Photochemically-Generated Intermediates in Synthesis -- Contents -- Preface -- 1 Photogenerated Intermediates: Principles and Practice -- 1.1 INTRODUCTION -- 1.2 STUDYING THE INTERMEDIATES: THE PHOTOCHEMICAL WAY -- 1.3 PHOTOGENERATED INTERMEDIATES. FROM MECHANISTIC INVESTIGATION TO ORGANIC SYNTHESIS -- 1.3.1 Light Sources for Preparative Photochemistry -- 1.3.2 Further Experimental Parameters -- 1.3.3 Practical Hints -- REFERENCES -- 2 Photogeneration of Carbon-Centered Radicals -- 2.1 INTRODUCTION -- 2.2 ALKYL RADICALS -- 2.2.1 Alkyl Radicals from Alkyl Halides -- 2.2.2 Alkyl Radicals from Carboxylic Acids -- 2.2.3 Alkyl Radicals from Alkanes -- 2.2.4 Alkyl Radicals from other Precursors -- 2.3 VINYL RADICALS -- 2.4 ARYL RADICALS -- 2.5 SUBSTITUTED CARBON-CENTERED RADICALS -- 2.5.1 α,α-Dioxy and α-Oxy Radicals -- 2.5.2 α-Thioalkyl Radicals -- 2.5.3 α-Amino- and α-Amidoalkyl Radicals -- 2.5.4 Halomethyl Radicals -- 2.5.5 α-Keto, α-Carboxyl, and α-Carbamoylalkyl Radical -- 2.5.6 Acyl Radicals -- 2.5.7 Carbamoyl Radicals -- REFERENCES -- 3 Photogeneration of Heteroatom-Centered Radicals -- 3.1 INTRODUCTION -- 3.2 RADICALS FROM IVA GROUP ELEMENTS -- 3.2.1 Silicon-Based Radicals -- 3.2.2 Germanium- and Tin-Based Radicals -- 3.3 RADICALS FROM VA GROUP ELEMENTS -- 3.3.1 Nitrogen-Based Radicals -- 3.3.2 Phosporus-Based Radicals -- 3.4 RADICALS FROM VIA GROUP ELEMENTS -- 3.4.1 Oxygen-Based Radicals -- 3.4.2 Sulfur-Based Radicals -- 3.4.3 Selenium- and Tellurium-Based Radicals -- 3.5 VIIA GROUP ATOMS -- 3.5.1 Fluorine in Radical Reactions -- 3.5.2 Chlorine Atoms -- 3.5.3 Bromine Atoms -- 3.5.4 Iodine Atoms -- REFERENCES -- 4 Photogeneration of Biradicals and Radical Pairs -- 4.1 INTRODUCTION -- 4.2 SYNTHESIS OF CYCLIC COMPOUNDS -- 4.2.1 Formation of a Three-Membered Ring -- 4.2.2 Formation of a Four-Membered Ring -- 4.2.3 Formation of a Five-Membered Ring.

4.2.4 Formation of a Six-Membered Ring -- 4.2.5 Formation of a >6-Membered Ring -- 4.3 SYNTHESIS OF OPEN-CHAIN COMPOUNDS -- 4.3.1 By Ring Opening -- 4.3.2 By Photoelimination -- 4.3.3 By Rearrangement -- 4.4 o-, p-BENZYNES AND α, n-DIDEHYDROTOLUENES (BERGMAN, MYERS-SAITO CYCLIZATIONS AND RELATED REACTIONS) -- REFERENCES -- 5 Photochemical Generation of Radical Ions -- 5.1 PHOTOCHEMICAL ACCESS TO RADICAL IONS -- 5.2 SUBSTITUTION -- 5.2.1 Aliphatic -- 5.2.2 Nonaliphatic -- 5.3 ADDITION TO ALKENES AND ALKYNES -- 5.3.1 Intermolecular Addition onto Double or Triple C-C Bonds -- 5.3.2 Intramolecular Addition onto C═C Bonds -- 5.4 ADDITION TO CARBONYLS, IMINE, AND IMINIUM SALTS -- 5.4.1 Addition onto C═O -- 5.4.2 Addition onto C═N -- 5.5 CYCLOADDITION -- 5.5.1 Formation of a Four-Membered Ring -- 5.5.2 Formation of a Five-Membered Ring -- 5.5.3 Formation of a Six-Membered Ring -- 5.6 FRAGMENTATION -- 5.7 OXIDATION -- REFERENCES -- 6 Photogeneration of Carbocations and Carbanions -- 6.1 INTRODUCTION -- 6.2 APPLICATION OF PHOTOGENERATED ANIONS -- 6.3 APPLICATION OF PHOTOGENERATED CATIONS -- 6.3.1 Alkyl Cations -- 6.3.2 Vinyl Cations -- 6.3.3 Phenyl Cations -- REFERENCES -- 7 Photogeneration of Carbenes and Nitrenes -- 7.1 CARBENES -- 7.1.1 Structure and Chemical Behavior -- 7.1.2 Cycloaddition via Photogenerated Carbenes -- 7.1.3 C-H and C-C Insertion -- 7.1.4 Ketenes from the Wolff Rearrangement -- 7.1.5 OH Insertion -- 7.1.6 Silyloxy Carbenes -- 7.2 NITRENES -- 7.2.1 Structure and Reactivity -- 7.2.2 Trapping of the Nitrene -- 7.2.3 Trapping of Benzoazirine and Didehydroazepine -- 7.2.4 Intramolecular Trapping -- 7.2.5 Other Effects -- 7.2.6 Acylnitrenes -- REFERENCES -- 8 Manipulating Intermediates the Photochemical Way -- 8.1 GENERATING INTERMEDIATES -- 8.1.1 Intermediates that Cannot Be Accessed Thermally.

8.1.2 Spin States that Cannot Be Accessed Thermally -- 8.2 CONTROL OF THE REACTION OF INTERMEDIATES -- 8.2.1 Controlling the Temperature -- 8.2.2 Controlling Electron Transfer -- 8.2.3 Control by the Choice of the Physical State -- 8.2.4 Control of the Process Through the Irradiation Conditions -- 8.3 CONCLUSION AND OUTLOOK -- REFERENCES -- Index.