Synthesis 2014; 46(02): 242-250
DOI: 10.1055/s-0033-1340215
paper
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Characterization of New Chiral Azolinium Salts, Precursors to N-Heterocyclic Carbenes, Derived from l-Proline

Amélia Thomasset
a   Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), UMR CNRS 8182, Université Paris-Sud, 91405 Orsay Cedex, France   Email: giang.vo-thanh@u-psud.fr
,
Lucie Bouchardy
a   Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), UMR CNRS 8182, Université Paris-Sud, 91405 Orsay Cedex, France   Email: giang.vo-thanh@u-psud.fr
,
Chloée Bournaud
a   Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), UMR CNRS 8182, Université Paris-Sud, 91405 Orsay Cedex, France   Email: giang.vo-thanh@u-psud.fr
,
Régis Guillot
b   CNRS, Délégation Ile de France Sud, Orsay, France
,
Martial Toffano
a   Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), UMR CNRS 8182, Université Paris-Sud, 91405 Orsay Cedex, France   Email: giang.vo-thanh@u-psud.fr
,
Giang Vo-Thanh*
a   Laboratoire de Catalyse Moléculaire, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), UMR CNRS 8182, Université Paris-Sud, 91405 Orsay Cedex, France   Email: giang.vo-thanh@u-psud.fr
› Author Affiliations
Further Information

Publication History

Received: 29 August 2013

Accepted after revision: 16 October 2013

Publication Date:
14 November 2013 (online)


Abstract

A short and flexible procedure for the preparation of seven chiral azolinium and five functionalized chiral azolinium salts, precursors to N-heterocyclic carbenes, derived from l-proline has been developed. Moderate to good overall yields were obtained. Some NHC dimers and thiones were isolated. X-ray crystal structure determinations of two [Rh-NHC] complexes were also reported.

Supporting Information

 
  • References

    • 1a Arduengo AJ, Harlow RL, Kline M. J. Am. Chem. Soc. 1991; 113: 361
    • 1b Fröhlich N, Pidun U, Stahl M, Frenking G. Organometallics 1997; 16: 442
    • 1c Herrmann WA. Angew. Chem. Int. Ed. 2002; 41: 1290
    • 1d Hahn FE. Angew. Chem. Int. Ed. 2006; 45: 1348
    • 1e Jacobsen H, Correa A, Poater A, Costabile C, Cavallo L. Coord. Chem. Rev. 2009; 253: 687
    • 1f Diez-Gonzalez S, Marion N, Nolan SP. Chem. Rev. 2009; 109: 3612
    • 1g Samojłowicz C, Bieniek M, Grela K. Chem. Rev. 2009; 109: 3708
  • 2 Bourissou D, Guerret O, Gabbaï FP, Bertrand G. Chem. Rev. 2000; 100: 39
    • 3a Lee HM, Lee CC, Cheng PJ. Curr. Org. Chem. 2007; 11: 1491
    • 3b Dröge T, Glorius F. Angew. Chem. Int. Ed. 2010; 49: 6940
    • 3c Benhamou L, Chardon E, Lavigne G, Bellemin-Laponnaz S, César V. Chem. Rev. 2011; 111: 2705
    • 4a Zinner SC, Herrmann WA, Kuhn FE. J. Organomet. Chem. 2008; 693: 1543
    • 4b Perry MC, Burgess K. Tetrahedron: Asymmetry 2003; 14: 951
    • 4c César V, Bellemin-Laponnaz S, Gade LH. Chem. Soc. Rev. 2004; 33: 619
    • 4d Glorius F. N-Heterocyclic Carbenes in Transition Metal Catalysis. Springer; Berlin: 2007
  • 5 Aupoix A, Bournaud C, Vo-Thanh G. Eur. J. Org. Chem. 2011; 2772
  • 6 Dalko P, Moisan L. Angew. Chem. Int. Ed. 2004; 43: 5138
    • 7a Wasserscheid P, Keim W. Angew. Chem. Int. Ed. 2000; 39: 3772
    • 7b Dupont J, De Souza RF, Suarez PA. Chem. Rev. 2002; 102: 3667
    • 7c Wasserscheid P, Welton T. Ionic Liquids in Synthesis . 2nd ed. Wiley-VCH; Weinheim: 2008
    • 7d Deetlefs M, Seddon KS. Green Chem. 2003; 5: 181
    • 7e Lévêque JM, Estager J, Draye M, Cravotto G, Boffa L, Bonrath W. Monatsh. Chem. 2007; 138: 1103
    • 7f Aupoix A, Pégot B, Vo-Thanh G. Tetrahedron 2010; 66: 1352
    • 7g Pârvulescu VI, Hardacre C. Chem. Rev. 2007; 107: 2615
    • 7h Van Rantwijk F, Sheldon RA. Chem. Rev. 2007; 107: 2757
    • 7i Greaves TL, Drummond CJ. Chem. Rev. 2008; 108: 206
    • 7j Martins MA. P, Frizzo CP, Moreira DN, Zanatta N, Bonacorso HG. Chem. Rev. 2008; 108: 2015
    • 7k Aupoix A, Vo-Thanh G. Synlett 2009; 1915
  • 8 Saba S, Brescia A, Kaloustian MA. Tetrahedron Lett. 1991; 32: 5031
    • 9a Arduengo AJ, Krafczyk R, Schmutzler R, Craig HA, Goerlich JR, Marshall WJ, Unverzagt M. Tetrahedron 1999; 55: 14523
    • 9b Ma Y, Song C, Jiang W, Wu Q, Wang Y, Liu X, Andrus MB. Org. Lett. 2003; 5: 3317
    • 9c Funk TW, Berlin JM, Grubbs RH. J. Am. Chem. Soc. 2006; 128: 1840
    • 9d Alder RW, Blake ME, Bufali S, Butts CP, Orpen AG, Schütz J, Williams SJ. J. Chem. Soc., Perkin Trans. 1 2001; 1586
    • 9e Van Veldhuizen JJ, Gillingham DG, Garber SB, Kataoka O, Hoveyda AH. J. Am. Chem. Soc. 2003; 125: 12502
  • 10 Aidouni A, Bendahou S, Demonceau A, Delaude L. J. Comb. Chem. 2008; 10: 886
  • 11 Rix D, Labat S, Toupet L, Crévisy C, Mauduit M. Eur. J. Inorg. Chem. 2009; 1989
    • 12a Vo-Thanh G, Pégot B, Loupy A. Eur. J. Org. Chem. 2004; 1112
    • 12b Varma RS, Namboodiri VV. Chem. Commun. 2001; 643
    • 12c Varma RS, Namboodiri VV. Pure Appl. Chem. 2001; 73: 1309
    • 12d Khadilkar BM, Rebeiro GL. Org. Process Res. Dev. 2002; 6: 826
    • 12e Law MC, Wong KY, Chan TH. Green Chem. 2002; 4: 328
    • 12f Varma RS, Namboodiri VV. Chem. Commun. 2002; 342
    • 12g Dubreuil JF, Famelart MH, Bazureau JP. Org. Process Res. Dev. 2002; 6: 374
    • 12h Cravotto G, Calcio-Gaudino E, Boffa L, Lévêque JM, Estager J, Bonrath W. Molecules 2008; 13: 149

