Isotope Effects and the Nature of Selectivity in Rhodium-Catalyzed Cyclopropanations

Journal of the American Chemical Society

Volumn 125, Issue 51, 2003, Pages 15902-15911

  Nowlan III, Daniel T ^a   Gregg, Timothy M ^b   Davies, Huw M L ^b   Singleton, Daniel A ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

^b UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; CARBON; CATALYST SELECTIVITY; COMPLEXATION; ISOTOPES; REACTION KINETICS; RHODIUM; STEREOCHEMISTRY;

DENSITY FUNCTIONAL THEORY (DFT); DIASTEREOSELECTIVITY; ENANTIOSELECTIVITY; ISOTOPE EFFECTS;

AROMATIC COMPOUNDS;

ACETIC ACID DERIVATIVE; ALKENE DERIVATIVE; BISRHODIUM TETRAKIS[N (DODECYLBENZENESULFONYL)PROLINATE]; CARBENOID; CARBON 13; DIRHODIUM TETRACARBOXYLATE; ISOTOPE; PHENYLDIAZOACETATE; RHODIUM DERIVATIVE; UNCLASSIFIED DRUG; VINYL DERIVATIVE;

ARTICLE; CALCULATION; CATALYSIS; CHEMICAL STRUCTURE; CHIRALITY; CYCLOPROPANATION; DENSITY FUNCTIONAL THEORY; GEOMETRY; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

ALKENES; AZO COMPOUNDS; CARBON ISOTOPES; CATALYSIS; CYCLIZATION; CYCLOPROPANES; KINETICS; MODELS, MOLECULAR; MOLECULAR CONFORMATION; ORGANOMETALLIC COMPOUNDS; RHODIUM; STEREOISOMERISM;

EID: 0346364994     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja036025q     Document Type: Article

References (53)

