Enantioselective thiourea-catalyzed additions to oxocarbenium ions

Journal of the American Chemical Society

Volumn 130, Issue 23, 2008, Pages 7198-7199

  Reisman, Sarah E ^a   Doyle, Abigail G ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; CHLORINE DERIVATIVE; ION; OXOCARBENIUM ION; THIOUREA;

ADDITION REACTION; ARTICLE; BINDING KINETICS; BIOTRANSFORMATION; CATALYSIS; CATALYST; CHIRALITY; COMPLEX FORMATION; DISSOCIATION CONSTANT; ENANTIOSELECTIVITY; HYDROGEN BOND; MANNICH REACTION; PICTET SPENGLER REACTION; REACTION ANALYSIS; STEREOCHEMISTRY;

ACETALS; CATALYSIS; CHROMANS; STEREOISOMERISM; THIOUREA;

EID: 44949230317     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja801514m     Document Type: Article

References (34)

1. For reviews, see: (a) Doyle, A. G.; Jacobsen, E. N. Chem. Rev. 2007, 107, 5713-5743.
2. (b) Taylor, M. S.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2006, 45, 1520-1543.
3. (c) Bolm, C.; Rantanen, T.; Schiffers, I.; Zani, L. Angew. Chem., Int. Ed. 2005, 44, 1758-1763.
4. (d) Pihko, P. M. Angew. Chem., Int. Ed. 2004, 43, 2062-2064.
5. (e) Oestreich, M. Nachr. Chem. 2004, 52, 35-38.
6. (f) Schreiner, P. R. Chem. Soc. Rev. 2003, 32, 289-296.
7. (a) Taylor, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 10558-10559.
8. (b) Taylor, M. S.; Tokunaga, N.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 6700-6704.
9. (c) Raheem, I. T.; Thiara, P. S.; Peterson, E. A.; Jacobsen, E. N. J. Am. Chem. Soc. 2007, 129, 13404-13405. See also:
10. (d) Pan, S. C.; Zhou, J.; List, B. Angew. Chem., Int. Ed. 2007, 46, 2971-2973.
11. For a reviews of C- and O-glycoside formation within total synthesis, see: (a) Du, Y. G.; Linhardt, R. J.; Vlahov, I. R. Tetrahedron 1998, 54, 9913-9959.
12. (b) Pellissier, H. Tetrahedron 2005, 61, 2947-2993.
13. For systematic studies of substituent effects on the nucleophilic addition to five- and six-membered oxocarbenium ions, see: (a) Ayala, L.; Lucero, C. G.; Romero, J. A. C.; Tabacco, S. A.; Woerpel, K. A. J. Am. Chem. Soc. 2003, 125, 15521.
14. (b) Larsen, C. H.; Ridgway, B. H.; Shaw, J. T.; Smith, D. M.; Woerpel, K. A. J. Am. Chem. Soc. 2005, 127, 10879-10884.
15. Braun, M.; Kotter, W. Angew. Chem., Int. Ed. 2004, 43, 514-517.
16. For additions of catalytically-generated chiral metal enolates to symmetric oxocarbenium ions, see: Evans, D. A.; Thomson, R. J. J. Am. Chem. Soc. 2005, 127, 10506-10507.
17. For ketalizations catalyzed by achiral thioureas, see: (a) Kotke, M.; Schreiner, P. R. Tetrahedron 2006, 62, 434-439.
18. (b) Kotke, M.; Schreiner, P. R. Synthesis 2007, 779-790.
19. Xu, Y. C.; Lebeau, E.; Gillard, J. W.; Attardo, G. Tetrahedron Lett. 1993, 34, 3841-3844.
20. 3-mediated preparation of α-chloroethers, see: Berger, D.; Overman, L. E.; Renhowe, P. A. J. Am. Chem. Soc. 1997, 119, 2446-2452.
21. Although 1-chloroisochroman (7) undergoes hydrolysis when exposed to moist air, it can be distilled and is stable indefinitely when stored under nitrogen in a-78°C freezer.
22. (a) Wenzel, A. G.; Lalonde, M. P.; Jacobsen, E. N. Synlett 2003, 1919-1922. The utility of bis(trifluoromethyl)aniline-derived thioureas in catalysis via H-bonding was established by Schreiner.
23. (b) Wittkopp, A.; Schreiner, P. R. Chem., Eur. J. 2003, 9, 407-414.
24. See Supporting Information for details.
25. Preparation of enantioenriched 2-arylpyrrolidines: Campos, K. R.; Klapars, A.; Waldman, J. H.; Dormer, P. G.; Chen, C. Y. J. Am. Chem. Soc. 2006, 128, 3538-3539.
26. TenBrink, R. E.; Bergh, C. L.; Duncan, J. N.; Harris, D. W.; Huff, R. M.; Lahti, R. A.; Lawson, C. F.; Lutzke, B. S.; Martin, I. J.; Rees, S. A.; Schlachter, S. K.; Sih, J. C.; Smith, M. W. J. Med. Chem. 1996, 39, 2435-2437.
27. A titanium-catalyzed dynamic kinetic resolution of configurationally stable indanols via ion-paired carbocationic intermediates has been reported. See ref 5.
28. (a) Antonisse, M. M. G.; Reinhoudt, D. N. Chem. Commun. 1998, 443-448.
29. (b) Hisaki, I.; Sasaki, S. I.; Hirose, K.; Tobe, Y. Eur. J. Org. Chem. 2007, 607-615.
30. (c) Jagessar, R. C.; Shang, M. Y.; Scheidt, W. R.; Burns, D. H. J. Am. Chem. Soc. 1998, 120, 11684-11692.
31. (d) Schmidtchen, F. P.; Berger, M. Chem. Rev. 1997, 97, 1609-1646.
32. Similar reactivity and slightly diminished enantioselectivity is observed using urea analogues of catalyst 15 for the addition of 17a to 7 (i.e., 84 versus 92% ee with 15). This renders highly unlikely any mechanism involving a direct, productive interaction of the the thiocarbonyl with either the 1-chloroisochroman or oxocarbenium intermediate.
33. For mechanistic studies on the addition of silyl ketene acetals to carbenium ions, see: Burfeindt, J.; Patz, M.; Muller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629-3634.
34. Preliminary results obtained in additions to both simple and stereochemically complex tetrahydropyranyl derivatives are included in the Supporting Information.