Dalton Transactions, Год журнала: 2021, Номер 50(10), С. 3394 - 3428
Опубликована: Янв. 1, 2021
The utility of pincer−nickel complexes in catalyzing reactions such as cross−coupling, oxidation, (de)hydrogenation, hydrofunctionalization, C−H activation and CO2 functionalization has been reviewed from a synthetic mechanistic point view.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(14), С. 5806 - 5815
Опубликована: Янв. 6, 2020
Abstract Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge gap between fields homogeneous and heterogeneous catalysis. Here we show that one‐pot combination Ru 1 /CeO 2 Rh SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted molecular in solution. Individually, monoatomic sites remarkable reaction specificity for double‐bond migration anti ‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity differences binding strength substrate centers. The single‐pot cooperation two allows production terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures internal olefins, alongside straightforward catalyst recycling reuse. These results demonstrate significance catalytic reactions, which are central intensification chemical processes.
Язык: Английский
Процитировано
97
Catalysts, Год журнала: 2020, Номер 10(7), С. 773 - 773
Опубликована: Июль 11, 2020
Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has potential play a fundamental role in this process, providing novel, efficient, at same time eco-friendly routes for both chemicals energy production. In particular, pincer-type ligation shows promising properties terms of long-term stability selectivity, as well allowing mild reaction conditions low catalyst loading. Indeed, pincer complexes have been applied plethora chemical processes, such hydrogen release, CO2 capture conversion, N2 fixation, biomass valorization synthesis high-value fuels. work, we show main advances last five years use transition metal key catalytic processes aiming more
Язык: Английский
Процитировано
97
Journal of Catalysis, Год журнала: 2018, Номер 365, С. 14 - 23
Опубликована: Июнь 28, 2018
Язык: Английский
Процитировано
92
The Journal of Organic Chemistry, Год журнала: 2018, Номер 83(7), С. 3657 - 3668
Опубликована: Март 13, 2018
A series of novel ruthenium(II) complexes supported by a symmetrical NNN ligand were prepared and fully characterized. These exhibited good performance in transfer hydrogenation to form new C–C bonds using alcohols as the alkylating agents, generating water only byproduct. broad range substrates, including (hetero)aryl- or alkyl-ketones alcohols, well tolerated under optimized conditions. Notably, α-substituted methylene ketones also investigated, which afforded α-branched steric hindrance products. potential application α-alkylation acetone synthesize donepezil was demonstrated, provided desired product 83% yield. Finally, this catalytic system could be applied one-pot double alkylation procedure with sequential addition two different alcohols. The current protocol is featured several characteristics, substrate scope, low catalyst (0.50 mol %) loadings, environmental benignity.
Язык: Английский
Процитировано
89
ACS Catalysis, Год журнала: 2019, Номер 9(10), С. 9317 - 9326
Опубликована: Сен. 16, 2019
A catalytic cascade system for CO2 hydrogenation to MeOH under acidic conditions is described. The reaction uses three catalysts which promote stepwise formation and conversion of formic acid formate ester intermediates. activities decomposition pathways different catalyst candidates each step were investigated. combination Ru(H)2[P(CH2CH2PPh2)3]/Sc(OTf)3/Ir(tBuPCP)(CO) was found be the most active MeOH. An overall TON 428 achieved after 40 h at 155 °C in EtOH, resulting a high concentration (1.07 M). Catalyst speciation studies upon completion indicated that carbonyl complexes [Ru[P(CH3CH2PPh2)3](H)(CO)](OTf), Ir(tBuPCP)(H)(CO)(OTf), [Ir(tBuPCP)(H)(CO)2](OTf) formed as major metal-containing species. Notably, [Ru[P(CH3CH2PPh2)3](H)(CO)](OTf) inactive hydrogenation, limiting productivity reaction.
