Metal‐Organic Frameworks of Cu₃(BTC)₂ Catalyzed Cascade C‐H Activation/C‐S Coupling/C‐O Cyclization Reaction Strategy: One‐Pot Efficient Synthesis of Phenoxathiines

Abstract

A novel synthetic strategy of cascade C−H activation/C−S coupling/C−O cyclization reaction by using metal organic framework material Cu3(BTC)2 as catalyst is investigated. In this method, Cu3(BTC)2 can effectively catalyze the hydroxylation of the ortho‐Csp2‐H of benzenethiol, and then the coupling reaction and intramolecular C−O coupling cyclization. Phenoxathiine derivatives are efficiently prepared by one‐pot method. In our work, a series of phenoxathiin derivatives were obtained in good yield by this method. At the same time, the reaction mechanism was explored through conditional control experiments.

Metal–organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C–H bond activation and functionalization reactions

“…154 In 2019, a one-pot domino C(sp 2 )-H activation/C-S coupling/ C-O cyclization reaction for the synthesis of valuable phenoxathiin (dibenzooxathiane) derivatives was reported over Cu 3 (BTC) 2 as a heterogeneous catalyst. 155 The copper ions in the framework were capable of effectively catalyzing the in situ hydroxylation of the ortho-Csp 2 -H of benzenethiol and subsequent the coupling reaction and intramolecular cyclization between thiophenols and 1,2-dihaloarenes in dimethyl sulfoxide, as the both oxidant and solvent, with cesium carbonate as the base at 130 1C (yields = 44-75%) (Scheme 75). 155 In 2020, the construction of useful hydroxyalkynylated naphthoquinones via direct and regioselective C-H functionalization by the tandem three-component reaction between naphthoquinone, alkenes and H 2 O was introduced (Scheme 76).…”

“…155 The copper ions in the framework were capable of effectively catalyzing the in situ hydroxylation of the ortho-Csp 2 -H of benzenethiol and subsequent the coupling reaction and intramolecular cyclization between thiophenols and 1,2-dihaloarenes in dimethyl sulfoxide, as the both oxidant and solvent, with cesium carbonate as the base at 130 1C (yields = 44-75%) (Scheme 75). 155 In 2020, the construction of useful hydroxyalkynylated naphthoquinones via direct and regioselective C-H functionalization by the tandem three-component reaction between naphthoquinone, alkenes and H 2 O was introduced (Scheme 76). 156 To achieve the highly selective synthesis of the desired product, a highly oriented Cu-MOF membrane catalyst with high porosity and controlled thickness and morphology was self-assembled on macroporous Cu foam by utilizing the surfactant PVA (poly-(vinyl alcohol)) as a soft-template during the synthesis of the MOF.…”

Improve the Conductivity of CuBTC by in‐situ Reduction to Core‐Shell CuTCNQ@CuBTC

“…Since their emergence, MOFs have attracted intensive attention as functional materials in hydrogen storage, [2–3] molecular recognition, [4] gas adsorption and separation, [5] selective catalyst, [6] and so on. For example, CuBTC and CuBTC‐derived composite materials are widely applied in the adsorption and removal of poluttant, [7–8] and Cu‐based organic reaction catalysts [9–11] . Recently, MOFs and their derivatives are investigated as active materials for electrochemical applications such as batteries, [12] supercapacitors, [13] and electrocatalysts [14] .…”

“…For example, CuBTC and CuBTC-derived composite materials are widely applied in the adsorption and removal of poluttant, [7][8] and Cu-based organic reaction catalysts. [9][10][11] Recently, MOFs and their derivatives are investigated as active materials for electrochemical applications such as batteries, [12] supercapacitors, [13] and electrocatalysts. [14] The large specific surface area of MOFs is conducive to electrochemical reactions, and transition metal ions with multiple valence and organic ligands can provide abundant active sites for the chemical reaction.…”

Synthesis of diaryl sulfides based on copper-doped OMS-2

“…We have also reported some methods for synthesizing aryl sulfides by heterogeneous catalysis. [12][13][14] Manganese oxide octahedral molecular sieves (OMS-2), the structure of which is similar to zeolite molecular sieves, are a new type of material that can supply a high specific surface area. Furthermore, the specialized framework structure of OMS-2 with a large number of mixed valence Mn ions (Mn 2+ , Mn 3+ , Mn 4+ ) allows it to perform well in redox reactions.…”