Reported herein is the first enantioselective β-elimination reaction catalyzed by a chiral cation-binding polyether. By using this catalytic protocol, a wide range of β-sulfonyl ketones could be effectively resolved with high stereoselectivity (S up to >300). Key to the success of this process is the favorable secondary interactions of the catalyst with the Lewis basic groups on the sulfone substrate. The enone product of this process can be easily converted into the racemic starting material, and allows an effective recycling and overall synthesis of chiral β-sulfonyl ketones in high yield and excellent enantioselectivity.

The enantioselective construction of axially chiral aryl-naphthopyran skeletons was realized by organocatalytic atroposelective intramolecular [4+2] cycloaddition of in situ generated vinylidene ortho-quinone methides, from 2-ethynylphenol derivatives, with alkynes. Through this method, the heteroatropisomers were obtained with excellent yields and enantioselectivities. Moreover, a speculative model of the stereochemical outcome is proposed based on preliminary mechanistic studies. The products having various functional groups can be easily transformed into valuable intermediates as either potential ligands or organocatalysts.

A copper-catalyzed 1,4-addition reaction of arylsulfonyl iodides with 1,3-enynes afforded various allenyl halides in high yields under mild conditions via a radical mechanism.