The Passerini reaction is a classical and well-known multicomponent reaction for accessing α-acyloxy amides. A single reactant replacement (SRR) approach of Passerini reaction is described, which involves aldehydes, carboxylic acids, and ynamides to constitute a one-pot synthesis of β-acyloxy amides in a convergent manner. When this method was subject to intramolecular reaction, the process would produce phthalide products. The scalability was demonstrated, and a crossover reaction was conducted to elucidate a plausible mechanism.

An iron(III)-promoted hydroalkynylation of unactivated alkenes toward Csp–Csp3 bond formation has been developed. Various alkenes, including mono-, di-, and trisubstituted alkenes, could all smoothly convert to structural diversified alkynes in this chemoselective protocol. Additionally, the scalability was unraveled and the further divergent transformations of products were conducted to demonstrate the synthetic utility.

A divergent synthesis of amides and nitriles from vinyl azides and p-quinone methides (p-QMs) was developed. The p-QMs could be activated by BF3-Et2O and then nucleophilically attacked by vinyl azides, leading to divergent rearrangement toward amides and nitriles.

A nickel-catalyzed acetamidation and lactamization of arylboronic acids via a one-pot reaction with ynamides and N-hydroxyphthalimide is described. This protocol features with mild reaction conditions and a broad substrate scope, and has been successfully applied to late-stage functionalization of pharmaceuticals. Moreover, control reactions were conducted to elucidate a plausible mechanism.

The para-quinone methides (p-QMs) are activated by Lewis acid and then attacked by diazo compounds. The following rearrangement leads to nitrogen gas extrusion and C–C double bond formation to constitute a metathesis reaction process. Therefore, the diazoester is transformed into tetrasubstituted alkenes, whereas the diazo-oxindole delivers the quinolinone products. Furthermore, the 13C-labeling experiments were also conducted to elucidate a possible mechanism.

A silver(I)-mediated phosphorylation/cyclization radical cascade of N-cyanamide alkenes has been developed. The addition of in situ generated phosphorus radical to N-cyanamide alkenes triggers the cascade, resulting in late-stage cyclization toward divergent access to 4-quinazolinones and dihydroisoquinolinones. Both terminal and internal N-cyanamide alkenes are applicable in this protocol, and the cyclizations are consistent with Baldwin’s rule.

A novel Fe-catalyzed hydroalkylation of olefins with para-quinone methides (p-QMs) for accessing phenols has been developed. In this protocol, various olefins could convert to alkyl radicals and undergo addition to para-quinone methides toward C–C bond formation and aromatization. The reaction conditions are mild and the substrate scopes are broad.

A novel Fe-catalyzed olefin hydroamination with diazo compounds for accessing hydrazones has been developed. Diazo compounds are used as radical acceptors and can be trapped by the in situ generated alkyl radical toward C–N bond formation. The reaction conditions are mild, and the substrate scope is broad. Additionally, this hydroamination protocol is applicable for intramolecular reactions to construct diverse heterocycles.

A Rh(III)-catalyzed C–H activation/cyclization of oximes and alkenes for facile and regioselective access to isoquinolines has been developed. This protocol features mild reaction conditions and easily accessible starting materials, and has been applied to the concise synthesis of moxaverine. A kinetic isotope effect study was conducted and a plausible mechanism was proposed.

A Rh(III)-catalyzed aromatic C–H bond carbenoid functionalization of triazenes by α-diazomalonates has been developed, with features of mild reaction condition and high efficiency. Furthermore, the functionalized triazenes could be subject to divergent synthesis.

An Fe-catalyzed reductive coupling of unactivated alkenes with β-nitroalkenes has been developed. The reaction proceeds through a radical pathway, with β-nitroalkenes serving as the vinylating reagents and the nitro group being cleaved in the process. Therefore, this method provides a viable synthetic approach to valuable secondary- and tertiary-alkylated styrene derivatives. Furthermore, control experiments were conducted and a plausible mechanism is proposed.

A Rh(III)-catalyzed one-pot reaction of benzamides, ketones, and hydrazines for facile access to isoindolinones is reported. In this method, various ketones are transformed into donor–donor diazo compounds, which sequentially engage in insertion with benzamides under Rh(III) catalysis to generate N-substituted quaternary isoindolinones.

A Rh(III)-catalyzed aldehyde C–H bond functionalization of salicylaldehydes with arylboronic acids has been developed, with features of mild reaction condition and high efficiency. Furthermore, the functionalized 2-hydroxybenzophenone could be subject to divergent synthesis of heterocycles.

A Rh(III)-catalyzed C–H activation–desymmetrization of diazabicycles with arenes as an expedient approach to functionalized cyclopentenes is reported. This protocol provides a novel and efficient strategy for the desymmetrization of diazabicycles, featuring simple starting materials, mild reaction conditions, high efficiency and broad substrate scope. Control experiments and a kinetic isotope effect study were conducted, and a plausible mechanism was proposed.

