Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO2 DOI
Yong‐Yuan Gui, Xiao‐Wang Chen,

Xiao-Yan Mo

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2919 - 2927

Опубликована: Янв. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Язык: Английский

Electrochemical reactor dictates site selectivity in N-heteroarene carboxylations DOI

Guo‐Quan Sun,

Peng Yu, Wen Zhang

и другие.

Nature, Год журнала: 2023, Номер 615(7950), С. 67 - 72

Опубликована: Янв. 5, 2023

Язык: Английский

Процитировано

185
Thermo-, Electro-, and Photocatalytic CO2 Conversion to Value-Added Products over Porous Metal/Covalent Organic Frameworks DOI

Qiu‐Jin Wu,

Jun Liang, Yuan‐Biao Huang

и другие.

Accounts of Chemical Research, Год журнала: 2022, Номер 55(20), С. 2978 - 2997

Опубликована: Сен. 26, 2022

ConspectusThe continuing increase of the concentration atmospheric CO2 has caused many environmental issues including climate change. Catalytic conversion using thermochemical, electrochemical, and photochemical methods is a potential technique to decrease simultaneously obtain value-added chemicals. Due high energy barrier however, this method still far from large-scale applications which requires activity, selectivity, stability. Therefore, development efficient catalysts convert different products urgent. With their well-engineered pores chemical compositions, surface area, elevated adsorption capability, adjustable active sites, porous crystalline frameworks metal-organic (MOFs) covalent organic (COFs) are materials for catalytic conversion. Here, we summarize our recent work on MOFs COFs thermocatalytic, electrocatalytic, photocatalytic describe structure-activity relationships that could guide design effective catalysts.The first section paper describes imidazolium-functionalized MOFs, liquid cationic with nucleophilic halogen ions, can promote thermocatalytically cycloaddition reaction epoxides toward cyclic carbonates at one bar pressure. A MOF takes role reservoir tackle low local concentrations in gas-liquid-solid heterogeneous reactions. Imidazolium-functionalized ions avoid use cocatalysts, leads milder more facile experimental conditions separation processes.In dealing electrocatalytic reduction (CO2RR), developed series conductive framework fast electron transmission capabilities, afford current densities outperform traditional COF have been reported. The intrinsically two-dimensional 2D nanosheets based fully π-conjugated phthalocyanine motif excellent transport capability were prepared, strong transporters also integrated into metalloporphyrin-based CO2RR. Cu2O quantum dots Cu nanoparticles (NPs) be uniformly dispersed MOFs/COFs synergistic and/or tandem electrocatalysts, achieve highly selective production CH4 or C2H4 CO2RR.A third efforts facilitate electron-hole photocatalysis. Our focus regulation coordination spheres fabrication architecture heterojunctions, engineering films reduction.Finally, discuss several problems associated studies consider some prospects

Язык: Английский

Процитировано

182
Visible-light photocatalytic di- and hydro-carboxylation of unactivated alkenes with CO2 DOI
Lei Song, Wei Wang, Jun‐Ping Yue

и другие.

Nature Catalysis, Год журнала: 2022, Номер 5(9), С. 832 - 838

Опубликована: Сен. 15, 2022

Язык: Английский

Процитировано

155
Recent advances of single-atom catalysts in CO2conversion DOI

Shunwu Wang,

Ligang Wang, Dingsheng Wang

и другие.

Energy & Environmental Science, Год журнала: 2023, Номер 16(7), С. 2759 - 2803

Опубликована: Янв. 1, 2023

The catalytic transformation of CO 2 into valuable fuels/chemicals is a promising and economically profitable process because it offers an alternative toward fossil feedstocks the benefit transforming cycling on scale-up.

