Oxidative amidation of phenols through the use of hypervalent iodine reagents: Development and applications

This contribution reviews a family of reactions devised in our laboratory that effect the oxidative conversion of phenols into 4-amido-dienones. A salient feature of this chemistry is the use of hypervalent iodine reagents, especially diacetoxyiodobenzene (DIB), as uniquely capable oxidants in the context of the new transformation. The advent of this methodology has created new opportunities in alkaloid synthesis. Our efforts toward FR-901483, TAN-1251C, cylindricine C, and other nitrogenous natural products illustrate some applications in that domain. 1 Introduction 2 Background 3 First-Generation Oxidative Amidation of Phenols: The Oxazoline Route 4 Initial Applications: Total Synthesis of FR-901483 and of TAN-1251C 5 Second-Generation Oxidative Amidation of Phenols: Sulfonamide Technology 6 Applications: Total Synthesis of (-)-Cylindricine C 7 Third-Generation Solution: The Bimolecular Reaction 8 Conclusion.