Язык: Английский
Процитировано
79
Accounts of Chemical Research, Год журнала: 2022, Номер 55(15), С. 2148 - 2161
Опубликована: Июль 19, 2022
The discovery and development of organometallic catalysts is paramount importance in modern organic synthesis, among which the ligand scaffolds play a crucial role controlling activity selectivity. Over past several decades, d8 transition-metal complexes pincer ligands have been developed extensively thanks to their easy structural modification, versatile reactivities, high stability. One paradigm bis(phosphine)-based iridium PCP-Ir, are highly active for alkane dehydrogenation, partly due thermostability. However, except dehydrogenation related transformations, few applications catalysis seen synthesis. This mainly arises from low functional-group compatibility poor substrate scope limited catalytic chemistry that invariably involves Ir(I/III) redox processes initiated by oxidative addition substrates 14-electron (PCP)Ir fragments (the proposed catalytically intermediates). In this Account, we describe our endeavor on new family PCN-Ir with initial intention creating more efficient catalysts. replacement soft, σ-donor phosphine arm PCP harder, π-acceptor N-heteroarene (pyridine or oxazoline) not only provides an additional platform modify properties but also offers modes bond activation novel reactivities catalysis. uniqueness system lies formation, via ortho-C(sp2)-H cyclometalation pyridine unit PCNPy ligand, neutral monohydride (PCC)IrIIIHL (L = ligand), catalyzes positional stereoselective 1-alkene-to-(E)-2-alkene isomerization. Moreover, effect ethanol without decarbonylation, allowing transfer hydrogenation unactivated alkenes trans-selective semihydrogenation internal alkynes user-friendly as H-donor. Another feature originates ability pentacoordinate hydrido chloride complex (PCN)IrIIIHCl undergo reversible solvent-coordination-induced-ionization (SCII), furnishing cationic [(PCN)IrIIIH(Sol)]+Cl- bearing uncoordinated Cl anion effects selective hydrometalation over corresponding (Z)-alkenes; resulting (PCN)IrIII(vinyl)Cl undergoes amine-assisted formal alcoholysis involving protonation activated IrIII-bound EtOH, again SCII pathway. Together these elementary reactions lay foundation cis-selective EtOH. Further, design oxazoline-containing chiral (PCNOxa)IrIIIHCl enables asymmetric alkenes/ketones ethanol. α-alkylation esters/amides alcohols another case showing benefit catalyst can offer. These examples illustrate profound impact We hope Account will provide in-depth view into fundamentals ultimately broaden its
Язык: Английский
Процитировано
41
Nature Communications, Год журнала: 2023, Номер 14(1)
Опубликована: Дек. 2, 2023
We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)-H arylation/alkylation alkanes, in which binary catalytic system based on earth-abundant iron nickel is applied. Reaction selectivity between two-component arylation three-component alkylation tuned by modulating the applied current light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) this protocol, thus enabling compatibility with variety functional groups (>70 examples). The robustness method further demonstrated preparative scale late-stage diversification natural products pharmaceutical derivatives.
Язык: Английский
Процитировано
31
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)
Опубликована: Май 22, 2024
Abstract Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering wealth untapped potential for discovery. In this minireview, we delve into the burgeoning field cobaloxime catalysis in organic synthesis, which mimics catalytic activity organometallic alkylcobalamine enzymes. Our focus lies on elucidating latest advancements area, as well delineating primary mechanistic pathways at play. By describing, and comparing these mechanisms, provide comprehensive overview current state‐of‐the‐art, while also shedding light key unresolved challenges that await further exploration.
Язык: Английский
Процитировано
11
Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(45), С. 14787 - 14791
Опубликована: Окт. 11, 2018
Abstract Oxidative dehydrogenative aromatization and selective sulfonylation reactions of N ‐heterocycles under visible‐light photoredox catalysis were established. The mild reaction conditions make this approach an appealing versatile strategy to functionalize/oxidize pyrrolidines whereby arylsulfonyl chlorides identified be both catalyst regeneration reagents.
Язык: Английский
Процитировано
70
Green Chemistry, Год журнала: 2020, Номер 23(2), С. 689 - 707
Опубликована: Дек. 17, 2020
In this critical review, the recent advances of CO2-assisted catalytic dehydrogenation light alkanes are summarized.
Язык: Английский
Процитировано
70