Palladium in Heterocyclic Chemistry, Volume 26, Second Edition: A Guide for the Synthetic Chemist (Tetrahedron Organic Chemistry)

659 Pages·2006·12.44 MB·English

by  Jie Jack Li

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Contributing authors
Nadia M.Ahmad Prof.Bert U.W.Maes
School of Chemistry Department of Chemistry
University of Nottingham University of Antwerp
University Park Groenenborgerlaan 171
Nottingham B-2020 Antwerp, Belgium
NG7 2RD, UK
Prof.Richard J.Mullins
Dr.Marudai Balasubramanian and Adam M.Azman
Research Informatics Department of Chemistry
Pfizer Global Research & Development Xavier University
2800 Plymouth Road 3800 Victory Parkway
Ann Arbor, MI 48105 Cincinnati, OH 45207-4221
Dr.Paul Galatsis Dr.Michael Palucki
Department of Chemistry Department of Process Research
Pfizer Global Research & Development Merck & Co., Inc.
2800 Plymouth Road Rahway, NJ 07065-0900
Ann Arbor, MI 48105
Prof.Kevin M.Shea
Prof.Gordon W.Gribble Department of Chemistry
Department of Chemistry Clark Science Center
6128 Burke Laboratory Smith College
Dartmouth College Northampton, MA 01063
Hanover, NH 03755
Prof.John P.Wolfe
Dr.Jie Jack Li Department of Chemistry
Department of Chemistry University of Michigan
Pfizer Global Research & Development 930 N. University Avenue
2800 Plymouth Road Ann Arbor, MI 48109-1055
Ann Arbor, MI 48105
Dr.Chris Limberakis
Chemistry Department
Pfizer Global Research & Development
2800 Plymouth Road
Ann Arbor, MI 48105
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PPrreeffaaccee to the second edition
The first edition of “Palladium in Heterocyclic Chemistry – A guide to the Synthetic
Chemist,” published five years ago, was warmly received by many readers. Five years
is a fleeting interval in scientific history, but palladium chemistry in general, and
palladium in heterocyclic chemistry in particular, has matured considerably. In order to
make the second edition more thorough and up-to-date, we are fortunate to have recruited
a group of stellar authors to take on the challenge. As a consequence, not only have we
attempted to improve and update each chapter, but we have also added three new
chapters: Chapter 12: Quinolines; Chapter 13: Pyridazines; Chapter 14: Industrial
scale palladium chemistry. We are indebted to all authors for their contributions.
We welcome your critique.
Jack Li and Gordon Gribble, March 2006
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PPrreeffaaccee to the first edition
Palladium chemistry, despite its immaturity, has rapidly become an indispensable tool for
synthetic organic chemists. Today, palladium-catalyzed coupling is the method of choice
for the synthesis of a wide range of biaryls and heterobiaryls. The number of applications
of palladium chemistry to the syntheses of heterocycles has grown exponentially.
Then, is there a need for a monograph dedicated solely to the palladium chemistry in
heterocycles? The answer is a resounding “yes!”:
1. Palladium chemistry of heterocycles has its “idiosyncrasies” stemming from their
different structural properties from the corresponding carbocyclic aryl compounds.
Even activated chloroheterocycles are sufficiently reactive to undergo Pd-catalyzed
reactions. As a consequence of αand γactivation of heteroaryl halides, Pd-catalyzed
chemistry may take place regioselectively at the activated positions, a phenomenon
rarely seen in carbocyclic aryl halides. In addition, another salient peculiarity in
palladium chemistry of heterocycles is the so-called “heteroaryl Heck reaction.”
For instance, while intermolecular Pd-catalyzed arylations of carbocyclic arenes are
rare, Pd-catalyzed arylations of azoles and many other heterocycles readily take place.
Therefore, the principal aim of this book is to highlight important Pd-mediated
reactions of heterocycles with emphasis on the unique characteristics of individual
heterocycles.
2. A myriad of heterocycles are biologically active and therefore of paramount importance
to medicinal and agricultural chemists. Many heterocycle-containing natural products
(they are highlighted in boxes throughout the text) have elicited great interest
from both academic and industrial research groups. Recognizing the similarities
between the palladium chemistry of arenes and heteroarenes, a critical survey of
the accomplishments in heterocyclic chemistry will keep readers abreast of such a
fast-growing field. We also hope this book will spur more interest and inspire ideas in
such an extremely useful area.
We have compiled important preparations of heteroaryl halides, boranes, and stannanes
for each heterocycle. The large body of data regarding Pd-mediated polymerization of
heterocycles in material chemistry is not focused here; neither is coordination chemistry
involving palladium and heterocycles.
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