Convenient Formation of Six- to Nine-Membered Carbocyclic Rings by 2-Pyridyl Radical Cyclization: A Generalized Synthesis of Pyridine-Fused Linear Tricyclic Systems

Sarbendu Maiti; Michael G. B. Drew; Ranjan Mukhopadhyay; Basudeb Achari; Asish Kr Banerjee

doi:10.1055/s-2005-916034

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Convenient Formation of Six- to Nine-Membered Carbocyclic Rings by 2-Pyridyl Radical Cyclization: A Generalized Synthesis of Pyridine-Fused Linear Tricyclic Systems

Sarbendu Maiti^a, Michael G. B. Drew^b, Ranjan Mukhopadhyay^a, Basudeb Achari^a, Asish Kr. Banerjee*^a
^a Medicinal Chemistry Division, Indian Institute of Chemical Biology, 4 Raja S. C. Mullick Road, Kolkata 700 032, India
Fax: +91(33)24735197; e-Mail: ashisbanerjee@iicb.res.in;
^b Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK
Fax: +44(118)3786331; e-Mail: m.g.b.drew@reading.ac.uk;

Abstract

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Abstract

Intramolecular cyclization of 2-pyridyl radicals derived from 2-bromopyridin-3-yl substituted methylenecycloalkanes 19-22, vinylcycloalkanols 23 and 24, allylcycloalkanols 26-28, and butenylcycloalkanols 32-34 proceed via 6-, 7-, 8-, and 9-endo-trig pathways, giving six-, seven-, eight-, and nine-membered ring annulated pyridines respectively. However, the vinyl cyclopentanol 25 produced only the 6-exo-cyclized product 46, while the substituted allylcyclohexanol 29 and the butenylcyclohexanol 31 failed to cyclize, producing only the double bond isomerized debrominated olefins. Thus the method provides a useful entry to diverse classes of fused pyridines, with the ring size of the cycloalkane and the presence of additional substituents in the ring playing an important role in determining the outcome of the reactions.

Key words

TBTH - 2-pyridyl radical cyclization - pyridine-fused tricyclic systems - endo-selective radical cyclization

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References

1a Giese B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds Pergamon; Oxford: 1986.

1b Jasperse CP. Curan DP. Fevig TL. Chem. Rev. 1991, 91: 1237

1c Curran DP. In Comprehensive Organic Synthesis Vol. 4: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.715-777

1d Curran DP. In Comprehensive Organic Synthesis Vol. 4: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.779-831

1e Giese B. Kopping B. Gobel T. Dickhaunt J. Thoma G. Kulicke KJ. Trach F. Org. React. 1996, 48: 301

1f Aldabbagh F. Bowman R. Contemp. Org. Synth. 1997, 4: 261

1g Banik BK. Curr. Org. Chem. 1999, 3: 469

1h Majumder KC. Basu PK. Mukhopadhyay PP. Tetrahedron 2004, 60: 6239

2a Abeywickrema AN. Beckwith ALJ. Gerba SJ. J. Org. Chem. 1987, 52: 4072 ; and references cited therein

2b Yet L. Tetrahedron 1999, 55: 9349

2c Gibson SE. Guillo N. Tozer M. J. Chem. Soc., Chem. Commun. 1997, 637

2d Ghosh AK. Ghosh K. Pal S. Ghatak UR. J. Chem. Soc., Chem. Commun. 1993, 809

2e Ghosh K. Ghatak UR. Tetrahedron Lett. 1995, 36: 4897

2f Pal S. Mukhopadhyay JK. Ghatak UR. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1999, 38: 264

2g Ghosh K. Ghatak UR. J. Indian Inst. Sci. 2001, 81: 239 ; and references cited therein; Chem. Abstr. 2004, 140: 76888

2h Curran DP. Fairweather N. J. Org. Chem. 2003, 68: 2972

2i Ishibashi H. Kobayashi P. Nakashima S. Tamura O. J. Org. Chem. 2000, 65: 9022

3a Mohanakrishnan AK. Srinivasan PC. Tetrahedron Lett. 1996, 37: 2659

3b Flanagan SR. Harrowven DC. Bradley M. Tetrahedron Lett. 2003, 44: 1795

3c Dobbs AP. Jones K. Veal KT. Tetrahedron Lett. 1997, 38: 5379

3d Yokoyama Y. Matsushima H. Takashima M. Suzuki T. Murakami Y. Heterocycles 1997, 46: 133

3e Comins DL. Hong H. Jianhua G. Tetrahedron Lett. 1994, 35: 5331

3f Kato I. Higashimoto M. Tamura O. Ishibashi H. J. Org. Chem. 2003, 68: 7983

4a Shankaran K. Solan CP. Snieckus V. Tetrahedron Lett. 1985, 26: 6001

4b Dobbes AP. Jones K. Veal KT. Tetrahedron Lett. 1997, 38: 5383

4c Jones K. Fiumana A. Escudero-Hernandez ML. Tetrahedron 2000, 56: 397

5 Maiti S. Achari B. Mukherjee R. Banerjee AK. J. Chem. Soc., Perkin Trans. 1 2002, 1769

6 Banerjee M. Mukherjee R. Achari B. Banerjee AK. Org. Lett. 2003, 5: 3931

7a Banik BK. Chakraborty AK. Ghatak UR. J. Chem. Res., Synop. 1986, 406

7b Banik BK. Chakraborty AK. Ghatak UR. J. Chem. Res., Miniprint 3391,

8 Hirst GC. Howard PN. Overman LE. J. Am. Chem. Soc. 1989, 111: 1514 ; and references cited therein

9 Hagishita S. Kuriyama K. Bull. Chem. Soc. Jpn. 1982, 55: 3216

10 Curran DP. Xu J. J. Am. Chem. Soc. 1996, 118: 3142

11 House HO. Gall M. Olmstead HD. J. Org. Chem. 1971, 36: 2361

12 Ghatak UR. Dasgupta R. Chakraborty J. Tetrahedron 1974, 30: 187

13 Krapcho AP. Weimaster JF. Eldridge JM. Jahngen EGE. Lovey AJ. Stephene WP. J. Org. Chem. 1978, 43: 139

14 Levy LA. Sashikumar VP. J. Org. Chem. 1985, 50: 1760

15a Gadwood RC. Lett RM. J. Org. Chem. 1982, 47: 2268

15b Robichaud AJ. Meyers AI. J. Org. Chem. 1991, 56: 2607

16 Imamoto T. Takiyama N. Nakamura K. Hatajima T. Kamiya Y. J. Am. Chem. Soc. 1989, 112: 4392

17a O’Shea MG. Kitching W. Tetrahedron 1989, 45: 1177

17b Ireland RE. Maienfisch P. J. Org. Chem. 1988, 53: 640

18 Kabsch W. J. Appl. Cryst. 1988, 21: 916

19 Sheldrick GM. ShelX 86; Acta Cryst. 1990, A46: 467

20 Sheldrick GM. ShelXL, Program for Crystal Structure Refinement University of Gottingen; Germany: 1993.