PDF herunterladen
Synlett 2011(1): 124-128  
DOI: 10.1055/s-0030-1259083
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Cross Metathesis of N-Allylamines and α,β-Unsaturated Carbonyl Compounds: A One-Pot Synthesis of Substituted Pyrroles

Syed Shafia, Mariusz Kędziorekb, Karol Grela*a,b
a Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
b Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
Fax: +48(22)3432109; e-Mail: klgrela@gmail.com;
Weitere Informationen

Publikationsverlauf

Received 9 October 2010
Publikationsdatum:
07. Dezember 2010 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A tandem reaction involving cross metathesis followed by concomitant cyclisation has been developed for the synthesis of substituted pyrroles. Various protected electron-deficient N-allylamines reacted with α,β-unsaturated carbonyl compounds in the presence of Lewis acids under the cross metathesis conditions using selected Ru olefin metathesis catalysts in order to form pyrroles.

Key words

ruthenium - catalysis - olefin metathesis - Lewis acids - heterocycles

    References and Notes

  • For reviews, see:
  • 1a Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed.  2005,  44:  4490 
    Suche in Google Scholar
  • 1b Handbook of Metathesis   Vol. 1-3:  Grubbs RH. Wiley-VCH; Weinheim: 2003.  p.1234 
  • 1c Furstner A. Angew. Chem. Int. Ed.  2000,  39:  3012 
    Suche in Google Scholar
  • 1d Blechert S. Connon SJ. Angew. Chem. Int. Ed.  2003,  42:  1900 
    Suche in Google Scholar
  • 1e Vernall AJ. Abell AD. Aldrichimica Acta  2003,  36:  93 
    Suche in Google Scholar
  • 2a Love JA. Morgan JP. Trnka TM. Grubbs RH. Angew. Chem. Int. Ed.  2002,  41:  4035 
    Suche in Google Scholar
  • 2b Garber SB. Kingsbury JS. Gray BL. Hoveyda AH. J. Am. Chem. Soc.  2000,  122:  8168 
    Suche in Google Scholar
  • 2c Scholl M. Ding S. Choon WL. Grubbs RH. Org. Lett.  1999,  1:  953 
    Suche in Google Scholar
  • 2d Kingsbury JS. Harrity JPA. Bonitatebus PJ. Hoveyda AH. J. Am. Chem. Soc.  1999,  121:  791 
    Suche in Google Scholar
  • 2e Schwab P. France MB. Ziller JW. Grubbs RH. Angew. Chem., Int. Ed. Engl.  1995,  34:  2039 
    Suche in Google Scholar
  • 3a Michaut A. Rodriguez J. Angew. Chem. Int. Ed.  2006,  45:  5740 
    Suche in Google Scholar
  • 3b Martin SF. Deiters A. Chem. Rev.  2004,  104:  2199 
    Suche in Google Scholar
  • 3c McReynolds MD. Dougherty JM. Hanson PRJM. Chem. Rev.  2004,  104:  2239 
    Suche in Google Scholar
  • 3d van Otterlo WAL. de Koning CB. Chem. Rev.  2009,  109:  3743 
    Suche in Google Scholar
  • 3e Donohoe TJ. Fishlock LP. Procopiou PA. Chem. Eur. J.  2008,  14:  5716 
    Suche in Google Scholar
  • 4 Donohoe TJ. Orr AJ. Bingham M. Angew. Chem. Int. Ed.  2006,  45:  2664 ; and references cited therein
    Suche in Google Scholar
  • 5a Bassindale MJ. Hamley P. Leitner A. Harrity JPA. Tetrahedron Lett.  1999,  40:  3247 
    Suche in Google Scholar
  • 5b Kinderman SS. Doodeman R. van Beijma JW. Russcher JC. Tjen KCMF. Kooistra TM. Mohaselzadeh H. van Maarseveen JH. Hiemstra H. Schoemaker HE. Rutjes FPJT. Adv. Synth. Catal.  2002,  344:  736 
    Suche in Google Scholar
  • 6a During the preparation of this manuscript, a related two-step approach to substituted pyrroles via olefin cross meta-thesis and subsequent acid-catalysed cyclisation was published by Donohoe et al., presenting also an excellent example of the application of this methodology towards the synthesis of the tetrasubstituted pyrrole subunit of Atorvastatin, see: Donohoe TJ. Race NJ. Bower JF. Callens CKA. Org. Lett.  2010,  12:  4094 
    Suche in Google Scholar
  • 6b Donohoe TJ. Bower JF. Proc. Natl. Acad. Sci. U.S.A.  2010,  107:  3373 
    Suche in Google Scholar
  • 6c Krische MJ. Proc. Natl. Acad. Sci. U.S.A.  2010,  107:  3279 
    Suche in Google Scholar
  • 7 Poulard C. Cornet J. Legoupy S. Dujardin G. Dhal R. Huet F. Lett. Org. Chem.  2009,  6:  359 
    CrossrefSuche in Google Scholar
  • 8 Saito A. Konishi T. Hanzawa Y. Org. Lett.  2010,  12:  372 ; and references cited therein
    Suche in Google Scholar
  • For selected examples of CM with allyl amines, see:
  • 9a Vedrenne E. Dupont H. Sabrina O. Elkaïm L. Grimaud L. Synlett  2005,  670 
  • 9b Dewi P. Blechert S. Eur. J. Org. Chem.  2006,  1852 
  • 9c Gebauer J. Dewi P. Blechert S. Tetrahedron Lett.  2005,  46:  43 
    Suche in Google Scholar
  • 9d Chatterjee AK. Choi T.-L. Sanders DP. Grubbs RH. J. Am. Chem. Soc.  2003,  125:  11360 
    Suche in Google Scholar
  • 10 Paulus O. Alcaraz G. Vaultier M. Eur. J. Org. Chem.  2002,  14:  2565 
    Suche in Google Scholar
11