      For reviews on microwave chemistry, see:
    • 13a Perreux L, Loupy A. Tetrahedron 2001; 57: 9199
    • 13b Lidström P, Tierney J, Wathey P, Westman J. Tetrahedron 2001; 57: 9225
    • 13c Hayes BL. Microwave Synthesis: Chemistry at the Speed of Light . CEM Publishing; Matthews NC: 2002
    • 13d Loupy A. Microwaves in Organic Synthesis . Wiley-VCH; Weinheim: 2006
    • 13e Kappe CO, Stadler A. Microwaves in Organic and Medicinal Chemistry . Wiley-VCH; Weinheim: 2005
    • 13f Polshettiwar V, Varma RS. Acc. Chem. Res. 2008; 41: 629
    • 13g Truong TK. T, Nguyen Van Buu O, Pégot B, Aupoix A, Vo-Thanh G. Curr. Org. Synth. 2012; 1: 53
    • 14a Zhang J, Qin X, Fu J, Wang X, Su X, Hu F, Jiao J, Shi M. Organometallics 2012; 31: 8275
    • 14b Makhloufi A, Wahl M, Frank W, Ganter C. Organometallics 2013; 32: 854
    • 15a Xu J, Fu X, Wu C, Hu X. Tetrahedron: Asymmetry 2011; 22: 840
    • 15b Held I, Larionov E, Bozler C, Wagner F, Zipse H. Synthesis 2009; 2267
    • 15c Kikuchi M, Inagaki T, Nishimaya H. Synlett 2007; 1075
    • 15d Fuentes de Arriba AL, Simon L, Raposo C, Alcazar V, Moran JR. Tetrahedron 2009; 65: 4841
    • 15e Kelleher F, Kelly S, Watts J, McKee V. Tetrahedron 2010; 66: 3525
    • 15f Carmona A, Corma A, Iglesias M, San José A, Sanchez F. J. Organomet. Chem. 1995; 492: 11
    • 15g Clapham B, Wilson NS, Michmerhuizen MJ, Blanchard DP, Dingle DM, Nemcek TA, Pan JY, Sauer DR. J. Comb. Chem. 2008; 10: 88
    • 15h Asami M, Ohno H, Kobayashi S, Mukaiyama T. Bull. Chem. Soc. Jpn. 1978; 51: 1869
    • 15i Amedjkouh M, Ahlberg P. Tetrahedron: Asymmetry 2002; 13: 2229
    • 15j Miao S, Bai J, Yang J, Zhang Y. Chirality 2010; 22: 855
    • 16a Tang Z, Jiang F, Cui X, Gong L.-Z, Mi A.-Q, Jiang Y.-Z, Wu Y.-D. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 5755
    • 16b Almaşi D, Alonso DA, Gómez-Bengoa E, Nagel Y, Nájera C. Eur. J. Org. Chem. 2007; 2328
  • 17 CEM Discover S class reactor, see www.cem.com.