Synthesis of Methyl 2-Amino-3H-1-benzazepine-4-carboxylates and 2-(Cyanomethyl)-2,3-dihydro-1H-indole-2-carboxylates from Morita-Baylis-Hillman Acetates of 2-(Acylamino)benzaldehydes

Hee Nam Lim; Young Seok Song; Kee-Jung Lee

doi:10.1055/s-2007-990809

PAPER

Synthesis of Methyl 2-Amino-3H-1-benzazepine-4-carboxylates and 2-(Cyanomethyl)-2,3-dihydro-1H-indole-2-carboxylates from Morita-Baylis-Hillman Acetates of 2-(Acylamino)benzaldehydes

Hee Nam Lim, Young Seok Song, Kee-Jung Lee*
Organic Synthesis Laboratory, Department of Chemical Engineering, Hanyang University, Seoul 133-791, Korea
Fax: +82(2)22984101; e-Mail: leekj@hanyang.ac.kr;

Abstract

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Abstract

Methyl 2-Amino-3H-1-benzazepine-4-carboxylates or methyl 2-(cyanomethyl)-2,3-dihydro-1H-indole-2-carboxylates were prepared from the reaction of 3-[2-formamido-, 2-acetamido-, or 2-(propanoylamino)phenyl]-substituted methyl 2-(cyanomethyl)propenoates with sodium methoxide in methanol, respectively. The latter were readily obtained from the Morita-Baylis-Hillman reaction of N-protected 2-aminobenzaldehydes with methyl acrylate followed by acetylation and cyanation.

Key words

Morita-Baylis-Hillman - 2-amino-3H-1-benzazepine - dihydroindole - N-protected 2-aminobenzaldehyde - 3-aryl-2-(cyanomethyl)propenoate

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References

References and Notes

1a Cooper CB, Lyssikatos JP, Mann DW, and Hecker SJ. inventors; EP 825,186. ; Chem. Abstr. 1998, 128, 192567

1b Doherty GA, Eary TC, Groneberg RD, and Jones Z. inventors; WO 2007,024,612. ; Chem. Abstr. 2007, 146, 274240

For reviews of the Morita-Baylis-Hillman reaction, see:

2a Drewes SE. Roos GHP. Tetrahedron 1988, 44: 4653

2b Basavaiah D. Rao PD. Hyma RS. Tetrahedron 1996, 52: 8001

2c Ciganek E. Org. React. 1997, 51: 201

2d Langer P. Angew. Chem. Int. Ed. 2000, 39: 3049

2e Kim JN. Lee KY. Curr. Org. Chem. 2002, 6: 627

2f Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev. 2003, 103: 811

2g Kataoka T. Kinoshita H. Eur. J. Org. Chem. 2005, 45

3a Song YS. Lee CH. Lee K.-J. J. Heterocycl. Chem. 2003, 40: 939

3b Lee CH. Song YS. Cho HI. Yang JW. Lee K.-J. J. Heterocycl. Chem. 2003, 40: 1103

3c Ko SH. Lee K.-J. J. Heterocycl. Chem. 2004, 41: 613

3d Lee CH. Lee K.-J. Synthesis 2004, 1941

3e Hong WP. Lee KJ. Synthesis 2005, 33

3f Hong WP. Lee K.-J. Synthesis 2006, 963

3g Yi H.-W. Park HW. Song YS. Lee K.-J. Synthesis 2006, 1953

4a Singh V. Pathak R. Batra S. Catal. Commun. 2007, 8: 2054

4b Yadav JS. Gupta MK. Pandey SK. Reddy BVS. Sarma AVS. Tetrahedron Lett. 2005, 46: 2761

4c Hong WP. Lim HN. Park HW. Lee K.-J. Bull. Korean Chem. Soc. 2005, 26: 655

5a Boger DL. Nishi T. Bioorg. Med. Chem. 1995, 3: 67

5b Cermenati L. Albini A. Pichat P. Guillard C. Res. Chem. Intermed. 2000, 26: 221

5c Thielges S. Meddah E. Bisseret P. Eustache J. Tetrahedron Lett. 2004, 45: 907

5d Manley PJ. Bilodeau MT. Org. Lett. 2004, 6: 2433

5e Gassman PG. Drewes HR. J. Am. Chem. Soc. 1978, 100: 7600

5f Sharma U. Ahmed S. Boruah RC. Tetrahedron Lett. 2000, 41: 3493

5g Dave RH. Hosangadi BD. Tetrahedron 1999, 55: 11295

5h Fürstner A. Jumbam DN. Tetrahedron 1992, 48: 5991

6a Mason PH. Emslie ND. Tetrahedron 1994, 50: 12001

6b Basavaiah D. Muthukumaran K. Sreenivasulu B. Synthesis 2000, 545

The ratio of cis- and trans-conformers was determined using ¹H NMR coupling constants between the formyl and NH protons (J _trans = 11 Hz/J _cis = 0-2 Hz) according to the following references:

