Pd-Catalyzed Intramolecular Aminohydroxylation of Alkenes with Hydrogen Peroxide as Oxidant and Water as Nucleophile

A palladium-catalyzed intramolecular
aminohydroxylation of alkenes
was developed, in which H2O2 was applied as
the sole oxidant. A variety of related alkyl alcohols could be successfully
obtained with good yields and excellent diastereoselectivities, which
directly derived from oxidation cleavage of alkyl C-Pd bond by H2O2. Facile transformation of these products provided
a powerful tool toward the synthesis of 2-amino-1,3-diols and 3-ol
amino acids. Preliminary mechanistic studies revealed that major nucleophilic
attack of water (SN2 type) at high-valent Pd center contributes
to the final C-O­(H) bond formation.