C O MMU N I C A T I O N S
(14) For examples of enantioselective catalytic Mukaiyama-Michael reactions
with electrophiles that cannot readily participate in 1,2-addition, see: (a)
Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Tedrow, J. S. J. Am. Chem.
Soc. 1999, 121, 1994-1995. (b) Evans, D. A.; Willis, M. C.; Johnston, J.
N. Org. Lett. 1999, 1, 865-868. (c) Evans, D. A.; Johnston, J. S.; Olhava,
E. J. J. Am. Chem. Soc. 2000, 122, 1635-1649. (d) Evans, D. A.; Rovis,
T.; Kozlowski, M. C.; Downey, C. W.; Tedrow, J. S. J. Am. Chem. Soc.
2000, 122, 9134-9142. (e) Evans, D. A.; Scheidt, K. A.; Johnston, J. N.;
Willis, M. C. J. Am. Chem. Soc. 2001, 123, 4480. (f) Kobayashi, S.; Suda,
S.; Yamada, M.; Mukaiyama, T. Chem. Lett. 1994, 97-100. (g) Bernardi,
A.; Colombo, G.; Scolastico, C. Tetrahedron Lett. 1996, 37, 8921-8924.
(h) Bernardi, A.; Karamfilova, K.; Sanguinetti, S. Scolastico, C. Tetra-
hedron 1997, 53, 13009-13026. (i) Kitajima, H.; Ito, K.; Katsuki, T.
Tetrahedron 1997, 53, 17015-17028. (j) Nishikori, H.; Ito, K.; Katsuki,
T. Tetrahedron: Asymmetry 1998, 9, 1165-1170.
(15) Diels-Alder: (a) Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. J.
Am. Chem. Soc. 2000, 122, 4243. (b) Northrup, A. B.; MacMillan, D. W.
C. J. Am. Chem. Soc. 2002, 124, 2458. Nitrone cycloaddition: (c) Jen,
W. S.; Wiener, J. J. M.; MacMillan, D. W. C. J. Am. Chem. Soc. 2000,
122, 9874. Pyrrole substitution: (d) Paras, N. A.; MacMillan, D. W. C.
J. Am. Chem. Soc. 2001, 123, 4370. Indole substitution: (e) Austin, J. F.;
MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172. Aniline
substitution: (f) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc.
2002, 124, 7894.
(16) For notable examples of enantioslective organocatalytic reactions, see:
Aldol reaction: (a) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39,
1615. (b) Eder, U.; Sauer, G.; Wiechert, R. Angew. Chem., Int. Ed. Engl.
1971, 10, 496. (c) Agami, C.; Meyneir, F.; Puchot, C. Tetrahedron 1984,
40, 1031. (d) List, B.; Lerner, R. A.; Barbas, C. F. J. Am. Chem. Soc.
2000, 122, 2395. (e) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001,
3, 573. (f) List, B. J. Am. Chem. Soc. 2000, 122, 9336. Phase-transfer
catalysis: (g) O’Donnell, M. J.; Bennett, W. D.; Wu, S. D. J. Am. Chem.
Soc. 1989, 111, 2353. (h) Corey, E. J.; Bo, Y. X.; Busch-Petersen, J. J.
Am. Chem. Soc. 1998, 120, 13000. (i) Corey, E. J.; Xu, F.; Noe, M. C. J.
Am. Chem. Soc. 1997, 119, 12414. Epoxidation: (j) Yang, D.; Yip, Y.
C.; Tang, M. W.; Wong, M. K.; Zheng, J. H.; Cheung, K. K. J. Am. Chem.
Soc. 1996, 118, 491. (k) Yang, D.; Wong, M. K.; Yip, Y. C.; Wang, X.
C.; Tang, M. W.; Zheng, J. H.; Cheung, K. K. J. Am. Chem. Soc. 1998,
120, 5943. (l) Tu, Y.; Wang, Z. X.; Shi, Y. J. Am. Chem. Soc. 1996, 118,
9806. (m) Tian, H. Q.; She, X. G.; Shu, L. H.; Yu, H. W.; Shi, Y. J. Am.
Chem. Soc. 2000, 122, 11551. (n) Denmark, S. E.; Wu, Z. C. Baylis-
Hillman Reaction (o) Iwabuchi, Y.; Nakatani, M.; Yokoyama, N.;
Hatakeyama, S. J. Am. Chem. Soc. 1999, 121, 10219. (p) Corey, E. J.;
Zhang, F. Y. Org. Lett. 1999, 1, 1287. Asymmetric Strecker synthesis:
(q) Vachal, P.; Jacobsen, E. N. Org. Lett. 2000, 2, 867. (r) Sigman, M.
S.; Vachal, P.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2000, 39, 1279.
(s) Corey, E. J.; Grogan, M. J. Org. Lett. 1999, 1, 157. Acyl transfer: (t)
Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J.; Miller,
S. J. J. Am. Chem. Soc. 1999, 121, 11638. Intramolecular Stetter: (u)
Kerr, M. S.; Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc. 2002, 124,
10298-10299. For an excellent review on enantioselective organocatalysis,
see: Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2001, 40, 3726.
(17) A Monte Carlo simulation using the MM3 force-field; Macromodel V6.5.
(18) Asaoka, M.; Miyake, K.; Takei, H. Chem. Lett. 1977, 167.
(19) To a 2-dram vial equipped with a magnetic stir bar and charged with
(2S,5S)-5-benzyl-2-tert-butyl-3-methyl-imidazolidin-4-one was added sol-
vent, 2,4-dinitrobenzoic acid and aldehyde, and then it was placed in a
bath at appropriate temperature. The solution was stirred for 10 min before
the addition of siloxy furan substrate in one portion. The resulting solution
was stirred at a constant temperature until the reaction was determined to
be complete by a GLC conversion assay using dibenzyl ether as an internal
standard. The reaction mixture was then transferred cold through a silica
gel plug with ethyl acetate into a flask and carefully concentrated in vacuo.
The resulting residue was purified by silica gel chromatography (solvents
noted) and fractions carefully concentrated in vacuo to provide the title
compounds. The enantioselectivity was determined by chiral GLC analysis.
(20) Inoue, K. Fureguransu Janaru 1983, 11, 53-55.
Acknowledgment. Financial support was provided by the
NIHGMS (R01 GM66142-01) and kind gifts from AstraZeneca,
Boehringer-Ingelheim, Bristol-Myers Squibb, Dupont, GlaxoSmith-
Kline, Johnson and Johnson, Lilly, Materia, Merck Research
Laboratories, Pfizer, Pharmacia, and Roche Biosciences. We also
thank Great Lakes for their generous donation of (S)-phenylalanine.
D.W.C.M is grateful for support from the Sloan Foundation and
Research Corporation under the Cottrell Scholarship and Research
Innovation programs.
Supporting Information Available: Experimental procedures,
structural proofs, and spectral data for all new compounds (PDF).
This material is available free of charge via the Internet at http://
pubs.acs.org.
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