Язык: Английский

Процитировано

145
Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities DOI Creative Commons
Binbin Huang, Zemin Sun, Genban Sun

и другие.

eScience, Год журнала: 2022, Номер 2(3), С. 243 - 277

Опубликована: Апрель 23, 2022

Compared with general redox chemistry, electrochemistry using the electron as a potent, controllable, yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis. With its environmentally benign features gradually being uncovered and studied, electrosynthesis is currently undergoing revival becoming rapidly growing area within synthetic community. Among electrochemical transformations, anodically enabled ones have been far extensively exploited than those driven by cathodic reduction, although both approaches are conceptually attractive. To stimulate development of cathodically reactions, this review summarizes recently developed reductive electrosynthetic protocols, discussing highlighting reaction features, substrate scopes, applications, plausible mechanisms reveal recent trends in area. Herein, reduction-enabled preparative transformations categorized into four types: reduction (1) unsaturated hydrocarbons, (2) heteroatom-containing carbon-based systems, (3) saturated C-hetero or C–C polar/strained bonds, (4) hetero-hetero linkages. Apart from net electroreductive few examples photo-electrosynthesis well paired electrolysis also introduced, which offer opportunities overcome certain limitations improve versatility. The electrochemically driven, transition metal-catalyzed cross-couplings that comprehensively discussed several other reviews not included here.

Язык: Английский

Процитировано

139
Visible-light photoredox-catalyzed selective carboxylation of C(sp3)−F bonds with CO2 DOI Creative Commons

Si‐Shun Yan,

Shihan Liu, Lin Chen

и другие.

Chem, Год журнала: 2021, Номер 7(11), С. 3099 - 3113

Опубликована: Авг. 27, 2021

Язык: Английский

Процитировано

132
Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO2 DOI Creative Commons

Guo‐Quan Sun,

Wei Zhang, Li‐Li Liao

и другие.

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Дек. 6, 2021

Electrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C-C bonds by using electron as the clean reductant. However, activated substrates used in most cases. Herein, we report a general practical electro-reductive Ni-catalytic system, realizing electrocatalytic carboxylation of unactivated aryl chlorides alkyl bromides with CO2. A variety bromides, iodides sulfonates can also undergo such reaction smoothly. Notably, realize electrochemical (pseudo)halides CO2 avoiding use sacrificial electrodes. Moreover, this economic strategy reductant features mild conditions, inexpensive catalyst, safe cheap electrodes, good functional group tolerance broad substrate scope. Mechanistic investigations indicate that might proceed via oxidative addition halides Ni(0) complex, reduction aryl-Ni(II) adduct Ni(I) species following

Язык: Английский

Процитировано

121
Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters DOI
Li‐Li Liao,

Zhe‐Hao Wang,

Ke-Gong Cao

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(5), С. 2062 - 2068

Опубликована: Янв. 27, 2022

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated a promising synthetic method. However, dicarboxylation C─C single bonds rarely investigated. Herein we report novel electrochemical ring-opening strained rings CO2. Structurally diverse glutaric acid adipic derivatives were synthesized from substituted cyclopropanes cyclobutanes moderate high yields. In contrast oxidative ring openings, this is also first realization an electroreductive reaction rings, including commercialized ones. Control experiments suggested that radical anions carbanions might be key intermediates reaction. Moreover, process features step atom economy, mild conditions (1 atm, room temperature), good chemoselectivity functional group tolerance, low electrolyte concentration, easy derivatization products. Furthermore, conducted polymerization corresponding diesters diols obtain potential UV-shielding material self-healing function fluorine-containing polyester, whose performance tests showed applications.

Язык: Английский

Процитировано

121
Photochemical and electrochemical strategies in C–F bond activation and functionalization DOI
Zhanghong Wang, Yu Sun,

Liu‐Yu Shen

и другие.

Organic Chemistry Frontiers, Год журнала: 2021, Номер 9(3), С. 853 - 873

Опубликована: Дек. 7, 2021

The recent advances in photochemical or electrochemical C–F bond activation and functionalization have been summarized discussed.

Язык: Английский

Процитировано

113
Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator DOI
Yanwei Wang, Zhiwei Zhao, Deng Pan

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(41)

Опубликована: Авг. 26, 2022

Herein, an electroreductive carboxylation of organic carbon-halogen bonds (X=Br and Cl) promoted by catalytic amounts naphthalene as mediator is reported. This transformation proceeds smoothly under mild conditions with a broad substrate scope 59 examples, affording the valuable versatile carboxylic acids in moderate to excellent yields without need costly transition metal, wasted stoichiometric metal reductants, or sacrificial anodes. Further late-stage carboxylations natural product drug derivatives demonstrate its synthetic utility. Mechanistic studies confirmed activation via single-electron transfer key role this reaction.

Язык: Английский

Процитировано

88