g, 1.65 ml, 1.5 eq.), palladium (II) acetate (2.8 mg, 0.12 mol%), triphenylphosphine (6.6 mg,
0.25 mol%), triethylamine (20 ml) and a magnetic stirrer bar. The flask is fitted with a condenser,
attached to a N2
supply with a pressure relief bubbler, and the two remaining ports stoppered after
the flask has been purged with N2. The solution is stirred and heated gently to 100ºC for 75 min.
The exothermic reaction will initially cause vigorous boiling, but this will subside as the reaction
nears completion.
The reaction mixture is cooled to room temperature and 2Mhydrochloric acid (42 ml) added. The
insoluble product is collected by filtration and dried in a drying pistol overnight. The product is
then sublimed at ~115ºC at 2-3 mmHg. The sublimate is dissolved in ~70% ethanol/water and left
in a fridge overnight to complete crystallisation. The crystals are finally collected and dried in
vacuo.
Record the yield, m.p., i.r. and n.m.r. spectra and give full interpretations of the spectral data.
The write up should conform to the RSC journalOrganic andBiomolecular Chemistrystyle
(Title, Abstract, Introduction, Results and Discussion, Experimental, References). Your
introduction must include discussion of the following points:
a)The mechanism of the reaction, including a proposal for the initial conversion of palladium
(II) to palladium (0).
b)One recent (1998 or later) example from the primary literature of the applications of
palladium catalysed reactions. Extra marks for choosing particularly original chemistry!
Principles and Applications of Organotransition
Metal Chemistry' by J.P. Collman, L.S. Hegedus, J.R. Norton and R.G.Finke,
University Science Books/OUP, 1987.
For a comprehensive account of palladium in organic synthesis, including full
experimental details, see 'Palladium Reagents in Organic Synthesis' by R.F. Heck,
Academic Press, 1985.
B.M. Trost and T.R. Verhoeven, in 'Comprehensive Organometallic Chemistry', eds
G. Wilkinson, F.G.A. Stone and E.W. Abel, Pergamon Press, 1982, vol. 8, pp. 799-
938.
T. Hayashi, M. Konishi and M. Kumada, Tetrahedron Lett., 1979, 1871
J.K. Stille, Angew. Chem. Int. Ed. Engl., 1986, 25, 508.
N. Miyaura, K. Yamada, H. Suginome and A. Suzuki, J. Am. Chem. Soc., 1985,
107, 972.
For this recent example see G. Wu, I. Shimoyama and E.I. Negishi, J. Org. Chem.,
1991, 56, 6506.
5.
6.
