Chiral allenes are readily accessed in a single pot operation in the reaction of terminal alkynes, aldehydes, chiral secondary amines, and zinc halides in good yields (up to 77% yield) and excellent enantioselectivities (up to 99% ee) in toluene at 120 °C. The reaction proceeds through initial formation of chiral propargylamine intermediates with creation of a new stereogenic center and subsequent chirality transfer via an intramolecular hydride shift to produce chiral allenes with high enantiomeric purities.

Copper bromide promoted reactions of aldehydes, 1-alkynes, and chiral 2-dialkylaminomethylpyrrolidine at 25 °C give the corresponding chiral propargylamine derivatives in up to 96% yield and 99:1 dr that are readily converted to the corresponding disubstitued chiral allenes in up to 81% yield and 99% ee upon reaction with CuI in dioxane at 100 °C.

Alkynyl hydrazones are synthesized conveniently from 2-oxo-3-butynoates and hydrazine by suppressing the susceptible formation of pyrazoles. The resultant hydrazones are transformed into alkynyl diazoacetates under metal-free and mild oxidative conditions in excellent yields. Further, the alkynyl cyclopropane and propargyl silane carboxylates are synthesized in good yields by developing an unprecedented copper-catalyzed alkynyl carbene transfer reaction.

An organocatalytic kinetic resolution of racemic secondary nitroallylic alcohols via Michael/acetalization sequence to give fully substituted tetrahydropyranols is described. The process affords the products with high to excellent stereoselectivities (up to 19.9:1.5:1 dr and 98% ee). The highly enantioenriched, less reactive (S)-nitroallylic alcohols 3 were isolated with good to high chemical yields (30-44%). The synthetic application of the resolved substrate is shown toward the synthesis of enantioenriched (+)-(2S,3R)-3-amino-2-hydroxy-4-phenylbutyric acid.

Two transition-metal-free methods to access substituted phenols via the arylation of silanols or hydrogen peroxide with diaryliodonium salts are presented. The complementary reactivity of the two nucleophiles allows synthesis of a broad range of phenols without competing aryne formation, as illustrated by the synthesis of the anesthetic Propofol. Furthermore, silyl-protected phenols can easily be obtained, which are suitable for further transformations.