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DOI: 10.1055/s-0028-1087991
A Base-Catalysed One-Pot Three-Component Coupling Reaction Leading to Nitrosubstituted Pyrroles
Publication History
Publication Date:
06 March 2009 (online)
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Abstract
Tosyl isocyanide and ethyl chloroformate react with nitrostyrenes to afford nitro-substituted pyrroles in good yield when a catch-and-release protocol was employed as a purification strategy.
Key words
pyrroles - immobilized reagents - heterocycles - multi-component
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1a
Davies DT. Aromatic Heterocyclic Chemistry OUP; Oxford: 1992. -
1b
Barton D.Ollis WD.Sammes PG. Comprehensive Organic Chemistry Vol. 4:Jackson AH. Pergamon Press; Oxford: 1979. p.276 -
1c
Lesage S.Xu H.Durham L. Hydrol. Sci. J. 1993, 38: 343 -
1d
The Porphyrins
Dolphin D. Academic Press; New York: 1977. -
1e
Joh Y.Kotate Y. Macromolecules 1970, 3: 337 -
1f
Anez M.Uribe G.Mendoza L.Contreras R. Synthesis 1981, 214 -
2a
Hui F.Peng P.Hamann MT.Hu J.-F. Chem. Rev. 2008, 108: 264 -
2b
Wang W.Namikoshi M. Heterocycles 2007, 74: 53 -
2c
Morris JC.Phillips AJ. Nat. Prod. Rep. 2008, 25: 95 -
2d
Hughes CC.Prieto-Davo A.Jensen PR.Fenical W. Org. Lett. 2008, 10: 629 -
2e
Donohoe TJ.Thomas RE. Chem. Rec. 2007, 7: 180 -
2f
Walsh CT.Garneau-Tsodikova S.Howard-Jones AR. Nat. Prod. Rep. 2006, 23: 517 -
2g
Gupton JT. In Topics in Heterocyclic Chemistry Springer; Berlin/Heidelberg: 2006. p.53-92 -
3a
Nogami T.Shigehara Y.Matsuda N.Takahashi Y.Naganawa H.Nakamura H.Hamada M.Muraoka Y.Takita T.Iitaka T.Takeuchi T. J. Antibiot. 1990, 43: 1192 -
3b
Jacobi PA.Coults LD.Guo JS.Leung SI. J. Org. Chem. 2000, 65: 205 -
3c
Fürstner A. Angew. Chem. Int. Ed. 2003, 42: 3582 -
3d
Domingo VM.Aleman C.Brillas E.Julia L. J. Org. Chem. 2001, 66: 4058 -
3e
Hong F.Zaidi J.Pang Y.-P.Cusack B.Richelson E. J. Chem. Soc., Perkin Trans. 1 1997, 2997 -
3f
Lea AP.McTavish D. Drugs 1997, 53: 828 -
3g
Higasio YS.Shoji T. Appl. Catal., A 2001, 221: 197 -
3h
Sigman DS.Chen CB. Annu. Rev. Biochem. 1990, 59: 207 -
3i
Skotheim TA. Handbook of Conducting Polymers Marcel Dekker; New York: 1986. - For a selection of the most generic methods see:
-
4a
De Kimpe N.Abbaspour TK.Stevens C.De Cooman P. Tetrahedron 1997, 53: 3693 ; and references cited therein -
4b
Crawley ML.Goljer I.Jenkins DJ.Mehlmann JF.Nogle L.Dooley R.Mahaney PE. Org. Lett. 2006, 8: 5837 -
4c
Martin R.Rivero MR.Buchwald SL. Angew. Chem. Int. Ed. 2006, 45: 7079 -
4d
Larionov OV.de Meijere A. Angew. Chem. Int. Ed. 2005, 117: 5809 -
4e
Gorin DJ.Davis NR.Toste FD. J. Am. Chem. Soc. 2005, 127: 11260 -
4f
Aydogan F.Demir AS. Tetrahedron 2005, 61: 3019 -
4g
Chien T.-C.Meade EA.Hinkley JM.Townsend LB. Org. Lett. 2004, 6: 2857 -
4h
Ramanathan B.Keith AJ.Armstrong D.Odom AL. Org. Lett. 2004, 6: 2957 -
4i
Trofimov BA.Zaitsev AB.Schmidt EY.Vasil’tsov AM.Mikhaleva AI.Ushakov IA.Vashchenko AV.Zorina NV. Tetrahedron Lett. 2004, 45: 3789 -
4j
Almerico AM.Montalbano A.Diana P.Barraja P.Lauria A.Cirrincione G.Dattolo G. ARKIVOC 2001, (vi): 129 -
4k
Trofimov BA.Markova MV.Morozova LV.Mikhaleva AI. ARKIVOC 2001, (ix): 24 -
4l
Trofimov BA.Tarasova OA.Mikhaleva AI.Kalinina NA.Sinegovskaya LM.Henkelmann J. Synthesis 2000, 1585 -
5a
Van Leusen AM.Siderius H.Hoogenboom BE.van Leusen D. Tetrahedron Lett. 1972, 52: 5337 -
