Synlett 2016; 27(07): 1096-1099
DOI: 10.1055/s-0035-1561558
letter
© Georg Thieme Verlag Stuttgart · New York

Metal-Mediated Debromination of gem-Dibromoalkenes under Mild Conditions

Raquel G. Soengas*
a   Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal   Email: artur.silva@ua.pt   Email: rsoengas@ua.pt
,
Humberto Rodríguez-Solla
b   Department of Organic and Inorganic Chemistry, University of Oviedo, Julián Clavería, 7, 33071 Oviedo, Spain
,
Artur M. S. Silva*
a   Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal   Email: artur.silva@ua.pt   Email: rsoengas@ua.pt
› Author Affiliations
Further Information

Publication History

Received: 21 November 2015

Accepted after revision: 30 December 2015

Publication Date:
20 January 2016 (online)


Abstract

We describe the facile and efficient metal-promoted reduction of C–Br bonds of gem-dibromides. When the reaction is mediated by indium, the corresponding vinyl bromides are obtained in good yields and high E-stereoselectivities. Alternatively, when the reduction is mediated by samarium diiodide, vinyl bromides are obtained in moderate yields and good Z-selectivities.

Supporting Information

 
  • References and Notes

  • 1 The Chemistry of Dienes and Polyenes . Vol. 1. Rappoport Z., Wiley; Chichester: 1997
    • 2a Concellón JM, Rodríguez-Solla H, Huerta M, Pérez-Andrés JA. Eur. J. Org. Chem. 2002; 1839
    • 2b Vedejs E, Peterson MJ. Top. Stereochem. 1994; 21: 1
    • 2c Chen J, Tao W, Zhao K. Tetrahedron Lett. 1994; 35: 2827
    • 2d Björkling F, Norin T, Unelius R. Synth. Commun. 1985; 15: 463
    • 2e Pasto DJ, Taylor RT. Org. React. (N. Y.) 1991; 41: 91
    • 2f Miller RB, McGarvey G. J. Org. Chem. 1978; 43: 4424
    • 2g Brown HC, Hamaoka T, Ravindran N. J. Am. Chem. Soc. 1973; 95: 6456
  • 3 Takai K, Nitta K, Utimoto K. J. Am. Chem. Soc. 1986; 108: 7408
    • 4a Miura K, Ichinose Y, Nozaki K, Fugami K, Oshima K, Utimoto K. Bull. Chem. Soc. Jpn. 1989; 62: 143
    • 4b Abbas S, Hayes CJ, Worden S. Tetrahedron Lett. 2000; 41: 3215
    • 5a Uenishi J, Kawahama R, Yonemitsu O. J. Org. Chem. 1998; 63: 8965
    • 5b Ranu BC, Samanta S, Guchhait SK. J. Org. Chem. 2001; 66: 4102
    • 6a Namy JL, Girard P, Kagan HB. Nouv. J. Chem. 1977; 1: 5
    • 6b Girard P, Namy JL, Kagan HB. J. Am. Chem. Soc. 1980; 102: 2693
  • 7 Concellón JM, Rodríguez-Solla H. Chem. Soc. Rev. 2004; 33: 599
  • 8 Steel PG. J. Chem. Soc., Perkin Trans. 1 2001; 2727
  • 9 Curran DP, Fevig TL, Jasperse CP, Totleben MJ. Synlett 1992; 943
  • 10 Kunishima M, Hioki K, Ohara T, Tani S. J. Chem. Soc., Chem. Commun. 1992; 219

    • For reviews on indium chemistry, see:
    • 11a Cintas P. Synlett 1995; 1087
    • 11b Li CJ. Tetrahedron 1996; 52: 5643
    • 11c Marshall JA. Chemtracts: Org. Chem. 1997; 10: 481
    • 11d Li CJ In Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes . Anastas P, Williamson TC. Oxford University Press; Oxford: 1998. Chap. 14
    • 11e Paquette LA In Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes . Anastas P, Williamson TC. Oxford University Press; Oxford: 1998. Chap. 15
    • 11f Li CJ, Chan TK. Tetrahedron 1999; 55: 11149

      Allylations:
    • 12a Araki S, Kamei T, Hirashita T, Yamamura H, Kawai M. Org. Lett. 2000; 2: 847
    • 12b Tan K.-T, Chang S.-S, Cheng H.-S, Loh T.-P. J. Am. Chem. Soc. 2003; 125: 2958

    • Propargylations:
    • 12c Isaac MB, Chan T.-H. J. Chem. Soc., Chem. Commun. 1995; 1003

    • Alkynylations:
    • 12d Augé J, Lubin-Germain N, Seghrouchni L. Tetrahedron Lett. 2002; 43: 5255

    • Nitromethylations:
    • 12e Soengas RG, Silva AM. S. Synlett 2012; 23: 873
    • 12f Rodríguez-Solla H, Soengas RG, Alvaredo N. Synlett 2012; 23: 2083
    • 13a Podlech J, Maier TC. Synthesis 2003; 633
    • 13b Ranu BC, Dutta P, Sarkar A. J. Chem. Soc., Perkin Trans. 1 1999; 1139
    • 13c Acúrcio R, Soengas RG, Silva AM. S. Synlett 2014; 25: 1561
    • 14a Soengas RG, Rodríguez-Solla H, Díaz-Pardo A, Acúrcio R, Concellón C, del Amo V, Silva AM. S. Eur. J. Org. Chem. 2015; 2524
    • 14b Cho S, Kang S, Keum G, Kang SB, Han S.-Y, Kim Y. J. Org. Chem. 2003; 68: 180
  • 15 Soengas R. G., Silva V. L. M.: Pinto J, Rodríguez-Solla H, Silva AM. S. Eur. J. Org. Chem. 2016; 99
  • 16 Concellón JM, Rodríguez-Solla H, Bardales E, Huerta M. Eur. J. Org. Chem. 2003; 1775
  • 17 Samarium-Promoted Reduction of gem-Dibromoalkenes 1 (Method A); General Procedure A 0.1 M solution of SmI2 in THF (0.8 mmol) was added to a stirred solution of the appropriate gem-dibromoalkene 1 (0.4 mmol) in THF (5 mL). Deoxygenated H2O (0.5 mL) was added and the mixture was stirred at r.t. for 3 h. The reaction was quenched with 0.1 M aq HCl (10 mL) and the mixture was extracted with CH2Cl2 (3 × 25 mL). The combined organic extracts were washed with sat. aq Na2S2O3 (20 mL), dried (MgSO4), filtered, and concentrated in vacuo.
  • 18 Indium-Promoted Reduction of gem-Dibromoalkenes 1 (Method B); General Procedure Indium metal (90 mg, 0.8 mmol), InCl3 (88 mg, 0.4 mmol), and Pd(PPh3)4 (18 mg, 2 mol%) were added to a solution of the gem-dibromoalkene 1 (0.4 mmol) in THF–H2O (1:1; 6 mL), and the mixture was stirred at r.t. for 3 h. The reaction was quenched with 1 M aq HCl (3 mL) and the mixture was diluted with H2O (25 mL) and extracted with Et2O (3 × 25 mL). The organic extracts were dried (Na2SO4), filtered, and concentrated under reduced pressure.
  • 19 The physical data for compounds 2 were similar to those reported in the corresponding literature; see refs. 2 and 3.