Synlett 2013; 24(5): 531-534
DOI: 10.1055/s-0032-1318075
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© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed Hydromagnesiation of Olefins

Mark D. Greenhalgh
School of Chemistry, Joseph Black Building, West Mains Road, Edinburgh, Scotland, EH9 3JJ, UK   Fax: +44(0)1316506453   Email: stephen.thomas@ed.ac.uk
,
Stephen P. Thomas*
School of Chemistry, Joseph Black Building, West Mains Road, Edinburgh, Scotland, EH9 3JJ, UK   Fax: +44(0)1316506453   Email: stephen.thomas@ed.ac.uk
› Author Affiliations
Further Information

Publication History

Received: 07 December 2012

Accepted after revision: 19 December 2012

Publication Date:
15 January 2013 (online)


Abstract

In 2012, three complementary iron-catalyzed methodologies for the hydromagnesiation of olefins have been developed. In each case, hydromagnesiation gives an alkyl, benzylic, or vinyl ­Grignard reagent that can be reacted with a variety of electrophiles to give functionalized products in good to excellent yields. The ­regio-, chemo-, and stereoselectivities of the reactions are evaluated.

 
  • References

  • 1 For a review, see: Sato F. J. Organomet. Chem. 1985; 285: 53

    • For the preparation of functionalized Grignard reagents, see:
    • 2a Knochel P, Dohle W, Gommermann N, Kneisel FF, Kopp F, Korn T, Sapountzis I, Vu VA. Angew. Chem. Int. Ed. 2003; 42: 4302
    • 2b Krasovskiy A, Knochel P. Angew. Chem. Int. Ed. 2004; 43: 3333

      For examples of hydromagnesiation using MgH2 and RMgH, see:
    • 3a Ashby EC, Smith T. J. Chem. Soc., Chem. Commun. 1978; 30
    • 3b Ashby EC, Ainslie RD. J. Organomet. Chem. 1983; 250: 1

    • For the uncatalyzed addition of MgH2 to alkenes, see:
    • 3c Podall HE, Foster WE. J. Org. Chem. 1958; 23: 1848
    • 4a Cooper GD, Finkbeiner HL. J. Org. Chem. 1962; 27: 1493
    • 4b Cooper GD, Finkbeiner HL. J. Org. Chem. 1962; 27: 3395
    • 5a Farády L, Bencze L, Markó L. J. Organomet. Chem. 1967; 10: 505
    • 5b Sato F, Ishikawa H, Sato M. Tetrahedron Lett. 1980; 21: 365
    • 5c Sato F, Kusakabe M, Kobayashi Y. J. Chem. Soc., Chem. Commun. 1984; 1130
    • 5d Colomer E, Corriu R. J. Organomet. Chem. 1974; 82: 367
    • 5e Sato F, Ishikawa H, Sato M. Tetrahedron Lett. 1981; 22: 85
  • 6 Tamura M, Kochi J. J. Organomet. Chem. 1971; 31: 289
  • 7 Shirakawa E, Ikeda D, Yamaguchi S, Hayashi T. Chem. Commun. 2008; 1214
  • 8 Shirakawa E, Ikeda D, Masui S, Yoshida M, Hayashi T. J. Am. Chem. Soc. 2012; 134: 272
  • 9 Ashby EC, Oswald J. J. Org. Chem. 1988; 53: 6068
  • 10 Shirakawa E, Yamagami T, Kimura T, Yamaguchi S, Hayashi T. J. Am. Chem. Soc. 2005; 127: 17164
    • 11a Stobbe H, Posnjak G. Justus Liebigs. Ann. Chem. 1909; 371: 287
    • 11b Cohen HL, Wright GF. J. Org. Chem. 1953; 18: 432
  • 12 For a nickel-catalyzed hydrocarboxylation of styrene derivatives, see: Williams CM, Johnson JB, Rovis T. J. Am. Chem. Soc. 2008; 130: 14936
  • 13 Greenhalgh MD, Thomas SP. J. Am. Chem. Soc. 2012; 134: 11900
  • 14 Zhang D, Ready JM. J. Am. Chem. Soc. 2006; 128: 15050
  • 15 Ilies L, Yoshida T, Nakamura E. J. Am. Chem. Soc. 2012; 134: 16951
    • 16a Phua P.-H, LeFort L, Boogers JA. F, Tristany M, de Vries JG. Chem. Commun. 2009; 3747
    • 16b Welther A, Bauer M, Mayer M, Jacobi von Wangelin A. ChemCatChem 2012; 4: 1088

    • For the preparation of iron nanoparticles using aryl Grignard reagents, see:
    • 16c Bedford RB, Betham M, Bruce DW, Davis SA, Frost RM, Hird M. Chem. Commun. 2006; 1398
  • 17 Iron-catalyzed protodehalogenation is also proposed to proceed via β-hydride elimination of an organoiron species, and again NMP is not used, see: Czaplik WM, Grupe S, Mayer M, Jacobi von Wangelin A. Chem. Commun. 2010; 46: 6350