General procedure: All reactions were performed using Schlenk techniques under an argon atmosphere. Solvents were degassed (using Freeze-Pump-Thaw techniques) before use. Metathesis catalysts and all commercially available chemicals were used as received. See the Supporting Information for full experimental procedures
and product characterisation data

12

Pyrrol-1-yl(1H-pyrrol-2-yl)methanone (10z); Typical procedure: In a dry Schlenk tube, substrate 10x (100 mg, 0.66 mmol), B(OPh)3 (19 mg, 10 mol%) and crotonaldehyde (233 mg, 3.3 mmol) were dissolved in anhydrous toluene (5 mL) and stirred for 5 min under an argon atmosphere. The first portion of the catalyst Hov-II (10.5 mg, 2.5 mol%) was added as a solid. The reaction mixture was heated to reflux and, after 15 min, the second portion of the catalyst was added (10.5 mg, 2.5 mol%) under an argon atmosphere and heating was continued until the reaction was complete according to TLC. The reaction mixture was cooled and the solvent was evaporated. The crude product was purified by flash chromatography (c-hexane-EtOAc, 19:1) to yield 10z as a colourless solid (64.01 mg, 60%); Mp 56-58 ˚C. ¹H NMR (500 MHz, CDCl3): δ = 6.36 (t, J = 2.30, 2.29 Hz, 2 H), 6.37-6.38 (m, 1 H), 6.98-6.99 (m, 1 H), 7.11-7.14 (m, 1 H), 7.52 (t, J = 2.29, 2.30 Hz, 2 H), 9.86 (br, 1 H). ¹³C NMR (125 MHz, CDCl3): δ = 111.19, 112.71, 117.61, 120.65, 123.92, 124.95, 159.01. IR (KBr): 3306, 3158, 2958, 2924, 1645, 1545, 1467, 1456, 1424, 1412, 1389, 1345, 1277, 1244, 1138, 1108, 1099, 1074, 1042, 990, 941, 887, 864, 842, 766, 751, 728, 630, 604 cm-¹. MS (EI): m/z (%) = 160 (91) [M]+ ˙ , 94 (100), 67 (48), 66 (28). HRMS (EI): m/z calcd for C9H8N2O: 160.06366; found: 160.06381. Anal. Calcd for C9H8N2O: C, 67.49; H, 5.03; N, 17.49. Found: C, 67.44; H, 4.88; N, 17.57.

13

This work was presented for the first time during the European Congress of Young Chemists ‘YoungChem 2009’, Warsaw, Poland, October 14-18, 2009: ‘Ru catalyzed imine formation followed by RCM of N- allylamines: A tandem reaction towards the synthesis of substituted pyrroles’; S. Shafi, oral presentation