Novel Synthesis of a New Skeletal Compound Benzonaphthazepine by Regioselective C-H Activation Utilizing the Intramolecular Coordination of an Amine to Pd

Takashi Harayama; Tomonori Sato; Akihiro Hori; Hitoshi Abe; Yasuo Takeuchi

doi:10.1055/s-2004-822371

PAPER

Novel Synthesis of a New Skeletal Compound Benzonaphthazepine by Regioselective C-H Activation Utilizing the Intramolecular Coordination of an Amine to Pd

Takashi Harayama*, Tomonori Sato, Akihiro Hori, Hitoshi Abe, Yasuo Takeuchi
Faculty of Pharmaceutical Sciences, Okayama University, Tsushima-naka 1-1-1, Okayama 700-8530, Japan
Fax: +81(86)2517963; e-Mail: harayama@pharm.okayama-u.ac.jp;

Abstract

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Abstract

The novel synthesis of a new skeletal compound, benzonaphthazepine, from N-bromobenzylnaphthylamine using a Pd reagent is described. In the biaryl coupling reaction of N-bromobenzylnaphthylamine using a Pd reagent, the intramolecular coordination of the benzylamino group to Pd causes regioselective C-H activation at the peri position relative to the amine group on the naphthalene ring, producing benzonaphthazepine in good to excellent yield. The bulkiness of the substituent at C₇ on the naphthalene ring affects the regioselectivity of the biaryl coupling reaction.

Key Words

C-H activation - heterocycles - palladium - regioselectivity - coordination

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References

1a Tsuji J. Palladium Reagents and Catalysts John Wiley & Sons Inc.; New York: 1995. p.125-252

1b Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry Pergamon; Oxford: 2000.

1c Dyker G. Angew. Chem. Int. Ed. 1999, 38: 1698

1d Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev. 2002, 102: 1359

2a Harayama T. Shibaike K. Heterocycles 1998, 49: 191

2b Harayama T. Akiyama T. Akamatsu H. Kawano K. Abe H. Takeuchi Y. Synthesis 2001, 444

2c Harayama T. Akamatsu H. Okamura K. Miyagoe T. Akiyama T. Abe H. Takeuchi Y. J. Chem. Soc., Perkin Trans. 1 2001, 523

2d Harayama T. Akiyama T. Nakano Y. Nishioka H. Abe H. Takeuchi Y. Chem. Pharm. Bull. 2002, 50: 519

2e Harayama T. Akiyama T. Nakano Y. Shibaike K. Akamatsu H. Hori A. Abe H. Takeuchi Y. Synthesis 2002, 237

2f Harayama T. Hori A. Nakano Y. Akiyama T. Abe H. Takeuchi Y. Heterocycles 2002, 58: 159

2g Harayama T. Sato T. Nakano Y. Abe H. Takeuchi Y. Heterocycles 2003, 59: 293

3a Harayama T. Morikami Y. Shigeta Y. Abe H. Takeuchi Y. Synlett 2003, 847

3b Harayama T. Hori A. Abe H. Takeuchi Y. Tetrahedron 2004, 60: 1611

4 Preliminary communication: Harayama T. Sato T. Hori A. Abe H. Takeuchi Y. Synlett 2003, 1141

5a Cope AC. Friedrich EC. J. Am. Chem. Soc. 1968, 90: 909

5b Bruce MI. Angew. Chem., Int. Ed. Engl. 1977, 16: 73

6a Clark PW. Dyke SF. J. Organomet. Chem. 1985, 243: 389

6b Martín-Mature B. Mateo CJ. Cárdenas D. Echavarren AM. Chem.-Eur. J. 2001, 7: 2341

6c Dyker G. Chem. Ber. 1997, 243: 1567

6d Jia C. Piao D. Oyamada J. Lu W. Kitamura T. Fujiwara Y. Science 2000, 287: 1992

7 Banwell MG. Flynn BL. Stewart SG. J. Org. Chem. 1998, 63: 9139

8

The coupling reaction of 5a using Pd₂(dba)₃ (0.2 equiv) in degassed DMF gave no product and this was accompanied by decomposition of the starting material.

9 Nakanishi T. Suzuki M. J. Prod. Chem. 1998, 61: 1263

10 Stermitz FR. Gillespie JP. Amoros LG. Romero R. Stermitz TA. J. Med. Chem. 1975, 18: 708

11 Dalla V. Cotelle P. Tetrahedron 1999, 55: 6923

12 Wu S.-J. Chen I.-S. Chern C.-Y. Teng C.-M. Wu T.-S. J. Chin. Chem. Soc. 1996, 43: 195

13a Vila JM. Suarez A. Pereira MT. Gayoso E. Gayoso M. Polyhedron 1987, 6: 1003

13b Teijido B. Fernández A. López-Torres M. Castro-Juiz S. Suárez A. Ortigueira JM. Vila JM. Fernández JJ. J. Organomet. Chem. 2000, 598: 71

14 Green GR. Mann IS. Mullane M. McKillop A. Tetrahedron 1998, 54: 9875