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DOI: 10.1055/s-2007-990888
Facile Regioselective Synthesis of Pyrazolo[5,1-a]isoquinolines via Ring-Opening Cyclization/Oxidation Reactions of Stable Aroyldiaziridines of 3,4-Tetrahydroisoquinoline with Alkynes
Publication History
Publication Date:
13 November 2007 (online)
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Abstract
Newly prepared, stable aroyldiaziridines of 3,4-tetrahydroisoquinolines undergo regioselective cycloaddition reactions with a number of both mono and disubstituted alkynes, affording five-membered ring products which, after oxidative aromatization of the pyrazoline ring, lead to the efficient preparation of pyrazolo[5,1-a]isoquinolines. The overall transformation is base-catalyzed and occurs more rapidly in the presence of oxygen, in halogenated solvents and in dioxane.
Key words
isoquinolines - diaziridines - cycloadditions - alkynes - oxidations
-
1a
El Ali B.Alper H. In Transition Metal Catalyzed ReactionsMurahashi S.-I.Davies SG. Blackwell Science; Malden MA: 1999. p.261 ; and references therein -
1b
Katritzky AR.Rees CW. In Comprehensive Heterocyclic Chemistry Parts 1 and 4B: Pergamon Press; Oxford: 1984. -
2a
Baeg JO.Bensimon C.Alper H. J. Am. Chem. Soc. 1995, 117: 4700 -
2b
Baeg JO.Alper H. J. Org. Chem. 1992, 57: 157 -
2c
Maas H.Bensimon C.Alper H. J. Org. Chem. 1998, 63: 17 -
3a
Larksarp C.Alper H. J. Am. Chem. Soc. 1997, 119: 3709 -
3b
Larksarp C.Alper H. J. Org. Chem. 1998, 63: 6229 - 4
Butler DCD.Inman GA.Alper H. J. Org. Chem. 2000, 65: 5887 - 5
Larksarp C.Sellier O.Alper H. J. Org. Chem. 2001, 66: 3502 - 6
Roberto D.Alper H. J. Chem. Soc., Chem. Commun. 1987, 212 -
7a
Cruz R.Arias ME.Soliveri J. Appl. Microbiol. Biotechnol. 2000, 53: 480 -
7b
Cruz R.Arias MS.Arias ME.Soliveri J. J. Antibiot. 1996, 49: 419 - For example, as kinase inhibitors, see:
-
8a
Majid TN,Hopkins C,Pedgrift BL,Collar N,Wirtz-Brugger F, andMerrill J. inventors; WO 2005,012,301. -
8b
Majid TN,Hopkins C,Pedgrift BL,Collar N,Wirtz-Brugger F, andMerrill J. inventors; US 2005,009,859. -
8c
Flohr S, andNaumann T. inventors; WO 2004,005,287. -
8d
Anand NK,Blazey CM,Bowles OJ,Bussenius J,Costanzo S,Curtis JK,Dubenko L,Kennedy AR,Khoury RG,Kim AI,Manalo J.-CL,Peto CJ,Rice KD, andTsang TH. inventors; WO 2005,009,389. As anaplastic lymphoma kinase modulators, see: -
8e
Xu X,Clare M,Lennon P,Metz S,Vazquez M,Weier RM, andWolfson SG. inventors; WO 2003,070,706. For the treatment of inflammation, see: - 8f As potential fluorescent markers for biomedical applications, see: Galunov N. Z., Krasovitskii B. M., Lyubenko O. N., Yermolenko I. G., Patsenker L. D., Doroshenko A. O.; J. Lumin.; 2003, 102-103: 119
-
8g As anticonvulsant, see:
Paronikyan EG.Sirakanyan SN.Noravyan AS.Paronikyan RG.Dzhagatspanyan IA. Pharm. Chem. J. 2001, 35: 8 - As plant growth regulators, see:
-
9a
Watanabe K.Kamuro Y.Taniguchi E. J. Agric. Food Chem. 1994, 42: 2311 - 9b Kamuro Y., Taniguchi E., Watanabe K.; EP 215,445 A2, 1987
-
9c
Watanabe K.Taniguchi E. Agric. Biol. Chem. 1986, 50: 2591 - As evaluated for pregnancy terminating activity in rats and hamsters, see:
-
9d
Toja E.Omodei-Sale A.Cattaneo C.Galliani G. Eur. J. Med. Chem. 1982, 17: 223 -
9e
Omodei-Sale A,Toja E,Galliani G, andLerner LJ. inventors; AU 516,343 B2. -
10a
El’natanov YI.Kostyanovskii RG. Russ. Chem. Bull. 1988, 37: 1661 ; Izv. Akad. Nauk, Ser. Khim. 1988, 1858 -
10b
Quast H.Ross KH.Spiegel E.Peters K.Von Schnering HG. Angew. Chem. 1977, 89: 202 -
10c
Heine HW.Hoye TR.Williard PG.Hoye RC. J. Org. Chem. 1973, 38: 2984 - 11
Carboni B.Toupet L.Carrie R. Tetrahedron 1987, 43: 2293 - 12
Lehman LS.Baclawski LM.Harris SA.Heine HW. J. Org. Chem. 1981, 46: 320 - 13
Molchanov AP.Sipkin DI.Koptelov YB.Kopf J.Kostikov RR. Russ. J. Org. Chem. 2004, 67 ; Zh. Org. Khim. 2004, 76 - 14
Schmitz E.Ohme R. Chem. Ber. 1962, 95: 2012 - 16
Schulz M.West G. J. Prakt. Chem. 1970, 312: 161 - 17
Tomaschewski G.Klein U.Geissler G. Tetrahedron Lett. 1980, 21: 4877 - For a summary of the azomethine imine reactions, see:
-
18a
Huisgen R. Proc. Chem. Soc. 1961, 357 ; and references cited therein -
18b
Huisgen R.Grashey R.Laur P.Leitermann H. Angew. Chem. 1960, 72: 416 -
18c
Huisgen R.Eckell A. Tetrahedron Lett. 1960, 12: 5 -
18d
Huisgen R.Fleischmann R.Eckell A. Tetrahedron Lett. 1960, 12: 1 -
18e
Truce WE.Allison JR. J. Org. Chem. 1975, 40: 2260 -
19a
Lober S.Hubner H.Gmeiner P. Bioorg. Med. Chem. Lett. 1999, 9: 97 -
19b
Tominaga Y.Ichihara Y.Mori T.Kamio Ch.Hosomi A. J. Heterocycl. Chem. 1990, 27: 263 - 20
Sundberg RJ.Ellis JE. J. Heterocycl. Chem. 1982, 19: 573 - 21
Sale AO,Toia E,Galliani G, andLerner LJ. inventors; US 4,075,342. - 22
Pelletier JC.Cava MP. J. Org. Chem. 1987, 52: 616
References
CCDC 643312 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.