Isatin-derived ketimines undergo enantioselective alkynylation reactions in the presence of copper iodide and easily accessible guanidine-amides. The corresponding 3-alkynyl-3-aminooxyindoles are obtained in up to 95% yield and 96% ee. The guanidine plays a role in the formation of copper acetylide and the enantiodetermining step and the basic additive is excluded.

An enantioselective synthesis of α‐aminoketone derivatives were readily available through a tandem insertion–[1,3] O‐to‐C rearrangement reaction. The rhodium salt and chiral N,N′‐dioxide‐indium(III) complex make up relay catalysis, which enables the O−H insertion of benzylic alcohols to N‐sulfonyl‐1,2,3‐triazoles, and asymmetric [1,3]‐rearrangement of amino enol ether intermediates, subsequently. Preliminary mechanistic studies suggested that the [1,3] O‐to‐C rearrangement step proceeded through an ion pair pathway.

An asymmetric three-component 1,3-dipolar cycloaddition of 3,4-dihydroisoquinolines, bromoacetates and α,β-unsaturated pyrazole amide is realized by using a chiral N,N'-dioxide-Y(OTf) 3 complex as the catalyst. The process includes a base-promoted formation of dihydroisoquinolium ylides in situ, and a chiral Lewis acid-catalyzed asymmetric [3 + 2] cycloaddition with α,β-unsaturated pyrazole amides. A series of hexahydropyrrolo-isoquinolines are obtained in moderate to good yields with excellent diastereo-and enantioselectivities.

Chiral polycyclic spiroindolenine is a frequently occurring structure unit in various biologically active natural products and pharmaceutical agents. The quest for facile and efficient methods for assembling such architecture from...