Synlett 2014; 25(08): 1045-1049
DOI: 10.1055/s-0033-1340674
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© Georg Thieme Verlag Stuttgart · New York

Post-Functionalization: A Useful Method for the Synthesis of Donor-Func­tionalized N-Heterocyclic Carbene–Transition-Metal Catalysts

Zhenbo Mo, Liang Deng*
  • State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, 200032 Shanghai, P. R. of China   Fax: +86(21)54925460   Email: deng@sioc.ac.cn
Further Information

Publication History

Received: 21 November 2013

Accepted after revision: 04 January 2014

Publication Date:
11 February 2014 (eFirst)

Abstract

Functionalized N-heterocyclic carbene ligands are particularly useful and widely applied ligands in transition-metal chemistry and catalysis. In this article we introduce an emerging synthetic method for functionalized N-heterocyclic carbene ligands developed from the reactivity study on cyclometalated N-hetero­cyclic carbene compounds, namely postfunctionalization. The status quo of this method for the preparation of novel donor-functionalized N-heterocyclic carbene complexes and their application in catalysis are discussed.

 
  • References and Notes

    • 2a Hahn MC, Jahnke MC. Angew. Chem. Int. Ed. 2008; 47: 3122
    • 2b Schuster O, Yang L, Raubenheimer HG, Albrecht M. Chem. Rev. 2009; 109: 3445
    • 2c Benhamou L, Chardon E, Lavigne G, Bellemin-Laponnaz S, César V. Chem. Rev. 2011; 111: 2705
    • 4a Tamm M, Hahn FE. Coord. Chem. Rev. 1999; 175
    • 4b Edwards PG, Hahn FE. Dalton Trans. 2011; 10278
    • 5a Bontemps S, Gornitzka H, Bouhadir G, Miqueu K, Bourissou D. Angew. Chem. Int. Ed. 2006; 45: 1611
    • 5b Anderson JS, Rittle J, Peters JC. Nature (London) 2013; 501: 84
    • 6a Mankad NP, Whited MT, Peters JC. Angew. Chem. Int. Ed. 2007; 46: 5768
    • 6b Morgan E, MacLean DF, McDonald R, Turculet L. J. Am. Chem. Soc. 2009; 131: 14234
    • 7a Frey GD, Masuda JD, Donnadieu B, Bertrand G. Angew. Chem. Int. Ed. 2010; 49: 9444
    • 7b Schmidt D, Berthel JH. J, Pietsch S, Radius U. Angew. Chem. Int. Ed. 2012; 51: 8881
    • 7c Stephan DW, Erker G. Angew. Chem. Int. Ed. 2010; 49: 46
    • 8a Hitchcock P, Lappert MF, Pye PL. J. Chem. Soc., Chem. Commun. 1977; 196
    • 8b Hitchcock P, Lappert MF, Pye PL, Thomas S. J. Chem. Soc., Dalton Trans. 1979; 1929
  • 9 Data based on the searching results on Cambridge Crystallographic Data Centre (CCDC) in November 2013.
    • 10a Huang J, Stevens ED, Nolan SP. Organometallics 2000; 19: 1194
    • 10b Jazzar RF. R, Macgregor SA, Mahon MF, Richards SP, Whittlesey MK. J. Am. Chem. Soc. 2002; 124: 4944
    • 10c Torres O, Martín M, Sola E. Organometallics 2009; 28: 863
    • 10d Choi G, Tsurugi H, Mashima K. J. Am. Chem. Soc. 2002; 135: 13149
    • 10e Ohki Y, Hatanaka T, Tatsumi K. J. Am. Chem. Soc. 2008; 130: 17174
    • 10f Rivada-Wheelaghan O, Ortunño MA, Díez J, Lledόs A, Conejero S. Angew. Chem. Int. Ed. 2012; 51: 3936
  • 11 Tang CY, Smith W, Thompson AL, Vidovic D, Aldridge S. Angew. Chem. Int. Ed. 2011; 50: 1359
  • 12 Navarro J, Torres O, Martín M, Sola E. J. Am. Chem. Soc. 2011; 133: 9738
  • 13 Rivada-Wheelaghan O, Ortunño MA, Dίez J, Garcia-Garrido SE, Maya C, Lledόs A, Conejero S. J. Am. Chem. Soc. 2012; 134: 15261
  • 14 Mo Z, Chen D, Leng X, Deng L. Organometallics 2012; 31: 7040
  • 15 Mo Z, Liu Y, Deng L. Angew. Chem. Int. Ed. 2013; 52: 10845
  • 16 Hatanaka T, Ohki Y, Tatsumi K. Eur. J. Inorg. Chem. 2013; 3966

    • Silyl-substituted NHC ligands could be synthesized by the conventional synthetic method. But the silyl groups on these NHC ligands only function as innocent substituents, rather than chelating donors. For examples, see:
    • 17a Aksin Ö, Türkmen H, Artok L, Çetinkaya B, Ni C, Büyükgüngör O, Özkal E. J. Organomet. Chem. 2006; 691: 3027
    • 17b Dastgir S, Coleman KS, Green ML. H. Dalton Trans. 2011; 40: 661
    • 17c Albright A, Eddings D, Black R, Welch CJ, Gerasimchuk NN, Gawley RR. J. Org. Chem. 2011; 76: 7341
    • 18a Chalk AJ, Harrod JF. J. Am. Chem. Soc. 1967; 89: 1640
    • 18b Archer NJ, Haszeldine RN, Parish RV. J. Chem. Soc., Chem. Commun. 1971; 524
    • 18c Archer NJ, Haszeldine RN, Parish RV. J. Chem. Soc., Dalton Trans. 1979; 695
  • 19 Albrecht M. Chem. Rev. 2010; 110: 576

    • Constructing phosphine- and pyridine-based chelating ligands from cyclometalated phosphine and pyridine compounds has precedents scattered in literature. For examples, see:
    • 20a Estevan F, García-Bernabé A, Lahuerta P, Sanaú M, Ubeda MA, Galán-Mascarós JR. J. Organomet. Chem. 2000; 596: 248
    • 20b Minato M, Zhou D.-Y, Zhang L.-B, Hirabayashi R, Kakeya M, Matsumoto T, Harakawa A, Kikutsuji G, Ito T. Organometallics 2005; 24: 3434
    • 20c Djukic J.-P, Sortais J.-B, Barloy L, Pfeffer M. Eur. J. Inorg. Chem. 2009; 817
    • 20d Scherl P, Wadepohl H, Gade LH. Organometallics 2013; 32: 4409