Electrophilic iodine(I) compounds induced semipinacol rearrangement via C-X bond cleavage.

Neutral electrophilic iodine(I) species proved to be efficient reagents for C-X bond cleavage of various cyclic and acyclic α-silyloxyhalides, and the induced desilylative semipinacol rearrangement provided the corresponding ketones in good yields. The reaction is operationally simple, and proceeds under mild conditions with good functional group compatibility. Mechanistic investigations, including computational studies, were also performed.

Catalytic asymmetric synthesis of the pentacyclic core of (-)-nakadomarin A via oxazolidine as an iminium cation equivalent.

A facile and catalytic asymmetric synthesis of the pentacyclic core of (-)-nakadomarin A, containing all the stereogenic centers of the natural product was achieved. The key intermediate involves the oxazolidine moiety as an iminium cation equivalent. An efficient method for the removal of the N-hydroxyethyl group is also described.

A powerful hydrogen-bond-donating organocatalyst for the enantioselective intramolecular oxa-Michael reaction of α,β-unsaturated amides and esters.

Tuning the organocatalyst: An unprecedented enantioselective intramolecular oxa-Michael reaction of unactivated α,β-unsaturated amides and esters catalyzed by a powerful hydrogen-bond-donating organocatalyst has been developed. Furthermore, the products obtained from this reaction have been used for the straightforward asymmetric synthesis of several natural products and biologically important compounds.