Journal of Organometallic Chemistry, Journal Year: 2023, Volume and Issue: 999, P. 122831 - 122831
Published: July 28, 2023
Language: Английский
Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(31), P. 14288 - 14296
Published: July 27, 2022
The application of abundant and inexpensive fluorine feedstock sources to synthesize fluorinated compounds is an appealing yet underexplored strategy. Here, we report a photocatalytic radical hydrodifluoromethylation unactivated alkenes with industrial chemical, chlorodifluoromethane (ClCF2H, Freon-22). This protocol realized by merging tertiary amine-ligated boryl radical-induced halogen atom transfer (XAT) organophotoredox catalysis under blue light irradiation. A broad scope readily accessible featuring variety functional groups drug natural product moieties could be selectively difluoromethylated good efficiency in metal-free manner. Combined experimental computational studies suggest that the key XAT process ClCF2H both thermodynamically kinetically favored over hydrogen pathway owing formation strong boron–chlorine (B–Cl) bond low-lying antibonding orbital carbon–chlorine (C–Cl) bond.
Language: Английский
Citations
97
Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(10)
Published: Dec. 27, 2021
The synthesis of small organic molecules with a difluoromethylated stereocenter is particularly attractive in drug discovery. Herein, we have developed an efficient method for the direct generation stereocenters through Ni0 -catalyzed regio- and enantioselective hydrosilylation gem-difluoroalkenes. reaction also represents construction carbon(sp3 )-silicon bonds nickel catalysis, which provides atom- step-economical route high-value optically active α-difluoromethylsilanes. This protocol features readily available starting materials commercial chiral broad substrates spanning range functional groups high yield (up to 99 % yield) excellent enantioselectivity 96 ee). enantioenriched products undergo variety stereospecific transformations. Preliminary mechanistic studies were performed.
Language: Английский
Citations
63
Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(5), P. 393 - 400
Published: May 12, 2022
Language: Английский
Citations
60
Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(7), P. 1975 - 1981
Published: May 11, 2023
Language: Английский
Citations
29
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(9)
Published: Jan. 4, 2022
The generation of sulfonyl radicals has long been known as a flexible strategy in wide range different sulfonylative transformations. Meanwhile their use alkylation processes somehow limited due to inherent difficulty evolving less-stable after sulfur dioxide extrusion. Herein we report convenient that involves gem-difluorinated sulfinates an "upgrading-mask", allowing these precursors decompose into corresponding alkyl radicals. electron-donor character the formation electron donor-acceptor (EDA) complex with transient iminium ions is displayed, achieving first example stereocontrolled light-driven insertion gem-difluoro derivatives unsaturated aldehydes. This methodology compatible flow conditions, maintaining identical levels enantiocontrol.
Language: Английский
Citations
33
Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2141 - 2148
Published: Jan. 1, 2022
The first approach of photoredox catalyzed radical–radical cross-coupling difluoromethylation C(sp 3 )−H bond was reported, featuring transition metal-free, good functional group tolerance, broad substrate scope and mild reaction conditions.
Language: Английский
Citations
30
Chemical Communications, Journal Year: 2022, Volume and Issue: 58(21), P. 3477 - 3480
Published: Jan. 1, 2022
A cascade strategy to synthesise gem-difluorinated 2H-furans from reactions of BrCF2CO2Et with enaminones has been described. The tolerate a wide variety functional groups under metal-free conditions. An active aminocyclopropane is proposed be key intermediate through the cyclopropanation difluorocarbene enaminones, which further triggers regioselective C-C bond cleavage in situ afford corresponding 2H-furans.
Language: Английский
Citations
23
Organic Letters, Journal Year: 2023, Volume and Issue: 25(3), P. 533 - 537
Published: Jan. 13, 2023
The difluoromethyl group (CF2H) is of great importance in medicinal chemistry. We report herein an efficient method for the synthesis diversified α-difluoromethyl amines through copper-catalyzed hydroamination gem-difluoroalkenes, where C-N bond formed via a α-CF2H transition-metal intermediate. This new reaction proceeds Cu-H insertion to gem-difluoroalkenes and gives valuable alkyl-CF2H-containing compounds, which overcome much more challenged β-F elimination from α-fluoroalkyl organocopper species. exhibits broad substrate scope with readily available starting materials commercial catalysis.
Language: Английский
Citations
16
Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(46), P. 9236 - 9241
Published: Jan. 1, 2023
A convenient and efficient method for the synthesis of difluoro/trifluoromethyl carbinol-containing chromone derivatives has been developed.
Language: Английский
Citations
13
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6432 - 6439
Published: April 11, 2024
Herein, we disclose a nickel-catalyzed dearomative reductive aryl-fluoroalkenylation of indoles by defluorinative coupling with gem-difluoroalkenes. The catalytic protocol affords facile assembly various monofluoroalkene-containing polycyclic fused indolines bearing two contiguous carbon stereocenters in high diastereo- and enantioselectivities tolerance diverse functional groups.
Language: Английский
Citations
5