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CONTENTS 1. Introduction 5004 2. Synthesis of Six-Membered Cyclic Oxime Ethers 1 and 2 5005 2.1. [4 þ 2]-Cycloaddition Reactions 5005 2.2. Intramolecular Cyclization of γ-Functionalized Oximes 5009 2.3. Intramolecular Cyclization of Functionalized O-Substituted Hydroxylamines 5012 2.4. Synthesis of SCOE from N-O-Containing Heterocyclic Derivatives 5012 2.4.1. Synthesis of SCOE from Other 1,2-Oxazines 5012 2.4.2. Synthesis of SCOE from Isoxazolines and Five-Membered Cyclic Nitronates 5014 2.5. Other Methods 5014 3. Chemical Properties of SCOE 5016 3.1. Reduction of SCOE 5016 3.1.1. Reduction of SCOE to Tetrahydro-2H-1,2oxazines 5018 3.1.2. Reduction of SCOE with 1,2-Oxazine Ring-Opening 5020 3.1.2.1. Reduction of SCOE to 1,4-Amino Alcohols. 5020 3.1.2.2. Reduction of SCOE to Carbonyl Compounds. 5021 3.1.2.3. Reduction of SCOE to γ-Hydroxyoximes. 5022 3.1.3. Reduction Reactions of SCOE with 1,2-Oxazine Ring Contraction 5022 3.1.3.1. Reduction of SCOE to Pyrrolidines. 5022 3.1.3.2. Reduction of SCOE to N-Hydroxypyrrolidines. 5023 3.1.3.3. Reduction of SCOE to Pyrroles. 5024 3.1.3.4. Reduction of SCOE to Aziridines. 5025 3.1.3.5. Reduction of SCOE to Furan Derivatives. 5025 3.2. Addition Reactions to the CdN Double Bond of SCOE 5026 3.3. 1,2-Oxazine Ring-Opening in SCOE 5027 3.4. Deoximation of SCOE 5028 3.5. 1,2-Oxazine Ring Rearrangements in SCOE 5028 3.6. 1,2-Oxazine Ring Fragmentation Reactions in SCOE 5030 4. SCOE in the Synthesis of Natural Products and Biologically Active Compounds 5031 4.1. Synthesis of Amino Acids 5032 4.2. Synthesis of Polyhydroxylated Pyrrolidines 5033 4.3. Synthesis of Pyrrolizidine and Indolizidine Alkaloids and Their Analogs 5033 4.4. Synthesis of Biologically Active 2-Aryl-Substituted Pyrrolidines and Amines 5035 4.5. Synthesis of Other Natural Compounds 5036 5. Conclusion 5037 Author Information 5037 Biographies 5038 Acknowledgment 5038 References 5038

An unusual intramolecular cyclization of tris(beta-oximinoalkyl)amines 1 into 4,6,10-trihydroxy-1,4,6,10-tetraazaadamantanes 2 was discovered. Compounds 2 are related to a previously unknown type of heteroadamantanes that contain the cage isomeric to urotropin. A simple three-step synthesis of tetraazaadamantanes 2 and their N-substituted derivatives 3 and 4 from ammonia and aliphatic nitro compounds via the intermediacy of available tris-oximes 1 was developed.