An experimental and theoretical study of the asymmetric lithiation of 1,2,3,5,6,7-hexahydro-3a,4a-diazacyclopenta[def]phenanthren-4-one

Journal of Organic Chemistry

Volumn 72, Issue 3, 2007, Pages 957-963

  Metallinos, Costa ^a   Dudding, Travis ^a   Zaifman, Josh ^a   Chaytor, Jennifer L ^a   Taylor, Nicholas J ^b  

^a BROCK UNIVERSITY   (Canada)

^b UNIVERSITY OF WATERLOO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

1,2,3,5,6,7-HEXAHYDRO-3A,4A-DIAZACYCLOPENTA[DEF]PHENANTHREN-4-ONE; ASYMMETRIC LITHIATION; ELECTROPHILE QUENCH; ENANTIOMERIC RATIO;

ACTIVATION ENERGY; BROMINE COMPOUNDS; COMPUTATIONAL METHODS; LITHIUM; SINGLE CRYSTALS; STEREOCHEMISTRY; UREA; X RAY ANALYSIS;

KETONES;

1,2,3,5,6,7 HEXAHYDRO 3A,4A DIAZACYCLOPENTA[DEF]PHENANTHREN 4 ONE; HYDROGEN; LITHIUM DERIVATIVE; PHENANTHRENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; EXPERIMENTAL STUDY; LITHIATION; STEREOCHEMISTRY; STRUCTURE ANALYSIS; THEORETICAL STUDY; X RAY CRYSTALLOGRAPHY;

EID: 33846932791     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo062244t     Document Type: Article

References (49)

