Organic reactions involving Pd are classified into oxidative reactions with Pd(II) salts and catalytic reactions with Pd(0) complexes. Pd(II) salts [PdCl2, Pd(OAc)2] are unique oxidizing or dehydrogenating reagents. The reactions promoted by
PdX2 + H2O A-H + B-H + 1/2 O2 A-B + H2O
[OX]
[OX]
Oxidative (dehydrogenative) reactions with Pd(II) compounds A-H + B-H + PdX2 A-B + Pd(0) + 2 HX Pd(0) + 2 HX + 1/2 O2
PdX2
+ H2C C
examples
H H
+ AcOH + 1/2 O2 H2C C OAc
+ H
+
H H + 1/2 O2 H2O
Pd(II)
Pd(II)
H2O
R R Nu Pd(0)-catalyzed reactions
example examples
+ HX +
+ + HX
Nu-H
X H R
R
H X
Ar-B + HX Pd(0)
X
Ar-X + RM′Y Ar-R + M′XY
Y2B
+ R R
+ BY2X Ar-X + B-H
Pd(0)
Pd(0)
Pd(0)
Pd(0)
Pd(II) can be expressed by the following general schemes. As a whole, two hydrogens are abstracted from two substrates A-H and B-H, generating Pd(0) and the product A-B. This reaction is stoichiometric with Pd(II), but the reaction becomes catalytic when Pd(0) is oxidized in situ to Pd(II) with appropriate oxi- dants (OX), and the whole reaction can be summarized by a third equation. For example, formation of vinyl acetate from ethylene and oxidative coupling of ben- zene can be understood formally as dehydrogenation reactions. These oxidative reactions using Pd(II) are considered in Chapter 2.
The Pd(0)-catalyzed reactions of Ar-X and B-H (or B-Y) can be expressed by the following general equations, which involve no oxidation. The Mizoroki–Heck reaction, allylation of nucleophiles, and cross-couplings are typical reactions of this type. They are treated in Chapters 3–8.
A clear understanding that these two types of reactions involving Pd(II) and Pd(0) are mechanistically quite different is required before studying organopalla- dium chemistry.
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Books3
A number of books and monographs treating organopalladium chemistry have been published as listed below. Particularly, there is an excellent encyclopedia of organopalladium chemistry, edited by E. Negishi, which was published in 2002 [9].
The book is 3279 pages long, covering all reactions either catalyzed or promoted by Pd(0) and Pd(II) compounds reported before 2000 and including ample experi- mental data and references. The Handbook is not only useful but also monumental in organopalladium chemistry.
On Palladium Chemistry
1. P. M. Maitlis,The Organic Chemistry of Palladium, Vols 1 and 2, Academic Press, New York, 1971.
2. J. Tsuji,Organic Synthesis with Palladium Compounds, Springer, Berlin 1980.
3. P. M. Henry, Palladium Catalyzed Oxidation of Hydrocarbons, D. Reidel, Rordrecht 1980.
4. B. M. Trost and T. R. Verhoeven, Organopalladium Compounds in Organic Synthesis and in Catalysis, inComprehensive Organometallic Chemistry, Pergamon Press, Oxford, 1982, Vol. 8, p. 799.
5. R. F. Heck, Palladium Reagents in Organic Syntheses, Academic Press, New York, 1985.
6. J. Tsuji,Palladium Reagents and Catalysts, Wiley, Chichester, 1995.
7. J. Tsuji (Ed.),Perspectives in Organopalladium Chemistry for the XXI Century, Elsevier, Amsterdam 1999;J. Organomet. Chem.,576(1999).
8. J. J. Li and G. W. Gribble, Palladium in Heterocyclic Chemistry, Pergamon Press, Oxford, 1999.
9. E. Negishi (Ed.),Organopalladium Chemistry for Organic Synthesis, Wiley, New York, 2002, Vols I and II.
On Organometallic Chemistry Applied to Synthesis
1. J. P. Collman, L. S. Hegedus, J. R. Norton, and R. G. Finke, Principles and Applica- tions of Organotransition Metal Chemistry, University Science Books, Mill Valley, CA, 1987.
2. P. J. Harrington,Transition Metals in Total Synthesis, Wiley, New York, 1990.
3. F. J. McQuillin, Transition Metals Organometallics for Organic Synthesis, Cambridge University Press, Cambridge, 1991.
4. H. M. Colquhoun, D. J. Thompson, and M. V. Twigg, Carbonylation, Plenum Press, New York, 1991.
5. L. S. Hegedus,Transition Metals in the Synthesis of Complex Organic Molecules, 2nd Edn, University Science Books, Mill Valley, CA, 1999.
6. S. Murahashi and S. G. Davies (Eds),Transition Metal Catalyzed Reactions, Chemistry for the 21st Century, Blackwell Science, Oxford, 1999.
7. J. Tsuji, Transition Metal Reagents and Catalysts, Innovations in Organic Synthesis, Wiley, Chichester, 2000.
3 These book references are not cited in the text.
Oxidative Reactions with Pd(II) Compounds