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X. Tang et al.
LETTER
for 30 min for the excess aluminium metal to settle. The light
brown supernatant solution of organoaluminium sesqui-
halide was ready to use. Method 2: Aluminium powder
(59 mg, 2.2 mmol) and Ga (14 mg, 0.2 mmol) were added to
a dry argon-flushed Schlenk tube. Organohalide (2 mmol)
was added and the reaction was stirred at 120 °C for 20 h.
Anhydrous toluene (1 mL) was added and the mixture was
stirred vigorously for 5 min. The reaction mixture was
allowed to cool to r.t. and left for 30 min for the excess
aluminium metal to settle. The light brown supernatant
solution of organoaluminium sesquihalide was ready to use.
(17) General Procedure for Reactions of Sesquihalide and
Acetyl Chloride: Acetyl chloride (1 mmol) was dissolved in
anhydrous toluene (2 mL), and sesquihalide (1 mmol)
prepared by method 2 was added. The reaction mixture was
stirred at r.t. for 3 h. The reaction was quenched with HCl (2
M) and extracted with Et2O. The organic phase was dried
over MgSO4 and concentrated to give the crude compound.
The crude material was purified by column chromatography
(light petroleum–Et2O) over silica gel to give the pure
product.
Acknowledgment
We thank the Engineering and Physical Sciences Research Council
for partial support of this programme through Grant EP/G026882/
1. X.T. thanks the Marie Curie Office of the European Commission
for support through contract MEST-CT-2005-019780 (INDAC-
CHEM).
References and Notes
(1) Tanaka, H.; Kuroboshi, M. Curr. Org. Chem. 2004, 8, 1027.
(2) Anderson, J. C.; Chapman, H. A. Synthesis 2006, 3309.
(3) Khurana, J. M.; Singh, S. J. Chem. Soc., Perkin Trans. 1
1999, 1893.
(4) Schroeck, C. W.; Johnson, C. R. J. Am. Chem. Soc. 1971, 93,
5305.
(5) Lui, Y.; Xu, D. Q.; Xu, Z.; Zhang, Y. Synlett 2007, 1671.
(6) Tanaka, H.; Nakahata, S.; Watanabe, H.; Zhao, J. F.;
Kuroboshi, M.; Torii, S. Inorg. Chim. Acta 1999, 296, 204.
(7) Kuroboshi, M.; Tanaka, M.; Kishimoto, S.; Goto, K.;
Tanaka, H.; Torii, S. Tetrahedron Lett. 1999, 40, 2785.
(8) Basile, T.; Bocoum, A.; Savoia, D.; Umani-Ronchi, A.
J. Org. Chem. 1994, 59, 7766.
(9) Chemistry of Aluminium, Gallium, Indium and Thalium;
Downs, A. J., Ed.; Chapman and Hall: London, 1993.
(10) Takai, K.; Ikawa, Y. Org. Lett. 2002, 4, 1727.
(11) Barbot, F.; Miginiac, L. Synth. Commun. 1997, 27, 2601.
(12) Barbot, F. Tetrahedron Lett. 1989, 30, 185.
(13) Grosse, A. V.; Mavity, J. M. J. Org. Chem. 1940, 5, 106.
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-st (Moscow) 1971, 47, 669; Chem. Abstr. 1972, 76, 24306.
(15) Flamini, D. O.; Saidman, S. B.; Bessone, J. B. Corrosion Sci.
2006, 48, 1413.
(16) General Procedure for the Synthesis of Sesquihalide;
Method 1: Aluminium powder (81 mg, 3 mmol) and HgCl2
(5 mg, 0.02 mmol) were added to a dry argon-flushed
Schlenk tube. Organohalide (2 mmol) was added and the
reaction was stirred at 120 °C for 3 h. Anhydrous toluene (1
mL) was added and the mixture was stirred vigorously for 5
min. The reaction mixture was allowed to cool to r.t. and left
(18) Biswas, K.; Prieto, O.; Goldsmith, P.; Woodward, S. Angew.
Chem. Int. Ed. 2005, 44, 2232.
(19) Biswas, K.; Chapron, A.; Cooper, T.; Fraser, P. K.; Novak,
A.; Prieto, O.; Woodward, S. Pure Appl. Chem. 2006, 78,
511.
(20) Woodward, S. Synlett 2007, 1490.
(21) Basha, A.; Lipton, M.; Weinreb, S. M. Tetrahedron Lett.
1977, 4171.
(22) General Procedure for Amide Formation: Amine
(1 mmol) was dissolved in anhyd toluene (2 mL), and sesqui-
halide (0.67 mmol) prepared by method 2 was added. The
reaction mixture was stirred at r.t. for 10 min. The ester (0.5
mmol) was added to the reaction mixture and the mixture
was heated to 80 °C for 3 h. The reaction was quenched with
HCl (2 M) and extracted with Et2O. The organic phase was
dried over MgSO4 and concentrated to give the crude
compound. The crude material was purified by column
chromatography (light petroleum–Et2O) over silica gel to
give the pure product.
Synlett 2010, No. 4, 636–638 © Thieme Stuttgart · New York