Origin of stereoselectivity in the imidazolidinone-catalyzed reductions of cyclic α,β-unsaturated ketones

Organic Letters

Volumn 11, Issue 19, 2009, Pages 4298-4301

  Gutierrez, Osvaldo ^a   Iafe, Robert G ^a   Houk, K N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTANE DERIVATIVE; IMIDAZOLIDINE DERIVATIVE; KETONE;

ARTICLE; CATALYSIS; CHEMICAL MODEL; CHEMICAL STRUCTURE; CHEMISTRY; COMPUTER SIMULATION; HYDROGENATION; OXIDATION REDUCTION REACTION; STEREOISOMERISM; SYNTHESIS;

CATALYSIS; COMPUTER SIMULATION; CYCLOPENTANES; HYDROGENATION; IMIDAZOLIDINES; KETONES; MODELS, CHEMICAL; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; STEREOISOMERISM;

EID: 70350145617     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol901586t     Document Type: Article

References (25)

1. Hantzsch, A. Justus Liebigs Ann. Chem. 1882, 215, 1.
2. (a) You, S. Chem. Asian J. 2007, 2, 820.
3. (b) Adolfsson, H. Angew. Chem., Int. Ed. 2005, 44, 3340.
4. (c) Ouellet, S. G.; Walji, A. M.; MacMillan, D. W. C. Acc. Chem. Res. 2007, 40, 1327.
5. Turtle, J. B.; Ouellet, S. G.; MacMillan, D. W. C. J. Am. Chem. Sac. 2006, 128, 12662.
6. Martin, N. J. A.; List, B. J. Am. Chem. Soc. 2006, 128, 13368.
7. Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 2458.
8. Yang, J. W.; Fonseca, M. T. H.; Vignola, N.; List, B. Angew. Chem., Int. Ed. 2004, 44, 108.
9. Ouellet, S. G.; Tuttle, J. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 32.
10. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
11. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B. 1988, 37, 785.
12. (a) Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724.
13. (b) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
14. (c) Hariharan, P. C.; Pople, J. A. Theor. Chem. Acta 1973, 28, 213.
15. Frisch, M. J. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford CT, 2004 (For full reference, see Supporting Information).
16. See, for example: (a) Um, J. M.; Houk, K. N.; Phillips, A. J. Org. Lett. 2008, 10, 3769.
17. (b) Iafe, R.; Houk, K. N. Org. Lett. 2006, 8 (16), 3469.
18. (c) Gordillo, R.; Carter, J.; Houk, K. N. Adv. Synth. Catal. 2004, 346, 1175.
19. The X-ray structures of the iminium ion intermediate derived from cinnamaldehyde and 2 are available, (a) Groselj, U.; Badine, D. M.; Schweizer, W. B.; Beck, A. K.; Seebach, D. Helv. Chim. Acta 2008, 91, 1999.
20. (b) Schweizer, W. B.; Ebert, M.; Seebach, D. K. Helv. Chim. Acta 2009, 92, 1.
21. For a detailed DFT study on conformers with 3 and cinnamaldehyde. Gordillo, R.; Houk, K. N. J. Am. Chem. Soc. 2006, 128, 3543.
22. The CH/π Interaction: Evidence, Nature, and Consequences; Nishio, M., Umezawa, H. Y., Eds.; Wiley-VCH: New York, 1998.
23. Single-point calculations on iminium ion intermediates at the B3LYP/6-311++G(d,p) revealed similar E/Z ratio of 62:38. A similar ratio, 66:34, was calculated for the iminium ions formed from the reaction from 3 and 3-m.ethyl-2-cyclopentenone at the B3LYP/6-31G(d) level.
24. Wu, Y.; Houk, K. N. J. Am. Chem. Soc. 1987, 109, 2226.
25. Calculated hydride attack transition, state structures for the reaction with 3-methyl-2-cyclope.nteno.ne imininium intermediate and Hantzsch ester 5 revealed a 0.8 kcal/mol reference for hydride attack on the (E) iminium ion. This result is consistent with experimental data which show a preference for the S product derived upon hydride attack by the t-butyl-substituted Hantzsch ester into the (E) iminium ion.