Solvent-free base-controlled addition reaction ofH-phosphonates andH-phosphine oxides to α-CF₃styrenes: facile synthesis of β-CF₃-substituted phosphonates and phosphine oxides

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(24), P. 4982 - 4987

Published: Jan. 1, 2023

An efficient solvent-free synthesis of β-CF 3 -substituted phosphonates and phosphine oxides via hydrophosphonylation hydrophosphinylation α-CF styrenes with H -phosphonates -phosphine was developed.

Language: Английский

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Nickel‐Catalyzed Selective C(sp²)−F Bond Alkylation of Industrially Relevant Hydrofluoroolefin HFO‐1234yf

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 20, 2023

The selective transition-metal catalyzed C-F bond functionalization of inexpensive industrial fluorochemicals represents one the most attractive approaches to valuable fluorinated compounds. However, C(sp2 )-F carbofunctionalization refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed alkylation HFO-1234yf with alkylzinc reagents. resulting 2-trifluoromethylalkenes can serve as versatile synthon for diversified transformations, including anti-Markovnikov type hydroalkylation and synthesis bioactive molecule analogues. Mechanistic studies reveal that lithium salt is essential promote oxidative addition Ni0 (Ln ) bond; less electron-rich N-based ligands, such bipyridine pyridine-oxazoline, feature comparable or even higher rates than phosphine ligands; strong σ-donating PMe3 , are detrimental transmetallation, but bulky facilitate transmetallation reductive elimination form final product.

Language: Английский

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Ni-Catalyzed Reductive Dibenzylation of Trifluoromethylalkenes for CF₃-Containing All-Carbon Quaternary Center Construction

Organic Letters, Journal Year: 2023, Volume and Issue: 25(32), P. 5995 - 6000

Published: Aug. 8, 2023

A Ni-catalyzed reductive dicarbofunctionalization of α-CF3 styrenes with benzyl bromides has been accomplished. This transformation obviates the commonly facile β-F elimination effectively and enables creation CF3-substituted all-carbon quaternary centers pharmaceutical interests. Preliminary mechanistic studies suggest a pathway consisting radical addition subsequent nickel-mediated benzylation resulting α-CF3-embedded tertiary C radical.

Language: Английский

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Light-Induced Iron-Catalyzed Trifluoromethylative Thiolation of Alkenes

Organic Letters, Journal Year: 2022, Volume and Issue: 24(43), P. 8057 - 8061

Published: Oct. 26, 2022

A series of novel trifluoromethylative thiolations alkene are realized by using visible light as a driving force and iron salts catalyst, 1,2-bis(trifluoromethylated) compounds could be obtained in moderate to good yields. These multicomponent protocols proceed an atom-economical way with broad substrate scope. Biologically active chemicals can also tolerated provide desired products, suggesting that the catalytic protocol viable for late-stage modification pharmaceutical discovery. At last, flow-setup synthesis product is successfully applied on gram scale, indicating synthetic power these reactions industrial applications.

Language: Английский

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MnBr₂‐Catalyzed Aerobic Oxyazidation of Fluoroolefins: Access to Fluoroalkylated β‐Hydroxy Aliphatic Azides

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(3), P. 342 - 354

Published: Jan. 18, 2023

Abstract MnBr 2 ‐catalyzed oxyazidation of fluoroolefins with molecular oxygen and TMSN 3 is reported. This method gives rise to various useful fluoroalkylated β‐hydroxy aliphatic azides in 36%–97% yields. Importantly, this protocol features mild conditions, operationally simple, gram‐scalable, it tolerates functional groups has been applied the synthesis diverse attractive bioactive compounds analogous. Mechanism studies enable detection intermediate indicate that a radical reaction process involved. The β‐fluoride elimination α‐fluoroalkylated radicals via radical‐polar crossover pathway was completely inhibited reaction. magnified image

Language: Английский

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Oxidation of Difluorocarbene by Pyridine N‐Oxide and Ensuing Access to Carbamoyl Fluorides^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(22), P. 2981 - 2987

Published: June 30, 2023

Comprehensive Summary A practical one‐pot preparation of carbamoyl fluorides from easily obtained pyridine N ‐oxide, commercially available secondary amines and synthetically versatile difluorocarbene precursors (Ruppert‐Prakash reagent or Chen's reagent) was developed herein, which dexterously resorted to the oxidation by external ‐oxide produce toxic gaseous fluorophosgene in situ . Notable features this method include nice functionality tolerance, late‐stage modification drug molecules recovery recycle quinoline.

Language: Английский

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Air‐Induced Hydroxyphosphorylation of α‐Trifluoromethyl Styrenes with H‐Phosphonates and H‐Phosphine Oxides

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: unknown

Published: Aug. 22, 2023

Abstract Efficient synthesis of β‐hydroxy‐β‐CF 3 ‐phosphonates and ‐phosphine oxides by Mn‐mediated or transition‐metal‐free hydroxyphosphorylation α‐trifluoromethy)styrenes with H the assistance air, respectively, was described.

Language: Английский

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Copper-Catalyzed Synthesis of 4-CF3-1,2,3-Triazoles: An Efficient and Facile Approach via Click Reaction

Molecules, Journal Year: 2024, Volume and Issue: 29(6), P. 1191 - 1191

Published: March 7, 2024

Incorporation of a trifluoromethyl group with 1,2,3-triazoles motifs was described. We explored click reaction approach for regioselective synthesis 1-susbstituted-4-trifluoromethyl-1,2,3-triazoles in which 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) reacts commercial 2-bromo-3,3,3-trifluoropropene (BTP) to form 3,3,3-trifloropropyne (TFP) situ. Arising from merits associated the availability and stability BTP, high efficiencies CuI/1,10-Phenanthroline (Phen)-catalyzed cycloaddition reactions azides alkynes, this readily performed process takes place target yields, wide azide substrate scope. The potential value protocol demonstrated by its application gram-scale reaction.

Language: Английский

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Two-step synthesis of vicinal trifluoromethyl primary amines from α-(trifluoromethyl)styrenes and phthalimide

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(23), P. 4641 - 4646

Published: Jan. 1, 2024

A novel two-step synthesis of β-trifluoromethyl primary amines from readily available α-(trifluoromethyl)styrenes and phthalimide is developed. The first step involves a hydroamination between (PhthNH) with the assistance base. Next, hydrazinolysis resulting

Language: Английский

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Divergent Synthesis of Benzo[4,5]imidazo[2,1-b][1,3]thiazines and α-Trifluoromethyl-β-arylthio Tertiary Alcohols from 2-Mercaptobenzimidazoles and α-CF₃ Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9610 - 9616

Published: Oct. 25, 2024

An efficient and metal-free approach for the divergent synthesis of 2-fluoro-3-aryl-4H-benzo[4,5]imidazo[2,1-b][1,3]thiazines α-trifluoromethyl-β-arylthio tertiary alcohols from 2-mercaptoimidazoles α-CF3 alkenes has been developed. The chemoselectivity was well controlled by base or light; a series were afforded via base-mediated sequential SN2′- SNV-type reactions. Meanwhile, could be selectively achieved through visible-light-driven electron donor–acceptor (EDA) complex-initiated radical cascade thiolation/hydroxylation in absence base, transition metal, external photocatalyst.

Language: Английский

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