A Rh(III)-catalyzed selective coupling of N-methoxy-1H-indole-1-carboxamide and aryl boronic acids is reported. The coupling is mild and efficient toward diverse product formation, with selective C–C and C–C/C–N bond formation. Kinetic isotope effects studies were conducted to reveal a mechanism of C–H activation and electrophilic addition.

Copper-catalyzed cyclization of an oxime ester toward divergent heterocycle synthesis is reported. Oxime ester serves as an enamine precursor to cyclize with malononitrile and aldehydes for access to 2-aminonicotinonitriles in a one-pot reaction, while cyclizing with N-sulfonylimines leads to synthesis of pyrazolines.

A simple synthesis of 2-hydroxylated (E)-stilbenes was accomplished in good yields via oxidative coupling of 2-hydroxystyrenes and arylboronic acids, with Rh(III)-catalyst and Cu(OAc)2 as oxidant. The antiproliferative evaluation of all the synthesized compounds were assessed on four different human cancer cell lines (Colo-205, MDA-468, HT29, and MGC80-3), and the results showed that several compounds exhibit strong antiproliferative activities (up to IC50 = 35 nM for MGC80-3).A simple synthesis of 2-hydroxylated (E)-stilbenes was accomplished in good yields via oxidative coupling of 2-hydroxystyrenes and arylboronic acids, with Rh(III)-catalyst and Cu(OAc)2 as oxidant. The antiproliferative evaluation of all the synthesized compounds were assessed on four different human cancer cell lines (Colo-205, MDA-468, HT29, and MGC80-3), and the results showed that several compounds exhibit strong antiproliferative activities (up to IC50 = 35 nM for MGC80-3.

We report herein a new strategy of the Rh(III)-catalyzed C–H activation/cyclization of indoles and pyrroles, for the divergent synthesis of privileged heterocycles. A simple derivation of indoles and pyrroles to N-carboxamides with oxidative bidentate directing group could enable rhodacycle formation and late-stage redox-neutral cyclization with alkynes, alkenes and diazo compounds, for access to five- and six-membered fused heterocycles, such as pyrimido[1,6-a]indol-1(2H)-one, 3,4-dihydropyrimido[1,6-a]indol-1(2H)-one, and 1H-imidazo[1,5-a]indol-3(2H)-ones. Kinetic isotope effect study was conducted, and a plausible mechanism was proposed. Furthermore, this protocol was applied to concise synthesis of 5-HT3 receptor antagonist in gram-scale.

An unprecedented Rh(III)-catalyzed C–H activation/cycloaddition of benzamides and methylenecyclopropanes for the selective synthesis of spiro dihydroisoquinolinones and furan-fused azepinones is reported. The process features simple starting materials, mild conditions, and high efficiency and is external oxidant free. The products could be easily converted to other biologically interesting heterocycles. Control experiments and kinetic isotope effect studies were conducted and a plausible mechanism is proposed.

Vinylcarbenoids are used as three-carbon components in Rh(III)-catalyzed C–H activation/[4 + 3] cycloaddition with benzamides to access azepinones. This transformation makes a feature of simple starting materials, mild reaction conditions and high efficiency. A kinetic isotope effect study was conducted and a plausible mechanism is proposed.

Vinylcarbenoids are used as three-carbon components in Rh(III)-catalyzed C–H activation/[4 + 3] cycloaddition with benzamides to access azepinones. This transformation makes a feature of simple starting materials, mild reaction conditions and high efficiency. A kinetic isotope effect study was conducted and a plausible mechanism is proposed.

An unprecedented Rh(III)-catalyzed C–H activation/cycloaddition of benzamides and methylenecyclopropanes for the selective synthesis of spiro dihydroisoquinolinones and furan-fused azepinones is reported. The process features simple starting materials, mild conditions, and high efficiency and is external oxidant free. The products could be easily converted to other biologically interesting heterocycles. Control experiments and kinetic isotope effect studies were conducted and a plausible mechanism is proposed.

A Rh(III)-catalyzed C–H activation–desymmetrization of diazabicycles with arenes as an expedient approach to functionalized cyclopentenes is reported. This protocol provides a novel and efficient strategy for the desymmetrization of diazabicycles, featuring simple starting materials, mild reaction conditions, high efficiency and broad substrate scope. Control experiments and a kinetic isotope effect study were conducted, and a plausible mechanism was proposed.

A Rh(III)-catalyzed C–H activation/cyclization of oximes and alkenes for facile and regioselective access to isoquinolines has been developed. This protocol features mild reaction conditions and easily accessible starting materials, and has been applied to the concise synthesis of moxaverine. A kinetic isotope effect study was conducted and a plausible mechanism was proposed.