Pd(II)-Catalyzed Aminoacetoxylation of Alkenes Via Tether Formation

A Pd-catalyzed method based on the use of a molecular tether is described for olefin difunctionalization. Enabled by an easily introduced trifluoroacetaldehyde-derived tether, a simultaneous introduction of oxygen and nitrogen heteroatoms across unsaturated carbon-carbon bonds was achieved under oxidative conditions, most probably via high-valent Pd inter-mediates. Good yields and high diastereoselectivity were obtained with aryl-substituted alkenes, whereas nonterminal alkyl-substituted olefins gave aza-Heck products. Tether cleavage under mild conditions fast access to functionalized alcohols.

Automated summary

A Pd-catalyzed method based on a molecular tether has been developed for olefin difunctionalization. Oxygen and nitrogen heteroatoms were introduced across unsaturated carbon-carbon bonds simultaneously under oxidative conditions, facilitated by a trifluoroacetaldehyde-derived tether. Good yields and high diastereoselectivity were achieved with aryl-substituted alkenes, while nonterminal alkyl-substituted olefins gave aza-Heck products. Cleavage of the tether provided access to functionalized alcohols under mild conditions.