A direct and regiocontrolled thiolation method to access β-amino sulfides through the palladium-catalyzed C(sp²)–H functionalization of stable enamines was described. The reaction was realized under mild conditions by adding an external phosphine ligand to prevent poisoning of the palladium catalyst by the sulfuric reagents. A possible mechanism was proposed according to the obtained results. The DFT calculation results were consistent with the experiment data, which gave the E isomers of the β-amino sulfides. The reaction was also performed on a gram scale and shows potential application in organic synthesis.

Dealkylation of alkyl aryl ethers has been extensively explored. In comparison to the reported methods, selective methods that work under mild reaction conditions remain to be developed. Herein we report the development of a method that is selective, dealkylating only one of the methyl groups in polymethylated aryl ether system. This selective dealkylative method is applied to the synthesis of a few advanced intermediates for drug synthesis. Detailed mechanistic studies have shown that this reaction probably proceeds via a single-electron transfer process.

An efficient and selective Rh-catalyzed direct CH functionalization reaction of enol phosphates was developed. The method is applicable to a variety of coupling partners, including activated alkenes, alkynes, and allenes, and leads to the formation of various valuable alkenylated and hydroalkenylated enol phosphates through the action of the phosphate directing group. The versatility and utility of the coupling products were demonstrated through further transformations into synthetically useful building blocks.

Copper-catalyzed enantioselective 1,4-conjugate addition of methyl 4,4,4-trifluorocrotonate with aliphatic Grignard reagents to access an asymmetric tertiary carbon center attached with a trifluoromethyl group was achieved under mild reaction conditions. The desired products could be obtained in reasonable yields and good enantioselectivities.

An efficient and selective Rh-catalyzed direct CH functionalization reaction of enol phosphates was developed. The method is applicable to a variety of coupling partners, including activated alkenes, alkynes, and allenes, and leads to the formation of various valuable alkenylated and hydroalkenylated enol phosphates through the action of the phosphate directing group. The versatility and utility of the coupling products were demonstrated through further transformations into synthetically useful building blocks.

The rhodium(III)-catalyzed ortho CH alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation.

In this study, a remarkably simple and direct strategy has been successfully developed to selectively label target cysteine residues in fully unprotected peptides and proteins. The strategy is based on the reaction between allenamides and the cysteine thiol, and proceeds swiftly in aqueous medium with excellent selectivity and quantitative conversion, thus forming a stable and irreversible conjugate. The combined simplicity and mildness of the process project allenamide as robust and versatile handles to target cysteines and has potential use in biological systems. Additionally, fluorescent-labeling studies demonstrated that the installation of a C-terminal allenamide moiety onto various molecules of interest may supply a new methodology towards the site-specific labeling of cysteine-containing proteins. Such a new labeling strategy may thus open a window for its application in the field of life sciences.

A highly enantioselective conjugate addition of Grignard reagents to 3-silyl unsaturated esters to deliver synthetically useful chiral β-silylcarbonyl compounds was developed. The synthetic value of this methodology was further illustrated by the synthesis of enantioenriched β-hydroxyl esters and the facile access granted to various α-chiral allylic silanes. A plethora of diastereoselective transformations of β-silylenolates were also investigated and afforded manifold organosilanes that contained contiguous stereogenic centers with excellent enantioselectivity.

In this study, a remarkably simple and direct strategy has been successfully developed to selectively label target cysteine residues in fully unprotected peptides and proteins. The strategy is based on the reaction between allenamides and the cysteine thiol, and proceeds swiftly in aqueous medium with excellent selectivity and quantitative conversion, thus forming a stable and irreversible conjugate. The combined simplicity and mildness of the process project allenamide as robust and versatile handles to target cysteines and has potential use in biological systems. Additionally, fluorescent-labeling studies demonstrated that the installation of a C-terminal allenamide moiety onto various molecules of interest may supply a new methodology towards the site-specific labeling of cysteine-containing proteins. Such a new labeling strategy may thus open a window for its application in the field of life sciences.

The rhodium(III)-catalyzed ortho CH alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation.

The role of excess ligand in the asymmetric 1,4-conjugate addition (ACA) of Grignard reagents to α,β-unsaturated esters compounds catalyzed by copper(I) iodide-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl (CuI-Tol-BINAP) is explored herein. In addition, this methodology allows asymmetric induction to be carried out using a non-chiral phosphine copper complex with excess of a chiral phosphine ligand.

A highly enantioselective carbonyl-ene reaction of trifluoropyruvate catalyzed by a recyclable indium(III)-pybox complex in ionic liquid afforded trifluoromethyl-containing tertiary homoallylic alcohols with excellent yields (up to 98%) and enantioselectivities (up to 98% ee). Notably, this catalytic system can be recycled up to seven cycles.

A new class of structurally rigid tricyclic chiral ligands based on the hexahydropyrrolo[2,3-b]indole skeleton has been rationally designed and the catalytic abilities in asymmetric catalysis have been shown in the enantioselective borane reduction of prochiral ketones to afford the chiral alcohols in excellent yields and high enantioselectivities (up to 97% ee).

A highly efficient asymmetric conjugate addition of methylmagnesium bromide (MeMgBr) to α,β-unsaturated esters catalyzed by copper(I) iodide-tolyl-BNIP (CuI-Tol-BINAP) is described.

An organocatalytic enantioselective direct vinylogous Michael addition of α,α-dicyanoolefins to maleimide has been developed; the products could be obtained in good yields and high enantioselectivities.

A pool of water-compatible catalysts, namely dialkyl-(S)-prolinols, has been developed for the enantioselective direct vinylogous Michael addition reaction of vinylmalononitriles to α,β-unsaturated aldehydes in aqueous medium. In many cases, the products can be obtained in almost optically pure form (>96% ee) after a single recrystallization.

In the presence of In or Zn/AgI/InCl₃, an efficient and practical method for the Barbier–Grignard-type alkylation reactions of simple imines by using a one-pot condensation of various aldehydes, amines (including the aliphatic and chiral version), and secondary alkyl iodides has been developed. The reaction proceeded more efficiently in water than in organic solvents. Without the use of CuI, it mainly gave the imine self-reductive coupling product, which was not the alkylated product. Good diastereoselectivities (up to 92:8 dr) were obtained when L-valine methyl ester was used as the substrate.