1. Hoppe, D.; Zschage, O. Angew. Chem., Int. Ed. Engl. 1989, 28, 69.
2. Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1991, 113, 9708.
3. Beak, P.; Kerrick, S. T.; Wu, S.; Chu, J. J. Am. Chem. Soc. 1994, 116, 3231.
4. Reviews of asymmetric lithiation: (a) Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2282.
5. (b) Beak, P.; Basu, A.; Gallagher, D. J.; Park, Y. S.; Thayumanavan, S. Acc. Chem. Res. 1996, 29, 552.
6. (c) Hoppe, D.; Hintze, F.; Tebben, P.; Paetow, M.; Ahrens, H.; Schwerdtfeger, J.; Sommerfeld, P.; Haller, J.; Guarnieri, W.; Kolczewski, S.; Hense, T.; Hoppe, I. Pure Appl. Chem. 1994, 66, 1479.
7. (d) Hoppe, D.; Kramer, T.; Schwark, J. R.; Zschage, O. Pure Appl. Chem. 1990, 62, 1999.
8. (e) Hoppe, D.; Christoph, G. In The Chemistry of Functional Groups; Rappoport, Z., Marek, I., Eds.; Wiley: Chichester, UK, 2004; pp 1077-1164.
9. Reviews of lithiation α to nitrogen: (a) Gawley, R. E.; O'Connor, S.; Klein, R. In Science of Synthesis; Majewski, M., Snieckus, V., Eds.; Thieme: Stuttgart, Germany, 2005; Vol. 8a, pp 677-757.
10. (b) Beak, P.; Johnson, T. A.; Kim, D. D.; Lim, S. H. In Topics in Organometallic Chemistry; Hodgson, D. M., Ed.; Springer-Verlag: Berlin, Germany, 2003; Vol. 5, pp 139-176.
11. Bailey, W. F.; Beak, P.; Kerrick, S. T.; Ma, S.; Wiberg, K. B. J. Am. Chem. Soc. 2002, 124, 1889.
12. Beak, P.; Lee, W. K. J. Org. Chem. 1993, 58, 1109.
13. (a) Dearden, M. J.; Firkin, C. R.; Hermet, J.-P.; O'Brien, P. J. Am. Chem. Soc. 2002, 124, 11870.
14. (b) Dixon, A. J.; McGrath, M. J.; O'Brien, P. Org. Synth. 2006, 83, 141-154.
15. McGrath, M. J.; Bilke, J. L.; O'Brien, P. J. Chem. Soc., Chem. Commun. 2006, 2607.
16. Metallinos, C.; Barrett, F. B.; Chaytor, J. L.; Heska M. E. A. Org. Lett. 2004, 6, 3641.
17. Metallinos, C.; Barrett, F. B; Wang, Y.; Xu, S.; Taylor, N. J. Tetrahedron 2006, 62, 11145.
18. Meyers, A. I.; Milot, G. J. Org. Chem. 1993, 58, 6538 and references cited therein.
19. Bertini Gross, K. M.; Jun, Y. M.; Beak, P. J. Org. Chem. 1997, 62, 7679.
20. For a review of Complex Induced Proximity Effects (CIPE), see: Whisler, M. C.; MacNeil, S.; Snieckus, V.; Beak, P. Angew. Chem., Int. Ed. 2004, 43, 2206.
21. See also: Bertini Gross, K. M.; Beak, P. J. Am. Chem. Soc. 2001, 123, 315.
22. Boltzmann distributions were calculated with Spartan02.
23. See the Supporting Information for an overlay of the conformational groupings.
24. Snieckus, V. Chem. Rev. 1990, 90, 879.
25. Smith, K.; El-Hiti, G.; Shukla, A. P. J. Chem. Soc., Perkin Trans. 1 1999, 2305.
26. (a) Clayden, J.; Turner, H.; Pickworth, M.; Adler, T. Org. Lett. 2005, 7, 3147.
27. (b) For lateral lithiations, see: Clayden, J.; Dufour, J. Tetrahedron Lett. 2006, 47, 6945.
28. Meigh, J.-P.; Álvarez, M.; Joule, J. A. J. Chem. Soc., Perkin Trans. 1 2001, 2012.
29. Hartung, C. G.; Fecher, A.; Chapell, B.; Snieckus, V. Org. Lett. 2003, 5, 1899.
30. All enantiomeric ratios were determined by chiral stationary phase (CSP) HPLC on a Chiralpak AS-H or a Chiralcel OD-H column.
31. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 116, 2516.
32. Thayumanavan, S.; Lee, S.; Liu, C.; Beak, P. J. Am. Chem. Soc. 1994, 116, 9755.
33. Berkheij, M.; van der Sluis, L.; Sewing, C.; den Boer, D. J.; Terpstra, J. W.; Hiemstra, H.; Bakker, W. I. I.; van den Hoogenband, A.; van Maarseveen, J. H. Tetrahedron Lett. 2005, 46, 2369.
34. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian '03; Gaussian, Inc.: Wallingford CT, 2004.
35. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
36. (b) Stephens, P. J.; Devlin, F. J.; Chabalowski, G. C.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
37. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B. 1987, 37, 785.
38. (a) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294.
39. (b) Frisch, M. J.; Pople, J. A.; Binkley, J. S. J. Chem. Phys. 1984, 80, 3265.
40. Gallagher, D. J.; Beak, P. J. Org. Chem. 1995, 50, 7092.
41. Würthwein, E.-U.; Hoppe, D. J. Org. Chem. 2005, 70, 4443.
42. The sum of two hydrogen van der Waals radii is 2.40 Å: Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press; Ithaca, NY, 1960; p. 260.
43. Phuan, P.-W.; Ianni, J. C.; Kozlowski, M. C. J. Am. Chem. Soc. 2004, 126, 15473 and references cited therein.
44. 2 effect will be discussed in a forthcoming communication.
45. Bijvoet, J. M.; Peerdeman, A. F.; Van Bommel, A. J. Nature 1951, 168, 271.
46. Bates, H. A.; Condulis, N.; Stein, N. L. J. Org. Chem. 1986, 51, 2228.
47. The procedure as used in the preparation of 1,2-dibromo-3,4,5,6- tetramethylbenzene was followed: (a) Kajigaeshi, S.; Kakinami, T.; Moriwaki, M.; Tanaka, T.; Fujisaki, S.; Okamoto, T. Bull. Chem. Soc. Jpn. 1989, 62, 439.
48. (b) Vorogushin, A. V.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 8146.
49. See the Supporting Information for an ORTEP plot of dibromide 26.