Rh(III)-Catalyzed Defluorinative [4 + 2] Annulation of N-Sulfonylarylamides with Ethyl 2-Diazo-3,3,3-trifluoropropanoate: Synthesis of 1,3,4-Functionalized Isoquinolines

Organic Letters, Journal Year: 2022, Volume and Issue: 24(49), P. 8969 - 8974

Published: Dec. 1, 2022

Using 2-diazo-3,3,3-trifluoropropanoate as a nontraditional two-carbon reaction partner, Rh(III)-catalyzed defluorinative [4 + 2] annulation for the synthesis of 1,3,4-functionalized isoquinolines was developed. The proceeds by sequential C-H carbenoid insertion, dual C-F bond cleavage/annulation, and N- to O-sulfonyl migration. resultant products were converted diverse 1,3,4-trisubstituted based on functionalization newly installed 1-sulfonate, 2-fluoro functional handles, and/or remaining ester motif.

Language: Английский

---

Organo-Photoredox Catalyzed gem-Difluoroallylation of Ketone-Derived Dihydroquinazolinones with α-Trifluoromethyl Alkenes via C(sp3)-C Bond and C(sp3)-F Bond Cleavage

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(27), P. 5561 - 5568

Published: Jan. 1, 2024

An organo-photoredox catalyzed defluorinative alkylation of ketone-derived dihydroquinazolinones with α-trifluoromethyl alkenes is described, providing a facile access to diverse set gem -difluoroalkenes.

Language: Английский

---

Synthesis of mono-fluorinated heterocycles with a ring-junction nitrogen atom via Rh(iii)-catalyzed CF₃-carbenoid C–H functionalization and defluorinative annulation

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(6), P. 1544 - 1550

Published: Jan. 1, 2023

A Rh-catalyzed two-fold C–F bond cleavage enabled [4 + 2] annulation reaction via CF 3 -carbenoid C–H functionalization of arenes with indoles or various classes azoles as the directing groups was developed.

Language: Английский

---

Visible-Light-Induced C–F and C–N Bond Cleavage for the Synthesis of gem-Difluoroalkenes

Organic Letters, Journal Year: 2022, Volume and Issue: 24(36), P. 6566 - 6570

Published: Sept. 2, 2022

Herein, we describe a novel and efficient photoredox catalytic radical addition/defluoroalkylation coupling reaction between primary amines trifluoromethyl-substituted alkenes. A series of gem-difluoroalkenes were synthesized via C–N bond cleavage α-3°, α-2°, α-1° under visible light irradiation. This is characterized by broad substrate scope good functional group tolerance.

Language: Английский

---

Organophotoredox and Hydrogen Atom Transfer Cocatalyzed C–H Alkylation of Quinoxalin-2(1H)-ones with Aldehydes, Amides, Alcohols, Ethers, or Cycloalkanes

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(21), P. 14580 - 14587

Published: Oct. 7, 2022

Described is a mild method that merges organophotoredox catalysis with hydrogen atom transfer to enable C–H alkylation of quinoxalin-2(1H)-ones feedstock aldehydes, amides, alcohols, ethers, or cycloalkanes. This reaction occurred under environmentally benign and external oxidant-free conditions, providing general sustainable access various C3-alkylated quinoxalinone derivatives broad substituent diversity good functional group compatibility.

Language: Английский

---

Synthesis of gem‐difluoroalkenes via photoredox‐catalyzed defluoroaryloxymethylation of α‐trifluoromethyl alkenes

Bulletin of the Korean Chemical Society, Journal Year: 2022, Volume and Issue: 44(1), P. 50 - 54

Published: Nov. 3, 2022

Abstract Herein, we present a novel method for the synthesis of gem ‐difluoroalkenes via visible‐light photoredox‐catalyzed defluoroaryloxymethylation α‐trifluoromethyl alkenes using α‐silyl ethers as aryloxymethyl radical precursors. This reaction shows good functional group tolerance and provides desired products in to excellent yields. Based on mechanistic studies, propose mechanism involving single‐electron oxidation an ether generate α‐aryloxymethyl radical.

Language: Английский

---

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

---

Solvent-Controllable C–F Bond Activation for Masked Formylation of α-Trifluoromethyl Alkenes via Organo-Photoredox Catalysis

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(1), P. 624 - 632

Published: Dec. 20, 2023

A solvent-controllable organo-photoredox-catalyzed C–F bond activation for masked formylation of α-trifluoromethyl alkenes with low-priced 1,3-dioxolane as formyl radical equivalent has been described. Consequently, a diversity formylated gem-difluoroalkenes and monofluoroalkenes are constructed in moderate to high yields. This approach merits readily available starting materials, mild reaction conditions, broad substrate scope. The feasibility this highlighted by the one-pot formylation/hydrolysis sequence form γ,γ-difluoroallylic aldehydes late-stage modification pharmaceutical natural product derivatives.

Language: Английский

---

Organophotoredox-catalyzed ring-opening gem-difluoroallylation of nonstrained cycloalkanols

Molecular Catalysis, Journal Year: 2022, Volume and Issue: 533, P. 112788 - 112788

Published: Nov. 4, 2022

Language: Английский

---

Visible Light Induced Selective Cleavage of Single C(sp3)-F Bond in Trifluoromethyl Groups Containing Compounds

Tetrahedron, Journal Year: 2024, Volume and Issue: 163, P. 134155 - 134155

Published: July 16, 2024

Language: Английский

---