Photochemically-Generated Intermediates in Synthesis

Examines the latest applications of photochemistry to generate important intermediates

Presenting the latest breakthroughs in the field of organic photochemistry, this book offers tested and proven photochemical approaches to synthesis, creating promising new possibilities and applications for photochemical reactions. It focuses on photoreactions involving an intermediate where mechanistic aspects control the course of the reaction and its synthetic value. Readers will discover new insights into the mechanisms and nature of photo-produced reactive intermediates for organic synthesis as well as the methods to generate them. Moreover, by focusing on highly efficient techniques for producing such species, the authors enable researchers to design and perform photoreactions within the framework of green, sustainable chemistry.

Photochemically-Generated Intermediates in Synthesis begins with a discussion of the principles and practice of photo-generated intermediates. Next, the book explores:

• Photogeneration of carbon-centered radicals
• Photogeneration of heteroatom-centered radicals
• Photogeneration of biradicals and radical pairs
• Photochemical generation of radical ions
• Photogeneration of carbocations and carbanions
• Photogeneration of carbenes and nitrenes

The book's final chapter is dedicated to the photochemical manipulation of intermediates. Each chapter includes key kinetic data for typical intermediates as well as detailed case examples, giving readers all the tools needed to perform their own photochemical reactions. Comparisons to non-photochemical methods are offered whenever possible.

Photochemically-Generated Intermediates in Synthesis sets the stage for greater collaboration among photochemists and synthetic organic chemists, enabling these two research communities to fully leverage photochemistry in order to generate key intermediates needed for a broad range of synthetic reactions in organic chemistry.

Preface vii

1 Photogenerated Intermediates: Principles and Practice 1

2 Photogeneration of Carbon-Centered Radicals 41

3 Photogeneration of Heteroatom-Centered Radicals 91

4 Photogeneration of Biradicals and Radical Pairs 131

5 Photochemical Generation of Radical Ions 168

6 Photogeneration of Carbocations and Carbanions 260

7 Photogeneration of Carbenes and Nitrenes 302

8 Manipulating Intermediates the Photochemical Way 328

Index 365

ANGELO ALBINI is Professor of Organic Chemistry at the University of Pavia. His scientific investigations focus on many aspects of organic photochemistry. In addition to publishing original research articles, he has coauthored or edited three books, including Handbook of Synthetic Photochemistry (Wiley). Dr. Albini is the recipient of the Federchimica Prize, awarded for creativity in chemistry.

MAURIZIO FAGNONI, PhD, is Associate Professor of Chemistry at the University of Pavia. His research emphasizes the application of photochemistry to sustainable organic synthesis, encompassing photocatalysis and phenyl cation chemistry. Dr. Fagnoni coedited Handbook of Synthetic Photochemistry (Wiley) and is the recipient of the Exploration of New Research Frontiers Award from Cariplo Foundation.