The search for efficient and selective routes for the synthesis of chiral aminocyclopropane derivatives is of great interest and importance as these structures are important components of biologically active natural products and pharmaceuticals. We herein report the enantioselective intermolecular hydroamination of substituted cyclopropenes with various amines catalyzed by chiral half-sandwich rare-earth-metal complexes. This method constitutes a 100 % atom-efficient route for the synthesis of a variety of chiral α-aminocyclopropane derivatives in high yields (up to 96 %) and excellent stereoselectivity (up to >20:1 d.r. and 99 % ee) under mild reaction conditions (25 °C).

An enantioselective C-H addition to a C=C bond represents the most atom-efficient route for the construction of chiral carbon-carbon skeletons, a central research topic in organic synthesis. We herein report the enantioselective yttrium-catalyzed C(sp )-H bond addition of 2-methyl azaarenes, such as 2-methyl pyridines, to various substituted cyclopropenes and norbornenes. This process efficiently afforded a new family of chiral pyridylmethyl-functionalized cyclopropane and norbornane derivatives in high yields and high enantioselectivities (up to 97 % ee).

The regioselective C–H borylation of aromatic ethers such as anisoles is of much interest and importance, but has remained a challenge to date. We report herein the catalytic ortho-selective C–H borylation of a wide range of aromatic ethers with pinacolborane (HBpin) by rare-earth metallocene complexes. This protocol offers an efficient and straightforward route for the synthesis of a variety of borylated aromatic ether derivatives. A proper metal/ligand combination for the rare-earth metal catalysts was found to be critically important to promote this transformation.

We herein report the diastereo- and enantioselective C­(sp)–H addition of terminal alkynes to cyclopropenes by a chiral half-sandwich gadolinium catalyst. This protocol constitutes the first example of asymmetric hydroalkynylation of cyclopropenes with terminal alkynes and offers a straightforward and 100% atom-efficient route for the synthesis of a wide range of enantioenriched alkynylcyclopropane derivatives in high yields (65–96%) and excellent stereoselectivity (>20:1 dr; 90–99% ee). Elaboration of some of the alkynylcyclopropane products through selective transformation of the CC moiety has also been demonstrated to give further diversified chiral cyclopropane derivatives which are otherwise difficult to access.

Highly anti-selective and enantioselective nitro-Mannich reactions have been achieved for a broad spectrum of substrates catalyzed by chiral bifunctional multiple hydrogen-bonding-donor amine-thioureas. Multiple hydrogen-bonding donors play a significant role in accelerating reactions and improving yields, diastereoselectivities, and enantioselectivities.