 1487;
76. Angew. Chem. Int. Ed. Engl. 1993, 32, 1467;
77. b) H. J. Reich, R. R. Dykstra, Angew. Chem. 1993, 105, 1489;
78. Angew. Chem. Int. Ed. Engl. 1993, 32, 1469;
79. c) see ref. [32];
80. d) R. W. Hoffmann, R. K. Dress, T. Ruhland, A. Wenzel, Chem. Ber. 1995, 128, 861. This suggests that the mechanism of enantiomerization of compound 7 must be comparable to that of the compounds studied in these references.
81. K. Stott, J. Keeler, Q. N. Van, A. J. Shaka, J. Magn. Reson. 1997, 125, 302.
82. D. Neuhaus, M. P. Williamson in The Nuclear Overhauser Effect in Structural and Conformational Analysis, Wiley, New York, 2000, p. 37, 74, and 364.
83. W. Bauer, A. Soi, A. Hirsch, Magn. Reson. Chem. 2000, 38, 500.
84. The physical data are in agreement with the values reported in the literature: Y. Ito, A. Sasaki, K. Tamoto, M. Sunagawa, S. Terashima, Tetrahedron 1991, 47, 2801.
85. SPARTAN, Version 5.0.1, Wavefunction, Inc., Irvine, CA (USA), 1995.
86. a) W. Huang, personal communication;
87. b) G. I. Csonka, J. Comput. Chem. 1993, 14, 895.
88. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
89. Gaussian 98 (Revision A.7), M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1998.
90. The temperature was calibrated using a method described by Reich: W. H. Sikorski, A. W. Sanders, H. J. Reich, Magn. Reson. Chem. 1998, 36, S118.
91. 6Li was prepared according to a procedure decribed in the literature: ref. [36a].