CuBr-mediated radical cascade difluoroacetamidation of acrylamides using α,α-difluoro-α-(TMS)-acetamides

@article{Liu2017CuBrmediatedRC,
  title={CuBr-mediated radical cascade difluoroacetamidation of acrylamides using $\alpha$,$\alpha$-difluoro-$\alpha$-(TMS)-acetamides},
  author={Kai Liu and Lin Sui and Qiao Jin and Deng-Yuan Li and Pei Nian Liu},
  journal={Organic chemistry frontiers},
  year={2017},
  volume={4},
  pages={1606-1610}
}
Radical cascade difluoroacetamidation of N-(arylsulfonyl)acrylamides with α,α-difluoro-α-(TMS)-acetamides has been achieved for the first time. This CuBr-mediated transformation is easy to perform, generates high yields and shows a good substrate scope. This cascade reaction proceeds via difluoroacetamidation, aryl migration and desulfonylation. The products can be readily transformed into synthetically useful compounds such as difluorofunctionalized esters and alcohols in excellent yields. 
8 Citations

Figures and Tables from this paper

Palladium-catalyzed carbonylative synthesis of α,β-unsaturated amides from aryl azides and alkenylaluminum reagent
Abstract In this work, an interesting procedure for the synthesis of α,β-unsaturated amides from aryl azides and alkenylaluminum reagent has been developed. With palladium as the catalyst and XPhosExpand
Silicon-based difluoromethylations, difluoromethylenations, pentafluoroethylations, and related fluoroalkylations
TLDR
This chapter will focus on the difluoromethylenation, pentafluoroethylation, and other related fluoroalkylation reactions reported using these silicon reagents. Expand
Recent advances in 1,4-functional group migration-mediated radical fluoroalkylation of alkenes and alkynes.
TLDR
In this article, some representative reactions of 1,4-FGM-mediated radical fluoroalkylation of N-(arylsulfonyl)acrylamides, tertiary alcohol-containing alkynes, tertiaries alcohol- containing alkenes and intermolecular 1, 4- FGM-type substrates have been discussed based on the types of substrates. Expand
Visible-light-induced intramolecular radical cascade of α-bromo-N-benzyl-alkylamides: a new strategy to synthesize tetracyclic N-fused indolo[2,1-a]isoquinolin-6(5H)-ones.
TLDR
This protocol not only exhibited a wide substrate scope but also provided a mild route to access a variety of tetracyclic N-fused indoles. Expand
The Fascinating Chemistry of α‐Haloamides
TLDR
A wide range of catalysts has been developed for the efficient incorporation of difluoroacetamido moieties into activated as well as unactivated substrates and cycloadditions with α‐halohydroxamate‐based azaoxyallyl cations have garnered significant attention. Expand
Copper-catalyzed [3 + 2]/[3 + 2] carboannulation of dienynes and arylsulfonyl chlorides enabled by Smiles rearrangement: access to cyclopenta[a]indene-fused quinolinones
  • Liwei Zhou, Xiaodong Liu, +4 authors Jin-Heng Li
  • Chemistry
  • Organic Chemistry Frontiers
  • 2021
A radical Smiles rearrangement strategy for allowing an unprecedented [3 + 2]/[3 + 2] carboannulation of dienynes with arylsulfonyl chlorides using cheap copper catalysis is described.
Radical cascade reactions of unsaturated C-C bonds involving migration
During the past few years, with the rapid development of mild methods for the generation of radical species, great progress in radical cascade reactions of unsaturated C-C bonds has been made. ManyExpand
Transcranial Magnetic Stimulation Meets Virtual Reality: The Potential of Integrating Brain Stimulation With a Simulative Technology for Food Addiction
The aim of this perspective is to propose and discuss the integration of transcranial magnetic stimulation (TMS) over the dorsolateral prefrontal cortex with virtual reality (VR) food exposure forExpand

