Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)
Published: Aug. 29, 2023
The involvement of manganese radical for halogen atom transfer (XAT) reactions has been esteemed as one reliable method but encountered with limited catalytic models. In this paper, a novel bimetallic relay catalysis Mn2 (CO)10 and cobaloxime developed divergent dehydrogenative difluoroalkylation alkenes using commercially available difluoroalkyl bromides. A wide range structurally diverse terminal, cyclic internal well tetrasubstituted are found to be good coupling partners deliver difluoroalkylated allylic products difluoromethylated products, accompanied the production H2 by-product. This strategy features broad substrate scope, mild reaction conditions excellent functional group compatibility. Its success represents an important step-forward expedite construction rich library products.
Language: Английский
Citations
21
Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: March 21, 2025
Methanolysis of hydrosilanes is catalyzed by incomplete cubane-type Mo3(μ3-S)(μ-S)3 clusters functionalized with diamino and imidazolyl amino ligands under mild conditions. Silane activation mediated the air-stable [Mo3(μ3-S)(μ-S)3Cl3(ImNH2)3]Cl (ImNH2 = (1-methyl-1H-imidazol-2-yl)methanamine) ([3]Cl) cluster salt has been elucidated through a comprehensive experimental theoretical study. Our results support operation sulfur-centered mechanism without direct participation metals in clear contrast all previously reported mechanisms transition metal complexes. The reaction proceeds two steps, first one being rate-determining step. process starts hydrosilane Si–H bond activation, which occurs at bridging sulfur atoms unit. This step takes place concerted asynchronous state methanol molecule to yield silyl ether product bis(hydrosulfido) intermediate. Analysis this reveals that its imaginary frequency basically associated silane hydride transfer formation Si–O agreement observed KIE results. second consists hydrogen release from intermediate, catalyst recovered. same operates for [Mo3S4Cl3(en)3]Cl (en ethylenediamine) ([1]Cl) [Mo3S4Cl3(dmen)3]+ (dmen N,N′-dimethylethylenediamine) ([2]Cl) salts. calculated free energy barriers those catalysts agree catalytic activities, giving further our mechanistic proposal.
Language: Английский
Citations
0
Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(2)
Published: Oct. 20, 2023
Abstract As a crucial class of functional molecules in organosilicon chemistry, silanols are found valuable applications the fields modern science and will be potentially powerful framework for biologically active compounds or materials. It has witnessed an increasing demand non‐natural organosilanols, as well progress synthesis these structural features. From classic preparative methods to catalytic selective oxidation hydrosilanes, electrochemical hydrolysis then construction most challenging silicon‐stereogenic silanols. This review summarized catalyzed via hydroxylation hydrosilanes last decade, with particular emphasis on latest elegant developments desymmetrization strategy enantioselective from dihydrosilanes.
Language: Английский
Citations
9
Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 2, 2024
ConspectusAlkenes and alkynes are fundamental building blocks in organic synthesis due to their commercial availability, bench-stability, easy preparation. Selective functionalization of alkenes is a crucial step for the value-added compounds. Precise control over these reactions allows efficient construction complex molecules with new functionalities. In recent decades, second- third-row precious transition metal catalysts (palladium, platinum, rhodium, ruthenium) have been pivotal development metal-catalyzed synthetic methodology. These metals exhibit excellent catalytic activity selectivity, enabling functionalized molecules. However, recovery reuse long challenge this field. years, exploration earth-abundant has interested both academic industrial researchers. The such systems offers promising approach overcome limitations catalysts. For example, manganese third most naturally abundant minimal toxicity biocompatibility. It exhibits good several reactions, including C-H bond functionalization, selective reduction, radical reactions. This Account outlines our progress dinuclear catalysis alkynes. We established elementary manganese(I)-catalysis transmetalation R-B(OH)
Language: Английский
Citations
2
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29373 - 29382
Published: Oct. 16, 2024
Owing to their unique properties, the silanols have attracted intense attention but remain challenging prepare from organocatalytic oxidation of hydrosilanes using H
Language: Английский
Citations
2
Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(12)
Published: Nov. 23, 2023
Abstract Site‐selective C( sp 3 )−H functionalization of unreactive hydrocarbons is always challenging due to its inherited chemical inertness, slightly different reactivity various C−H bonds, and intrinsically high bond dissociation energies. Here, a site‐selective alkylation naphthoquinone with unactivated using Mn 2 (CO) 10 as catalyst under blue‐light (457 nm) irradiation without any external acid or base pre‐functionalization presented. The selective tertiary over secondary primary bonds in abundant feedstocks was achieved, hydroxylation quinones realized situ by employing the developed methodology. This protocol provides new catalytic system for direct construction high‐value‐added compounds, namely, parvaquone (a commercially available drug used treat theileriosis ) derivatives ambient reaction conditions. Moreover, this operationally simple applies linear‐, branched‐, cyclo‐alkanes degrees site selectivity irradiated conditions could provide rapid straightforward access versatile methodologies upgrading feedstock chemicals. Mechanistic insight radical trapping, scavenging, EPR, other controlled experiments well corroborated DFT studies suggest that proceeds pathway.
Language: Английский
Citations
5
Chemical Synthesis, Journal Year: 2023, Volume and Issue: 3(4)
Published: Oct. 11, 2023
Decacarbonyldimanganese (Mn2(CO)10), one of the most long-standing organometallic reagents, bears a weak Mn-Mn bond, which occurs homo-cleavage feasibly under heating or light-irritation, delivering an active manganese-centered radical. This highly reactive metallic radical could activate Si-H C-halogen N-halogen S-halogen and O=O generating corresponding Mn species Si, C, N, S, O radicals. wonderful reactivity enables extensive utilization this dimeric manganese in catalytic atom-transfer reactions oxidation reactions. In review, we offer comprehensive review growing area recent decades. Critical comparisons mechanism analyses are provided, along with personal perspectives for future studies.
Language: Английский
Citations
2
Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(42)
Published: Aug. 29, 2023
Abstract The involvement of manganese radical for halogen atom transfer (XAT) reactions has been esteemed as one reliable method but encountered with limited catalytic models. In this paper, a novel bimetallic relay catalysis Mn 2 (CO) 10 and cobaloxime developed divergent dehydrogenative difluoroalkylation alkenes using commercially available difluoroalkyl bromides. A wide range structurally diverse terminal, cyclic internal well tetrasubstituted are found to be good coupling partners deliver difluoroalkylated allylic products difluoromethylated products, accompanied the production H by‐product. This strategy features broad substrate scope, mild reaction conditions excellent functional group compatibility. Its success represents an important step‐forward expedite construction rich library products.
Language: Английский
Citations
1
Chemical Research in Chinese Universities, Journal Year: 2023, Volume and Issue: 39(6), P. 1077 - 1083
Published: Oct. 12, 2023
Language: Английский
Citations
1
Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Language: Английский
Citations
0