5b
ten Have R.Leusink FR.van Leusen AM. Synthesis 1996, 871 -
6a
Barton DHR.Zard SZ. J. Chem. Soc., Chem. Commun. 1985, 1098 -
6b
Barton DHR.Kervagoret J.Zard SZ. Tetrahedron 1990, 21: 7587 -
6c
Bergman J.Rehn S. Tetrahedron 2002, 58: 9179 -
7a
Cohen BJ.Kraus MA.Patchornik A. J. Am. Chem. Soc. 1977, 99: 4165 -
7b
Cainelli G.Contento M.Manescalchi F.Regnoli R. J. Chem. Soc., Perkin Trans. 1 1980, 2516 -
7c
Cohen BJ.Kraus MA.Patchornik A. J. Am. Chem. Soc. 1981, 103: 7620 -
7d
Bergbreiter DE. Chem.-Tech. 1987, 17: 686 -
7e
Brown SD.Armstrong RW. J. Am. Chem. Soc. 1996, 118: 331 -
7f
Wentworth P.Janda KD. Chem. Commun. 1999, 1917 - For selected reviews and application articles see:
-
8a
Solinas A.Taddei M. Synthesis 2007, 2409 -
8b
Bhattacharyya S. Mol. Diversity 2005, 9: 253 -
8c
Storer RI.Takemoto T.Jackson PS.Brown DS.Baxendale IR.Ley SV. Chem.-Eur. J. 2004, 10: 2529 -
8d
Kirschning A.Wittenberg R. In Merging Solid-Phase and Solution-Phase Synthesis - The ”Resin-Capture-Release" Hybrid Technique, Organic Synthesis Highlights V Wiley-VCH; Weinheim: 2003. p.265-279 -
8e
Ley SV.Baxendale IR. Chem. Rec. 2002, 2: 377 -
8f
Ley SV.Baxendale IR.Brusotti G.Caldarelli M.Massi A.Nesi M. Farmaco 2002, 57: 321 -
8g
Ley SV.Baxendale IR. Nat. Rev. Drug Discovery 2002, 1: 573 -
8h
Ley SV.Baxendale IR.Bream RN.Jackson PS.Leach AG.Longbottom DA.Nesi M.Scott JS.Storer RI.Taylor SJ. J. Chem. Soc., Perkin Trans. 1 2000, 3815 -
8i
Baxendale IR.Ley SV. Bioorg. Med. Chem. Lett. 2000, 10: 1983 -
8j
Kirschning A.Wittenberg R.Monenschein H. Chem.-Eur. J. 2000, 6: 4445 -
8k
Flynn DL.Devraj RV.Parlow JJ. Curr. Opin. Drug Discovery Dev. 1998, 1: 41 -
8l
Flynn DL.Crich JZ.Devraj RV.Hockerman SL.Parlow JJ.South MS.Woodard SS. J. Am. Chem. Soc. 1997, 119: 4874 -
8m
Kaldor SW.Siegel MG.Fritz JE.Dressmann BA.Hahn PJ. Tetrahedron Lett. 1996, 37: 7193 -
8n
Booth RJ.Hodges JC. J. Am. Chem. Soc. 1997, 119: 4882 -
8o
Kaldor SW.Fritz JE.Tang J.McKinney ER. Bioorg. Med. Chem. Lett. 1996, 6: 3041 - 12
Fornicola RS.Oblinger E.Montgomery J. J. Org. Chem. 1998, 63: 3528
References
PS-BEMP refers to 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine on polystyrene 2% DVB, loading 2.2 mmol/g. Commercially available from Aldrich Cat No. 20026-XXG where XX is the quantity in grams.
10PS-TBD refers to 1,5,7-triazabicyclo[4.4.0]dec-5-ene-polystyrene cross-linked with 2% DVB, loading 1.33 mmol/g. Commercially available from Biotage Cat. No. 800422.
11Available from Varian Inc. named as Bond Elut silica packed cartridges.
13Experiments to try and exclude the possibility of excess ethyl chloroformate being responsible for the secondary products following addition to the nitrostyrene were conducted using sub-stoichiometric quantities to quench the original TosMIC anion. These reactions gave comparable crude mixtures accompanied by the components from the standard Barton-Zard condensation. The possibility that the TosMIC could still act as a leaving group and consequently as an ethyl formate transfer agent can still not be excluded.
14The reaction between the lithio enolate 4 and ethyl acrylate gave only a mixture of products from which only 7% of a rearrangement product (ethyl 5-tosylpyrrole-1H-3-carboxylate) could be isolated. ¹H NMR and X-ray analysis was used to confirm the structure.