Iridium-Catalyzed Enantioselective Allylic Substitution with Aqueous Solutions of Nucleophiles

The iridium-catalyzed
asymmetric allylic substitution under biphasic
conditions is reported. This approach allows the use of various unstable
and/or volatile nucleophiles including hydrazines, methylamine, t-butyl hydroperoxide, N-hydroxylamine,
α-chloroacetaldehyde and glutaraldehyde. This transformation
provides rapid access to a broad range of products from simple starting
materials in good yields and up to >99% ee and 20:1 d.r. Additionally,
these products can be elaborated efficiently into a diverse set of
cyclic and acyclic compounds, bearing up to four stereocenters.