Synlett 2003(15): 2440-2441  
DOI: 10.1055/s-2003-43340
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

Gallium Trichloride

Dhiren Chandra Barman*
Technical Development Centre (Custom Chemical Services), Dr. Reddys Laboratory, Hyderabad, India 500049
e-Mail: mrdhiren@yahoo.com;

Further Information

Publication History

Publication Date:
21 November 2003 (online)

Biographical Sketches

Dhiren Chandra Barman was born in 1976 and received his MSc degree (Chemistry) in 1999 from Gauhati University, Assam, India. Thereafter he joined Dr. J. S. Sandhu’s group in the Medicinal Chemistry Division of the Regional Research Laboratory (CSIR) Jorhat, Assam, India. His PhD focused on cycloaddition reactions for the synthesis of novel heterocycles of biological significance and some functional group transformations. After submitting his thesis he continued to study cycloaddition reactions with Dr. D. Prajapati Sc. E II at the same institute. Presently he is working in Dr. Reddys Laboratory, Hyderabad, India.

Introduction

Like some of the other group 13 trihalides (not Al, In, and Tl), galliumtrichloride has a (bridged dimer) molecular lattice as shown (Figure 1).

The dimmer molecules are arranged in sheets. The low intermolecular forces are responsible for the low mp (77.9 °C, the lowest of the Al, Ga, In, and Tl trihalides). [1] GaCl3 is evidently a weaker acid then AlCl3. Its application in organic synthesis has been known for a long time e.g. in the Fridel-Crafts synthesis of benzophenone from benzene and benzoyl chloride GaCl3 results in a faster reaction than AlCl3, [2] the reaction of benzene with alkyl halides is also quicker with gallium. [3]

Preparation

GaCl3 is available commercially or can be prepared by burning gallium in a stream of Cl2 [4] [5] or by the action of HCl or SOCl2 (> ca 200 °C) Ga2O3. [4] [6] The pure anhydrous compound can be obtained by redistillation in a steam of Cl2 (or Cl2/ N2) followed by vacuum sublimation or by zone refining. [4]

Abstracts

(A) In the presence of GaCl3, silyl enol ethers are ethynylated at the a-carbon atom with chlorotrimethylsilyl ethyne to give a-ethynylated aryl ketones possessing a-protons without isomerization to conjugated allenyl ketones. [7]

(B) Trimethylsilylethyne and silyl enol ether were reacted with GaCl3 in methylcyclohexane at r.t. and after treatment with THF and 6 M H2SO4, a- ethenyl ketone was obtained in high yield. Employment of GaCl3 was essential, and no reaction occured with AlCl3, InCl3, or other Lewis acids of group 13 elements. [8]

(C) Treatment of alkynes with allyl trimethyl silanes in the presence of GaCl3 gives 1,4-dienes via allylgallation. [9]

(D) Treatment of aryl halides with alkenyl gallium dichloride, prepared from GaCl3 and alkenyl magnesium bromide, in the presence of a catalytic amount of palladium provided cross-coupling product in good yield. [10]

(E) GaCl3 catalyzes the tandem ring opening of epoxides and cyclization with alkynes to generate naphthalene derivatives with complete regiocontrol. [11]

(F) In the presence of GaCl3, silyl enol ethers derived from substituted ketoesters or malonates are ethenylated at the carbon atom with trimethylsilylethyne in high yields. Ethenylmalonates can also be synthesized by this method. [12]

(G) A gallium hydride reagent, HGaCl2, was found to act as a ­radical mediator, like Bu3SNH. Treatment of alkyl halides with HGaCl2, generated from GaCl3 and sodium bis-(2-methoxyethoxy)aluminium hydride, provided the corresponding reduced products in excellent yields. Radical cyclization of halo-acetals was also successful with both a stoichiometric amount of gallium reagent but also a catalytic amount of GaCl3 combined with a ­stoichiometric amount of AlH3 as a hydride source. [13]

