An efficient Fe(TPP)Cl catalyzed insertion reaction of in situ generated benzylic carbenes from N-tosylhydrazones into X-H (X = Si, Sn, Ge) was developed. Silanes bearing tertiary, secondary, and primary (3°, 2°, and 1°) Si-H bonds all reacted well to afford insertion products in moderate to high yields (up to 97%), and the reaction time could be significantly shortened to 1 h under microwave irradiation. A programmable stepwise double insertion strategy was developed for the synthesis of unsymmetrical tetrasubstituted silanes.

An iron(III)-BPsalan complex was found to efficiently catalyze the asymmetric chlorination reaction of cyclic β-keto esters and N-Boc oxindoles, affording the corresponding chlorinated products in high yield and up to 92% ee with NCS as chlorination reagent under mild reaction conditions.

A practical, highly efficient iron-catalyzed asymmetric Diels-Alder reaction of various alkylidene β-ketoesters with dienes was developed. Both cyclic and acyclic alkylidene β-ketoesters underwent the reaction well with Fe-BPsalan complex as...