References

SHOWING 1-10 OF 64 REFERENCES
CuSO4-Mediated Decarboxylative Difluoroacetamidation of α,β-Unsaturated Carboxylic Acids.
TLDR
The first example of decarboxylative difluoroacetamidation of α,β-unsaturated carboxylic acids by using difLUoromethyl-substituted carbonyl compounds was disclosed and furnished a broad range of diffluorinated alkenes in remarkable yields. Expand
Silver-Catalyzed Difluoroamidation of Activated Alkenes for the Construction of Difluorinated 3,3-Disubstituted Oxindoles.
TLDR
The mechanistic studies revealed that a radical pathway was involved in the transformation and the product could be efficiently derived to the corresponding difluorofunctionalized alcohol, ketone, and ester in high yields. Expand
Pd-Catalyzed α-Arylation of Trimethylsilyl Enolates of α,α-Difluoroacetamides
TLDR
This palladium-catalyzed cross-coupling reaction provides a versatile platform to generate a range of α,α-difluoro carbonyl compounds, such as α-aryl-α, α- difluoroketones, -acetaldehydes, - acetates, and acetic acids, and d ifluoroalkyl derivatives, under mild conditions. Expand
AgSCF3-mediated trifluoromethylthiolation of α,α-diaryl allylic alcohols via radical neophyl rearrangement
A novel example of AgSCF3-mediated oxidative radical trifluoromethylthiolation of α,α-diaryl allylic alcohols is presented, producing various α-aryl-β-trifluoromethylthiolated carbonyl ketones viaExpand
Copper-mediated difluoromethylation of aryl and vinyl iodides.
TLDR
The reaction of electron-neutral, electron-rich, and sterically hindered aryl and vinyl iodides with the combination of CuI, CsF and TMSCF(2)H leads to the formation of difluoromethyl-substituted products in high yield with good functional group compatibility. Expand
Transition-Metal-Free Dehydrosilylative Difluoroamidation of Tetrahydroisoquinolines under Mild Conditions.
TLDR
The dehydrosilylative difluoroamidation of α-Csp(3)-H of tetrahydroisoquinolines with α,α-difluorosoro-α-TMS-acetamides provides direct access to a broad range of α, α-dIFluoroacetamide-substituted tertiary amine derivatives in high yields. Expand
Synthesis of Aryldifluoroamides by Copper-Catalyzed Cross-Coupling.
A copper-catalyzed coupling of aryl, heteroaryl, and vinyl iodides with α-silyldifluoroamides is reported. The reaction forms α,α-difluoro-α-aryl amides from electron-rich, electron-poor, andExpand
Palladium-Catalyzed Radical Cascade Iododifluoromethylation/Cyclization of 1,6-Enynes with Ethyl Difluoroiodoacetate.
TLDR
A novel and convenient Pd-catalyzed radical cascade iododifluoromethylation/cyclization of 1,6-enynes with ethyl difluoroiodoacetate with high stereoselectivity under mild and facile reaction conditions is demonstrated, thereby allowing an efficient access to a variety of iodine-containing dif fluorine-containing pyrrolidines. Expand
Copper- and iron-catalyzed decarboxylative tri- and difluoromethylation of α,β-unsaturated carboxylic acids with CF3SO2Na and (CF2HSO2)2Zn via a radical process.
TLDR
A copper-catalyzed decarboxylative trifluoromethylation of various α,β-unsaturated carboxylic acids by using a stable and inexpensive solid, sodium trif LUM, Langlois reagent, was developed. Expand
Copper-Catalyzed Cascade Transformation of Homopropargyl Azides into Trifluoromethylated Nitriles via C-C Cleavage.
A cascade reaction of homopropargyl azides in the presence of a Cu catalyst was achieved, affording 3-(trifluoromethyl)but-3-enenitriles with good yields and excellent regioselectivity. This reactionExpand
...
1
2
3
4
5
...