7a Hosseini-Sarvari M. Sharghi H. J. Org. Chem. 2006, 71: 6652

7b Enomoto N. Kondo M. Bull. Chem. Soc. Jpn. 1972, 45: 2665

8a Baldwin JE. J. Chem. Soc., Chem. Commun. 1976, 738

8b Baldwin JE. Thomas RC. Kruse LI. Silberman L. J. Org. Chem. 1977, 42: 3846

9a Glennon RA. J. Med. Chem. 1987, 30: 1

9b Boger DL. Boyce CW. Garbaccio RM. Goldberg JA. Chem. Rev. 1997, 97: 787

10a Creasey WA. In Cancer: A Comprehensive Treatise Vol. 5: Becker FF. Plenum; New York: 1977. p.379-395

10b Gorman M. Neuss N. Biemann K. J. Am. Chem. Soc. 1962, 84: 1058

11 Neuss N. Gorman M. Hargrove W. Cone NJ. Biemann K. Büchi G. Manning RE. J. Am. Chem. Soc. 1964, 86: 1440

12a Preobrazhenskaya MN. Russ. Chem. Rev. 1967, 36: 753

12b Sundberg RJ. Chemistry of Indoles Academic Press; New York: 1970.

12c Indoles Houlihan WJ. Wiley-Interscience; New York: 1972-1979. parts 1-3.

12d Sakamoto T. Kondo Y. Yamanaka H. Heterocycles 1988, 27: 2225

12e Pindur U. Adam R. J. Heterocycl. Chem. 1988, 25: 1

12f Joule JA. Mills K. Smith GF. Heterocyclic Chemistry 3rd ed.: Chapman and Hall; New York: 1995. p.305-349

13a Sloan CP. Cuevas JC. Quesnelle C. Snieckus V. Tetrahedron Lett. 1988, 29: 4685

13b Molander GA. Harring LS. J. Org. Chem. 1990, 55: 6171

13c Wolff S. Hoffmann HMR. Synthesis 1988, 760

13d Boger DL. Palanki MSS. J. Am. Chem. Soc. 1992, 114: 9318

13e Rao AVR. Gurjar MK. Bose DS. Devi RR. J. Org. Chem. 1991, 56: 1320

13f Boger DL. Yun W. Teegarden BR. J. Org. Chem. 1992, 57: 2873

13g Boisvert G. Giasson R. Tetrahedron Lett. 1992, 33: 6587

13h Clive DLJ. Etkin N. Joseph T. Lown JW. J. Org. Chem. 1993, 58: 2442

13i Rai R. Collum DB. Tetrahedron Lett. 1994, 35: 6221

13j Itoh T. Ohara H. Emoto S. Tetrahedron Lett. 1995, 36: 3531

14a Bailey WF. Punzalan ER. J. Am. Chem. Soc. 1994, 116: 6577

14b Bailey WF. Jiang X.-L. J. Org. Chem. 1996, 61: 2596

14c Zhang D. Liebeskind LS. J. Org. Chem. 1996, 61: 2594

14d Bailey WF. Carson MW. J. Org. Chem. 1998, 63: 9960

14e Nakao J. Inoue R. Shinokubo H. Oshima K. J. Org. Chem. 1997, 62: 1910

14f Uchiyama M. Kameda M. Mishima O. Yokoyama N. Koike M. Kondo Y. Sakamoto T. J. Am. Chem. Soc. 1998, 120: 4934

14g Gil GS. Groth UM. J. Am. Chem. Soc. 2000, 122: 6789

15a Mori M. Kudo S. Ban Y. J. Chem. Soc., Perkin Trans. 1 1978, 771

15b Larock RC. Babu S. Tetrahedron Lett. 1987, 28: 5291

15c Larock RC. Stinn DE. Tetrahedron Lett. 1988, 29: 4687

15d Hegedus LS. Angew. Chem., Int. Ed. Engl. 1988, 27: 1113

15e Pattenden G. Chem. Soc. Rev. 1988, 17: 361

15f Larock RC. Stinn DE. Tetrahedron Lett. 1989, 30: 2767

15g Iqbal J. Bhatia B. Nayyar NK. Chem. Rev. 1994, 94: 519

15h Olivero S. Clinet JC. Dunach E. Tetrahedron Lett. 1995, 36: 4429

15i Riguet E. Klement I. Reddy CK. Cahiez G. Knochel P. Tetrahedron Lett. 1996, 37: 5865

15j Vaupel A. Knochel P. J. Org. Chem. 1996, 61: 5743

15k Nakao J. Inoue R. Shinokubo H. Oshima K. J. Org. Chem. 1997, 62: 1910

16 Curran DP. Totleben MJ. J. Am. Chem. Soc. 1992, 114: 6050

17 Fonseca MH. Eibler E. Zabel M. König B. Tetrahedron: Asymmetry 2003, 14: 1989

18 The cis/trans ratio was determined from the ¹H NMR coupling constants C3-H and C4-H (J _cis = 3.4 Hz/J _trans = 9.3 Hz) according to: Makino K. Hara O. Takiguchi Y. Katano T. Asakawa Y. Hatano K. Hamada Y. Tetrahedron Lett. 2003, 44: 8925