Catalysis Science & Technology, Год журнала: 2022, Номер 12(15), С. 4753 - 4762
Опубликована: Янв. 1, 2022
β-Alkylation of alcohols has been efficiently accomplished using readily available 3d metal Cr under microwave conditions in air. Well-defined molecular is involved with a KIE 7.33 and insertion α-alkylated ketone into Cr–H bond as the RDS.
Язык: Английский
Chem, Год журнала: 2020, Номер 7(5), С. 1180 - 1223
Опубликована: Дек. 9, 2020
Язык: Английский
Процитировано
218
Chemical Society Reviews, Год журнала: 2022, Номер 51(11), С. 4386 - 4464
Опубликована: Янв. 1, 2022
The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.
Язык: Английский
Процитировано
163
Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144
Опубликована: Апрель 17, 2024
Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed
Язык: Английский
Процитировано
39
Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(1), С. 215 - 220
Опубликована: Окт. 25, 2019
Highly selective β-methylation of alcohols was achieved using an earth-abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)
Язык: Английский
Процитировано
111
Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(4), С. 1485 - 1490
Опубликована: Ноя. 19, 2019
Abstract We report an earth‐abundant‐metal‐catalyzed double and single methylation of alcohols. A manganese catalyst, which operates at low catalyst loadings short reaction times, mediates these reactions efficiently. broad scope primary secondary alcohols, including purely aliphatic examples, 1,2‐aminoalcohols can be methylated. Furthermore, alcohol for the synthesis pharmaceuticals has been demonstrated. The system tolerates many functional groups among them hydrogenation‐sensitive examples upscaling is easily achieved. Mechanistic investigations are indicative a borrowing hydrogen or autotransfer mechanism involving bimetallic K‐Mn catalyst. accepts as proton hydride from alcohols efficiently reacts with chalcone via transfer.
Язык: Английский
Процитировано
106
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
Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(28), С. 11384 - 11389
Опубликована: Апрель 25, 2020
We report herein an unprecedented highly efficient Guerbet-type reaction at room temperature (catalytic TON up to >6000). This β-alkylation of secondary methyl carbinols with primary alcohols has significant advantage delivering higher-order in economical, redox-neutral fashion. In addition, the first enantioselective Guerbet also been achieved using a commercially available chiral ruthenium complex deliver moderate yield and 92 % ee. both reactions, use traceless ketone promoter proved be beneficial for catalytic efficiency.
Язык: Английский
Процитировано
96
Journal of the American Chemical Society, Год журнала: 2019, Номер 141(44), С. 17487 - 17492
Опубликована: Окт. 29, 2019
A method for the synthesis of substituted cycloalkanes was developed using diols and secondary alcohols or ketones via a cascade hydrogen borrowing sequence. non-noble air-stable manganese catalyst (2 mol %) used to perform this transformation. Various 1,5-pentanediols (3-4 equiv) (1 were investigated prepare collection cyclohexanes in diastereoselective fashion. Similarly, cyclopentane, cyclohexane, cycloheptane rings constructed from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, sterically hindered following (4 + 1), (5 (6 1) strategy, respectively. This reaction provides an atom economic methodology construct two C-C bonds at single carbon center generating high-value readily available as feedstock earth-abundant metal catalyst.
Язык: Английский
Процитировано
87
Coordination Chemistry Reviews, Год журнала: 2020, Номер 411, С. 213241 - 213241
Опубликована: Март 4, 2020
Язык: Английский
Процитировано
82
The Journal of Organic Chemistry, Год журнала: 2019, Номер 84(12), С. 7927 - 7935
Опубликована: Май 22, 2019
A general and chemoselective catalytic alkylation of nitriles using a homogeneous nonprecious manganese catalyst is presented. This reaction uses naturally abundant alcohols readily available as coupling partners. The tolerates wide range functional groups heterocyclic moieties, efficiently providing useful cyanoalkylated products with water the only side product. Importantly, methanol can be used C1 source C-methylation achieved. mechanistic investigations support multiple role metal-ligand catalyst, dehydrogenative activation alcohol, α-C-H nitrile, hydrogenation in-situ-formed unsaturated intermediate.
Язык: Английский
Процитировано
81