1. Doyle, M. P.; Griffin, J. H.; Bagheri, V.; Dorow, R. L. Organometallics 1984, 3, 53-61.
2. Doyle, M. P.; Bagheri, V.; Wandless, T. J.; Harn, N. K.; Brinker, D. A.; Eagle, C. T.; Loh, K.-L. J. Am. Chem. Soc. 1990, 112, 1906-1912.
3. Davies, H. M. L.; Hodges, L. M.; Matasi, J. J.; Hansen, T.; Stafford, D. G. Tetrahedron Lett. 1998, 39, 4417-4420.
4. The only effective catalysts for highly enantioselective and diasteoselective cyclopropanations with ethyl diazoacetate have been ruthenium-based catalysts. For examples, see: (a) Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J. Am. Chem. Soc. 1994, 116, 2223-2224.
5. (b) Frauenkron, M.; Berkessel, A. Tetrahedron Lett. 1997, 38, 7175-7176.
6. (c) Bachmann, S.; Furler, M.; Mezzetti, A. Organometallics 2001, 20, 2102-2108.
7. (d) Werle, T.; Maas, G. Adv. Synth. Catal. 2001, 343, 37-40.
8. (a) Doyle, M. P.; Austin, R. E.; Bailey, A. S.; Dwyer, M. P.; Dyatkin, A. B.; Kalinin, A. V.; Kwan, M. M. Y.; Liras, S.; Oalmann, C. J.; Pieters, R. J.; Protopopova, M. N.; Raab, C. E.; Roos, G. H. P.; Zhou, Q.-L.; Martin, S. F. J. Am. Chem. Soc. 1995, 117, 5763-5775.
9. (b) Doyle, M. P.; Zhou, Q.-L.; Dyatkin, A. B.; Ruppar, D. A. Tetrahedron Lett. 1995, 36, 7579-7582.
10. (a) Davies, H. M. L.; Clark, T. J.; Church, L. A. Tetrahedron Lett. 1989, 30, 5057-5060.
11. (b) Davies, H. M. L.; Bruzinski, P. R.; Fall, M. J. Tetrahedron Lett. 1996, 37, 4133-4136.
12. (c) Davies, H. M. L.; Boebel, T. A. Tetrahedron Lett. 2000, 41, 8189-8192.
13. Davies, H. M. L.; Bruzinski, P. R.; Lake, D. H.; Kong, N.; Fall, M. J. J. Am. Chem. Soc. 1996, 118, 6897-6907.
14. (a) Davies, H. M. L.; Hu, B. J. Org. Chem. 1992, 57, 4309-4312.
15. (b) Davies, H. M. L.; Hu, B. J. Org. Chem. 1992, 57, 3186-3190.
16. (c) Davies, H. M. L.; Clark, T. J.; Smith, H. D. J. Org. Chem. 1991, 56, 3817-3824.
17. (d) Davies, H. M. L.; Stafford, D. G.; Doan, B. D.; Houser, J. H. J. Am. Chem. Soc. 1998, 120, 3326-3331.
18. (a) Davies, H. M. L.; Hutcheson, D. K. Tetrahedron Lett. 1993, 34, 7243-7246.
19. (b) Davies, H. M. L.; Townsend, R. J. J. Org. Chem. 2001, 66, 6595-6603.
20. Davies, H. M. L.; Panaro, S. A. Tetrahedron Lett. 1999, 40, 5287-5290.
21. Davies, H. M. L.; Xiang, B.; Kong, N.; Stafford, D. G. J. Am. Chem. Soc. 2001, 123, 7461-7462.
22. Singleton, D. A.; Thomas, A. A. J. Am. Chem. Soc. 1995, 117, 9357-9358.
23. Anciaux, A. J.; Hubert, A. J.; Noels, A. F.; Petiniot, N.; Teyssié, P. J. Org. Chem. 1980, 45, 695-702.
24. Davies, H. M. L.; Rusiniak, L. Tetrahedron Lett. 1998, 39, 8811-8812.
25. 13C KIEs observed here are consistent with those observed in asynchronous but concerted Diels-Alder reactions. See: (a) Singleton, D. A.; Merrigan, S. R.; Beno, B. R.; Houk, K. N. Tetrahedron Lett. 1999, 40, 5817-21.
26. (b) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A. A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149-5160.
27. 4, would have increased concerns over the identity of the actual catalyst.
28. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; 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.; 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. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.11.2; Gaussian, Inc.: Pittsburgh, PA, 2001.
29. (a) Sheehan, S. M.; Padwa, A.; Snyder, J. P. Tetrahedron Lett. 1998, 39, 949-952.
30. (b) Padwa, A.; Snyder, J. P.; Curtis, E. A.; Sheehan, S. M.; Worsencroft, K. J.; Kappe, C. O. J. Am. Chem. Soc. 2000, 122, 8155-8167.
31. Nakamura, E.; Yoshikai, N.; Yamanaka, M. J. Am. Chem. Soc. 2002, 124, 7181-7192.
32. For a discussion of theoretical methods applied to transition-metal containing systems, see: Siegbahn, P. E. M.; Blomberg, M. R. A. Chem. Rev. 2000, 100, 421-437.
33. Yates, P. J. Am. Chem. Soc. 1952, 74, 5376-5381.
34. Cotton, F. A.; Hilliard, E. A.; Murillo, C. A. J. Am. Chem. Soc. 2002, 124, 5658-5660.
35. Pirrung, M. C.; Liu, H.; Morehead, A. T., Jr. J. Am. Chem Soc. 2002, 124, 1014-1023.
36. Lynch, B. J.; Truhlar, D. G. J. Phys. Chem. A 2001, 105, 2936.
37. Doering, W. v. E.; Henderson, W. A., Jr. J. Am. Chem. Soc. 1958, 80, 5274-5277.
38. Keeting, A. E.; Merrigan, S. R.; Singleton, D. A.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3933-38.
39. The potential energy barrier is 2.6 kcal/mol (including zpe) versus a weak π complex with a carbene-styrene separation of 3.5 Å. The π complex is kinetically irrelevant because it would not be a bound species on the free energy surface at 25°C, but its energy is relevant in showing the shape of the potential energy surface.
40. Davies, H. M. L.; Panaro, S. A. Tetrahedron 2000, 56, 4871-4880.
41. The calculations used the program QUIVER (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989-8994) with Becke3LYP frequencies scaled by 0.9614. (Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502-16513).
42. The calculations used the program QUIVER (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989-8994) with Becke3LYP frequencies scaled by 0.9614. (Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502-16513).
43. (a) Bigeleisen, J.; Mayer, M. G. J. Chem. Phys. 1947, 15, 261.
44. (b) Wolfsberg, M. Acc. Chem. Res. 1972, 5, 225.
45. (c) Bigeleisen, J. J. Chem. Phys. 1949, 17, 675.
46. Bell, R. P. The Tunnel Effect in Chemistry; Chapman & Hall: London, 1980; pp 60-63.
47. 13C KIE arises from a temperature-independent ratio of imaginary frequencies for the isotopomers. Because of this, there is very little variation in the predicted KIEs with temperature.
48. Houk, K. N.; Rondan, N. G. J. Am. Chem. Soc. 1984, 106, 4293-4294.
49. In the particular case of 11, taking steps of 0.05 Å along the minimum-energy path in both directions afforded geometries with a lower predicted free energy (including entropy and enthalpic and zpe corrections calculated from unscaled frequencies at 298 K). Thus, despite the low potential energy barrier, other effects appear to have relatively little impact on the position of the transition state.
50. 4 affords mainly the trimer (see ref 3) but gives cyclopropanation adducts in an approximately 12:1 ratio.
51. These studies used default parameters in CS Chem3D Pro, Version 5.0 (1999), CambridgeSoft Corp.: Cambridge, MA, treating the carboxylate carbons as alkenyl carbons. Several of the parameters employed were unrealistic-for example the Rh-O bond distance was only ≈ 1.93 Å-but were likely satisfactory for the purpose of identifying accessible conformations.
52. Doyle, M. P.; Winchester, W. R.; Hoorn, J. A. A.; Lynch, V.; Simonsen, S. H.; Ghosh, R. J. Am. Chem. Soc. 1993, 115, 9968.
53. An 8% error from NMR in the ratio of the product to the starting material would correspond to a change from 84:16 (5.25:1) to 85:15 (5.67:1) (5.67/5.25 = 1.08).