Metal-free catalytic C-H silylation of a series of aromatic compounds such as N,N-disubstituted anilines with various hydrosilanes has been achieved for the first time using commercially available B(C6F5)3 as a catalyst. This protocol features simple and neutral reaction conditions, high regioselectivity, wide substrate scope (up to 40 examples), Si-Cl bond compatibility, and no requirement for a hydrogen acceptor.

The functionalization of aminoheterocycles by using a pyrylium tetrafluoroborate reagent (Pyry-BF ) is presented. This reagent efficiently condenses with a great variety of heterocyclic amines and primes the C-N bond for nucleophilic aromatic substitution. More than 60 examples for the formation of C-O, C-N, C-S, or C-SO R bonds are disclosed herein. In contrast to C-N activation through diazotization and polyalkylation, this method is characterized by its mild conditions and impressive functional-group tolerance. In addition to small-molecule derivatization, Pyry-BF allows the introduction of functional groups in a late-stage fashion to furnish highly functionalized structures.

The substituent redistribution of hydrosilanes on silicon through C-Si and Si-H bond cleavage and reformation is of great interest and importance, but this transformation is usually difficult to achieve in a selective fashion. By using electron-rich aromatic hydrosilanes, we have achieved for the first time the selective C-Si/Si-H bond homo- and cross-metathesis of a series of hydrosilanes in the presence of a boron catalyst B(CF). This protocol features simple reaction conditions, high chemoselectivity, wide substrate scope, and high functionality tolerance, offering a new pathway for the synthesis of multisubstituted functional silanes.

The C-H addition of sulfides to alkenes is an atom-efficient route for the functionalization and modification of sulfide compounds through C-C bond formation, but this transformation is highly challenging. We report here the regioselective α-C(sp)-H addition of a wide range of methyl sulfides to a variety of olefins and dienes by a half-sandwich scandium catalyst. This protocol provides a unique route for the synthesis of diverse sulfide derivatives through C-C bond formation at a sulfur-adjacent carbon atom in a 100% atom efficient fashion.

Well‐connected: The palladium‐catalyzed addition of indoles to nitriles affords 3‐acylindoles. The reaction proceeds with high selectivity, wide substrate scope, broadly available starting materials, and an operationally simple procedure. Combination with the palladium‐catalyzed intramolecular oxidative coupling of 3‐indolylarylketone gives access to indenoindolones in a one‐pot synthesis.

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.

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.

A palladium-catalyzed regioselective decarboxylative direct C-H arylation of boron dipyrromethenes (BODIPYs) at the 2,6-positions has been developed as a late-stage approach to rapidly assemble a diversity-oriented BODIPY library. With the complement of this protocol, the direct C-H arylation of BODIPYs becomes regiocontrollable at α- and β-positions. A new type of indole-fused BODIPY exhibiting bright red/NIR fluorescence with a large molar extinction coefficient (145,500 M(-1) cm(-1)) and a high quantum yield (71%) has been synthesized for the first time.