Covers the vastly expanding subject of oxidative processes mediated by copper ions within biological systems

Copper-mediated biological oxidations offer a broad range of fundamentally important and potentially practical chemical processes that cross many chemical and pharmaceutical disciplines. This newest volume in theWiley Series on Reactive Intermediates in Chemistry and Biology is divided into three logical areas within the topic of copper/oxygen chemistry biological systems, theory, and bioinorganic models and applicationsto explore the biosphere for its highly evolved and thus efficient oxidative transformations in the discovery of new types of interactions between molecular oxygen and copper ion. Featuring a diverse collection of subject matter unified in one complete and comprehensive resource, Copper-Oxygen Chemistry probes the fundamental aspects of copper coordination chemistry, synthetic organic chemistry, and biological chemistry to reveal both the biological and chemical aspects driving the current exciting research efforts behind copper-oxygen chemistry. In addition, Copper-Oxygen Chemistry:

Addresses the significantly increasing literature on oxygen-atom insertion and carbon-carbon bond-forming reactions as well as enantioselective oxidation chemistries

Progresses from biological systems to spectroscopy and theory, and onward to bioinorganic models and applications

Covers a wide array of reaction types such as insertion and dehydrogenation reactions that utilize the cheap, abundant, and energy-containing O2 molecule

With thorough coverage by prominent authors and researchers shaping innovations in this growing field, this valuable reference is essential reading for bioinorganic chemists, as well as organic, synthetic, and pharmaceutical chemists in academia and industry.

Kenneth D. Karlin is Ira Remsen Professor of Chemistry at Johns Hopkins University. His bioinorganic research focuses on coordination chemistry relevant to biological and environmental processes, involving copper or heme (porphyrin-iron) complexes. Dr. Karlin's main approach involves synthetic modeling, i.e., biomimetic chemistry. He is the winner of the prestigious F. Albert Cotton Award in Synthetic Inorganic Chemistry and the Sierra Nevada Distinguished Chemist Award, both awarded in 2009.

Shinobu Itoh focuses his current research on chemical modeling and application of novel active sites in biological systems. He was formerly an assistant professor at Osaka University, where he worked on the chemistry of coenzyme PQQ and cofactor TTQ as well as model compounds of galactose oxidase. In 1994, he was promoted to associate professor at Osaka University, where he collaborated with Professor Shunichi Fukuzumi in copper-dioxygen chemistry research. In 1999, he moved to Osaka City University as a full professor and started biological studies of dinuclear copper proteins, such as hemocyanin and tyrosinase. He returned to Osaka University in 2008 and further expanded his research interests to the design of artificial non-heme metalloenzymes using genetic engineering.

Preface to Series vii

Introduction ix

Contributors xi

1 Insights into the Proposed CopperOxygen Intermediates that Regulate the Mechanism of Reactions Catalyzed by Dopamine b-Monooxygenase, Peptidylglycine a-Hydroxylating Monooxygenase, and Tyramine b-Monooxygenase 1Robert L. Osborne and Judith P. Klinman

2 Copper Dioxygenases 23Jozsef Kaizer, Jozsef Sandor Pap, and Gabor Speier

3 Amine Oxidase and Galactose Oxidase 53Dalia Rokhsana, Eric M. Shepard, Doreen E. Brown, and David M. Dooley

4 Energy Conversion and Conservation by Cytochrome Oxidases 107Angela Paulus and Simon de Vries

5 Multicopper Proteins 131Takeshi Sakurai and Kunishige Kataoka

6 Structure and Reactivity of CopperOxygen Species Revealed by Competitive Oxygen-18 Isotope Effects 169Justine P. Roth

7 Theoretical Aspects of Dioxygen Activation in Dicopper Enzymes 197Kazunari Yoshizawa

8 Chemical Reactivity of Copper Active-Oxygen Complexes 225Shinobu Itoh

9 Cytochrome c Oxidase and Models 283Zakaria Halime and Kenneth D. Karlin

10 Supramolecular Copper Dioxygen Chemistry 321Jean-Noel Rebilly and Olivia Reinaud

11 Organic Synthetic Methods Using Copper Oxygen Chemistry 361Marisa C. Kozlowski

Index 445