(H) Alkenyl Fischer chromium carbene complexes react with various kinds of simple imines to produce 3-pyrroline derivatives in the presence of a catalytic amount of GaCl3. [14]

(I) The allylgallium reagent which may be prepared by mixing GaCl3 and an equimolar amount of allylmagnesium chloride, al­lylated carbonyl compounds in good yields in aqueous media and organic solvents. [15]

(J) (Trimethylsilyl)acetylene upon treatment with GaCl3 in CH2Cl2 and methylcyclohexane, trimerized rapidly giving acyclic conjugated trienes. [16]

    References

  • 1 Wallorck SC. Worral IJ. J. Chem. Soc.  1965,  1816 
  • 2 Id Z. Electrochemistry  1935,  41:  509 
  • 3 Ulich H. Angew. Chem.  1942,  55:  37 
  • 4 Bruer G. Handbook of Preparative Inorganic Chemistry   Academic Press; New York: 1963.  2nd Ed..
  • 5 Beck JD. Wood RH. Greenwood NN. Inorg. Chem.  1970,  9:  86 
  • 6 Ivashenlsev YI. Konakova VA. Zh. Neorg. Chim.  1967,  12:  1763 
  • 7 Arisawa M. Amemiya R. Yamaguchi M. Org. Lett.  2002,  4:  2209 
  • 8 Yamaguchi M. Tsukagoshi T. Arisawa M. J. Am. Chem. Soc.  1999,  121:  4074 
  • 9 Yamaguchi M. Sotokawa T. Hirama M. J. Chem. Soc., Chem. Commun.  1997,  743 
  • 10 Mikami S. Yorimitsu H. Oshima K. Synlett  2002,  1137 
  • 11 Viswanathan GS. Li C.-J. Synlett  2002,  1553 
  • 12 Arisawa M. Akamatsu K. Yamaguchi M. Org. Lett.  2001,  3:  789 
  • 13 Mikami S. Fujita K. Nakamura T. Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Org. Lett.  2001,  3:  1853 
  • 14 Kagoshima H. Akiyam T. J. Am. Chem. Soc.  2000,  122:  11741 
  • 15 Tsuji T. Usugi S. Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Chem. Lett.  2002,  4:  2 
  • 16 Kido Y. Yamaguchi M. J. Org. Chem.  1998,  63:  8089 

    References

  • 1 Wallorck SC. Worral IJ. J. Chem. Soc.  1965,  1816 
  • 2 Id Z. Electrochemistry  1935,  41:  509 
  • 3 Ulich H. Angew. Chem.  1942,  55:  37 
  • 4 Bruer G. Handbook of Preparative Inorganic Chemistry   Academic Press; New York: 1963.  2nd Ed..
  • 5 Beck JD. Wood RH. Greenwood NN. Inorg. Chem.  1970,  9:  86 
  • 6 Ivashenlsev YI. Konakova VA. Zh. Neorg. Chim.  1967,  12:  1763 
  • 7 Arisawa M. Amemiya R. Yamaguchi M. Org. Lett.  2002,  4:  2209 
  • 8 Yamaguchi M. Tsukagoshi T. Arisawa M. J. Am. Chem. Soc.  1999,  121:  4074 
  • 9 Yamaguchi M. Sotokawa T. Hirama M. J. Chem. Soc., Chem. Commun.  1997,  743 
  • 10 Mikami S. Yorimitsu H. Oshima K. Synlett  2002,  1137 
  • 11 Viswanathan GS. Li C.-J. Synlett  2002,  1553 
  • 12 Arisawa M. Akamatsu K. Yamaguchi M. Org. Lett.  2001,  3:  789 
  • 13 Mikami S. Fujita K. Nakamura T. Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Org. Lett.  2001,  3:  1853 
  • 14 Kagoshima H. Akiyam T. J. Am. Chem. Soc.  2000,  122:  11741 
  • 15 Tsuji T. Usugi S. Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Chem. Lett.  2002,  4:  2 
  • 16 Kido Y. Yamaguchi M. J. Org. Chem.  1998,  63:  8089