Palladium-catalyzed synthesis of cyclopentane-fused benzocyclobutenes via tandem directed carbopalladation/ C-H bond functionalization

Organic Letters

Volumn 9, Issue 16, 2007, Pages 3073-3075

  Bertrand, Myra Beaudoin ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZOCYCLOBUTENE; CYCLOPENTANE DERIVATIVE; PALLADIUM; POLYCYCLIC HYDROCARBON; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

CATALYSIS; CYCLOPENTANES; MOLECULAR STRUCTURE; PALLADIUM; POLYCYCLIC COMPOUNDS; STEREOISOMERISM;

EID: 34547956358     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol071120f     Document Type: Article

References (28)

1. (a) Ney, J. E.; Wolfe, J. P. Angew. Chem., Int. Ed. 2004, 43, 3605.
2. (b) Bertrand, M. B.; Wolfe, J. P. Tetrahedron 2005, 61, 6447.
3. (c) Ney, J. E.; Wolfe, J. P. J. Am. Chem. Soc. 2005, 127, 8644.
4. (d) Bertrand, M. B.; Wolfe, J. P. Org. Lett. 2006, 8, 2353.
5. (e) Wolfe, J. P. Eur. J. Org. Chem. 2007, 571 and references cited therein.
6. Bertrand, M. B.; Leathen, M. L.; Wolfe, J. P. Org. Lett. 2007, 9, 457.
7. Dpe-Phos = bis(2-diphenylphosphinophenyl) ether.
8. For Pd-catalyzed reactions of aryl bromides with norbornene and related bicyclo[2.2.n]alkenes that afford benzocyclobutene products, see: (a) Catellani, M.; Chiusoli, G. P.; Ricotti, S. J. Organomet. Chem. 1985, 296, C11.
9. (b) Catellani, M.; Chiusoli, G. P.; Ricotti, S.; Sabini, F. Gazz. Chim. Ital. 1985, 115, 685.
10. (c) Catellani, M.; Ferioli, L. Synthesis 1996, 769.
11. (a) Sadana, A. K.; Saini, R. K.; Billups, W. E. Chem. Rev. 2003, 103, 1539.
12. (b) Mehta, G.; Kotha, S. Tetrahedron 2001, 57, 625.
13. Farona, M. F. Prog. Polym. Sci. 1996, 21, 505.
14. These structures were assigned by comparison of NMR spectra to those obtained for isolated samples of 5, 12, and a previously described N-aryl analogue of 10. See ref 1c.
15. The remainder of the mixture consisted of 5% N-arylated substrate and 8% of unidentified products.
16. A similar result was obtained with 2-bromo-m-xylene, which afforded a 5-aryl azabicyclo[3.3.0]octane in 30% yield (ca. 40% conversion). See the Supporting Information for complete details.
17. Amino complex refers to coordination of the neutral carbamate, whereas amido complex refers to coordination of the deprotonated, anionic carbamate. For discussion of kinetic and thermodynamic effects in amido complex formation, see: (a) Meyers, C.; Maes, B. U. W.; Loones, K. T. J.; Bal, G.; Lemiere, G. L. F.; Dommisse, R. A. J. Org. Chem. 2004, 69, 6010.
18. (b) Driver, M. S.; Hartwig, J. F. Organometallics 1997, 16, 5706.
19. When NaOtBu is employed as base the amido complex could also be generated via reaction of 13 with deprotonated carbamate, or through reaction of the carbamate with a LnPd(Ar)(OtBu) complex. See: Shekhar, S.; Hartwig, J. F Organometallics 2007, 26, 340.
20. For early examples, see: (a) Kasahara, A.; Izumi, T.; Takeda, T.; Imamura, H. B. Chem. Soc. Jpn. 1974, 47, 183.
21. (b) Andersson, C.-M.; Larsson, J.; Hallberg, A. J. Org. Chem. 1990, 55, 5757.
22. For a recent review see: Oestreich, M. Eur. J. Org. Chem. 2005, 783.
23. For recent reviews, see: (a) Campeau, L.-C.; Fagnou, K. Chem. Commun. 2006, 1253.
24. (b) Catellani, M. Synlett 2003, 298.
25. For tandem intermolecular carbopalladation/C-H functionalization processes involving alkenylpalladium intermediates, see: (a) Pinto, A.; Neuville, L.; Retailleau, P.; Zhu, J. Org. Lett. 2006, 8, 4927.
26. (b) Furuta, T.; Asakawa, T.; Iinuma, M.; Fujii, S.; Tanaka, K.; Kan, T. Chem. Commun. 2006, 3648.
27. (a) Campora, J.; Gutierrez-Puebla, E.; Lopez, J. A.; Monge, A.; Palma, P.; del Rio, D.; Carmona, E. Angew. Chem., Int. Ed. 2001, 40, 3641
28. (b) Catellani, M.; Frignani, F.; Rangoni, A. Angew. Chem., Int. Ed. 1997, 36, 119.