The first catalytic enantioselective ring-opening reaction of donor-acceptor cyclopropanes with water is described. By employing Cy-TOX/Cu(II) as catalyst, the reaction performed very well over a broad range of substrates, leading to the ring-opening products in 70-96% yields with up to 95% ee under mild conditions. The current method provides a new approach to direct access to γ-substituted GBH derivatives very efficiently. Importantly, Cu(ClO4)2·6H2O proves to serve as both a Lewis acid and a source of water, which affords a fine system to controllably release water as a nucleophile in the asymmetric catalysis.

The preparation of 2-(N-alkylamino)benzothiazoles via regioselecive N-alkylation of 2-aminobenzothiazoles has been accomplished by using benzylic alcohols as alkylating agents.

Facile and effective access for the asymmetric construction of the useful and important skeleton of the bicyclic N,O-acetals is described. Cu(II) /SaBOX could catalyze the reaction of β,γ-unsaturated α-ketoesters with cyclic enamines efficiently, thus affording the desired products in excellent yields with excellent stereoselectivities (21 examples; up to 99 % yields; up to >95:5 d.r.; and 95-99 % ee). This reaction can be well performed on gram scale, even with only 1 mol % catalyst loading. The single-crystal structures of the copper complexes lead to a good understanding of the stereo-synergistic effects of the sidearm.

Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.

Nucleophilic aromatic substitution (SNAr) is a powerful strategy for incorporating a heteroatom into an aromatic ring by displacement of a leaving group with a nucleophile, but this method is limited to electron‐deficient arenes. We have now established a reliable method for accessing phenols and phenyl alkyl ethers via catalytic SNAr reactions. The method is applicable to a broad array of electron‐rich and neutral aryl fluorides, which are inert under classical SNAr conditions. Although the mechanism of SNAr reactions involving metal arene complexes is hypothesized to involve a stepwise pathway (addition followed by elimination), experimental data that support this hypothesis is still under exploration. Mechanistic studies and DFT calculations suggest either a stepwise or stepwise‐like energy profile. Notably, we isolated a rhodium η5‐cyclohexadienyl complex intermediate with an sp3‐hybridized carbon bearing both a nucleophile and a leaving group.

A biomimetic enantioselective transamination of α-keto ester derivatives can be realized under mild conditions by using chiral quaternary ammonium arenecarboxylates in the absence of base additives. The corresponding α-amino acids can be used as versatile intermediates for further synthetic transformations that furnish chiral pyrrolidine and octahydroindolizine derivatives.

In the presence of the [Cp*IrCl 2 ] 2 /NaOH system, the direct N-alkylation of 2-aminoquinazolines and 2-aminopyrimidines with alcohols afforded the N-exosubstituted 2-(N-alkylamino)quinazolines and 2-(N-alkylamino)pyrimidines with 71-96% yields and complete regioselectivities. The protocol is highly attractive because of easily available starting materials, high atom efficiency and environmental friendliness.

We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (S N Ar) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the S N Ar amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a η 6 -complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.