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Total synthesis of the anticancer peptide natural product yaku'amide A is reported. Its β‐tert‐hydroxy amino acids were prepared by regioselective aminohydroxylation involving a chiral mesyloxycarbamate reagent. Stereospecific construction of the E‐ and Z‐ΔIle residues was accomplished through a one‐pot reaction featuring anti dehydration, azide reduction, and O→N acyl transfer. Alkene isomerization was negligible during this process. These methods enabled a highly convergent and efficient synthetic route to the natural product. [ABSTRACT FROM AUTHOR]

Abstract: The synthesis of functionalized nitriles via microwave‐promoted radical fragmentations of cyclic O‐phenyl oxime ethers is reported. A variety of radical traps can be employed, permitting the generation of diverse adducts via C−O, C−C, C−N, or C−X bond formation. Other salient features include a simple and practical protocol, very short reaction times, and the avoidance of metal catalysts and toxic cyanide reagents. The utility of this method is demonstrated by the ring‐distortion of a steroid‐derived substrate. [ABSTRACT FROM AUTHOR]