Computational studies of nucleophilic substitution at carbonyl carbon: The SN2 mechanism versus the tetrahedral intermediate in organic synthesis

Journal of Organic Chemistry

Volumn 69, Issue 21, 2004, Pages 7317-7328

  Fox, Joseph M ^a   Dmitrenko, Olga ^a   Liao, Lian An ^a   Bach, Robert D ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; ADDITION REACTIONS; HYDROGEN BONDS; IONIZATION; MOLECULAR STRUCTURE; ORGANIC COMPOUNDS; PROTONS; SUBSTITUTION REACTIONS;

CARBONYL CARBON; FUNCTIONAL GROUPS; NUCLEOPHILIC SUBSTITUTION; PROTONATION;

CARBON;

1,3 DIPHENYLCYCLOPROP 2 ENE CARBOXYLIC ANHYDRIDE; 3 LITHIO 4 PHENYLOXAZOLIDINONE; ACID ANHYDRIDE; CARBON; CARBONYL DERIVATIVE; CARBOXYLIC ACID; CHLORIDE ION; ESTER; FLUORIDE ION; LITHIUM CHLORIDE; METHANOL; N ACYLOXAZOLIDINONE DERIVATIVE; ORGANIC COMPOUND; OXAZOLIDINONE DERIVATIVE; UNCLASSIFIED DRUG;

ADDITION REACTION; ARTICLE; ELIMINATION REACTION; ENANTIOMER; HYDROGEN BOND; METHANOLYSIS; PROTON TRANSPORT; SOLVOLYSIS; STRUCTURE ANALYSIS; SUBSTITUTION REACTION; THERMODYNAMICS;

CARBON; COMPUTER SIMULATION; CYCLOPROPANES; KINETICS; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANIC CHEMICALS; OXAZOLIDINONES;

EID: 5444271246     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049494z     Document Type: Article

References (49)

1. (a) March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992; pp 330-335.
2. (b) Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row: New York, 1987.
3. N2 mechanisms in solvolysis reactions of acyl chlorides, see Bentley, T. W.; Llewellyn, G.; McAlister, J. A. J. Org. Chem. 1996, 61, 7927.
4. Bender, M. L. J. Am. Chem. Soc. 1951, 73, 1626.
5. Capon, B.; Ghosh, A. K.; Grieve, D. M. A. Acc. Chem. Res. 1981, 14, 306.
6. McClelland, R. A.; Santry, L. J. Acc. Chem. Res. 1983, 16, 394.
7. Bender, M. L.; Matsui, H.; Thomas, R. J.; Tobey, S. W. J. Am. Chem. Soc. 1961, 83, 4193.
8. Shain, S. A.; Kirsch, J. F. J. Am. Chem. Soc. 1968, 90, 5848.
9. McClelland, R. A. J. Am. Chem. Soc. 1984, 106, 7579.
10. Williams, A. Acc. Chem. Res. 1989, 22, 387.
11. Ba-Saif, S.; Luthra, A. K.; Williams, A. J. Am. Chem. Soc. 1989, 111, 2647.
12. Ba-Saif, S.; Luthra, A. K.; Williams, A. J. Am. Chem. Soc. 1987, 109, 6362.
13. (a) Chrystiuk, E.; Williams, A. J. Am. Chem. Soc. 1987, 109, 3040.
14. (b) Um, I. H.; Han, H. J.; Ahn, J. A.; Kang, S.; Buncel, E. J. Org. Chem. 2002, 67, 8475.
15. Wilbur, J. L.; Brauman, J. I. J. Am. Chem. Soc. 1994, 116, 9216.
16. Wilbur, J. L.; Brauman, J. I. J. Am. Chem. Soc. 1994, 116, 5839.
17. Craig, S. L.; Zhong, M.; Brauman, J. I. J. Am. Chem. Soc. 1999, 121, 11790.
18. Zhong, M.; Brauman, J. I. J. Am. Chem. Soc. 1999, 121, 2508.
19. Kim, J. K.; Caserio, M. C. J. Am. Chem. Soc. 1981, 103, 2124.
20. Guthrie, J. P. J. Am. Chem. Soc. 1991, 113, 3941.
21. Kevill, D. N.; Kim, C. B. J. Chem. Soc., Perkin Trans. 2 1988, 7, 1353.
22. Bentley, T. W.; Harris, H. C. J. Chem. Soc., Perkin Trans. 2 1986, 619.
23. Yamabe, S.; Minato, T. J. Org. Chem. 1983, 48, 2972.
24. Blake, J. F.; Jorgenson, W. L. J. Am. Chem. Soc. 1987, 109, 3856.
25. Lee, I.; Kim, C. K.; Li, H. G.; Sohn, C. K.; Kim, C. K.; Lee, H. W.; Lee, B.-S. J. Am. Chem. Soc. 2000, 122, 11162.
26. Liao, L.-a.; Fox, J. M. J. Am. Chem. Soc. 2002, 124, 14322.
27. Liao, L.-a.; Zhang, F.; Yan, N.; Golen, J. A.; Fox, J. M. Tetrahedron 2004, 60, 1803.
28. Vedejs, E.; Daugulis, O.; Mackay, J. A.; Rozners, E. Synlett 2001, 1499.
29. Spivey, A. C.; Maddaford, A.; Redgrave, A. J. Org. Prep. Proced. Int. 2000, 32, 331.
30. Fu, G. C. Acc. Chem. Res. 2000, 33, 412.
31. Willis, M. C. J. Chem. Soc., Perkin Trans. 1 1999, 1765.
32. (a) Glukhovtsev, M. N.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1994, 116, 5961.
33. (b) Bach, R. D.; Baboul, A. G.; Schlegel, H. B. J. Am. Chem. Soc. 2001, 123, 5787 and references therein.
34. 2v were both found to be transition states. With inclusion of electron correlation [MP3/MP2/6-31+G(d)], the tetrahedral TS was energetically favored. However, the planar σ TS is also a second-order saddle point at the MP2 as well as the B3LYP level. Analytical second derivatives were not available to confirm the earlier saddle points.
35. The proton affinity of methanol at the B3LYP/6-311+G-(d,p)+ZPVE level is 178.8 kcal/mol and that of acetyl chloride is 174.0 kcal/mol. The PA of water is lower at 168.9 kcal/mol. The PA of the carbonyl oxygen of methyl acetate is calculated to be 190.9 kcal/mol at this level.
36. Zhan, C.-G.; Landry, D. W.; Ornstein, R. L. J. Am. Chem. Soc. 2000, 122, 1522.
37. Liao, L.-a.; Zhang, F.; Dmitrenko, O.; Bach, R. D.; Fox, J. M. J. Am. Chem. Soc. 2004, 126, 4490.
38. Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835.
39. Ho, G.-J.; Mathre, D. J. J. Org. Chem. 1995, 60, 2271.
40. (a) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
41. (b) Barone, V.; Cossi, M.; Tomasi, J. J. Comput. Chem. 1998, 19, 404.
42. (a) Schlegel, H. B. J. Comput. Chem. 1982, 3, 214.
43. (b) Schlegel, H. B. Adv. Chem. Phys. 1987, 67 (Pt. 1), 249.
44. (c) Schlegel, H. B. In Modern Electronic Structure Theory; Yarkony, D. R., Ed.; World Scientific: Singapore, 1995; p 459.
45. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
46. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
47. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
48. (b) Stevens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
49. Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Rassolov, V.; Pople, J. A. J. Chem Phys. 1998, 109, 7764.