Palladium-Catalyzed Carbonylative Coupling and C–H Activation - New Trends in Cross-Coupling: Theory and Applications - page 479

CHAPTER 10
Palladium-Catalyzed
Carbonylative Coupling and
C-H Activation
XIAO-FENG WU* a AND CHRISTOPHER F. J. BARNARD* b
a Leibniz-Institut f¨r Katalyse eV, Albert-Einstein-Strasse 29a, Rostock,
D-18059, Germany; b Johnson Matthey Technology Centre, Blount's Court,
Sonning Common, Reading, RG4 9NH, UK
*Email: [e-mail]; [e-mail]
10.1 Introduction
Early studies by Henry, Heck and others developed the carbonylation of aryl
halides to give a wide variety of functionalized derivatives, providing useful
compounds and intermediates for further reactions in chemical synthesis. 1
As palladium-catalysed coupling chemistry was developed to employ a wide
range of reactants (e.g. alkenes - Heck, arenes - Suzuki, alkynes - Sonoga-
shira), so the mechanisms of these reactions became better understood and
the potential for extending these reactions was appreciated. Thus, the
development of carbonylative versions of these classic coupling reactions
was achieved (Figure 10.1). Here, examples are given of carbonylative Heck,
Suzuki and Sonogashira reactions, where control of the catalyst and the
reaction conditions can lead to high selectivity favouring the carbonyl
insertion product over the direct coupling product.
The above-described reactions still require the preparation of aryl halides
and potentially other reagents as their starting materials, and such prepar-
ations can, on occasion, be di cult owing to the poor stability of some of the