Copper‐Catalyzed One‐Pot Trifluoromethylation/Aryl Migration/Carbonyl Formation with Homopropargylic Alcohols

Gao, Pin; Shen, Yuemao; Fang, Ran; Hao, Xin‐Hua; Qiu, Zihang; Yang, Fan; Yan, Xiao‐Biao; Wang, Qiang; Gong, Xiang-Jun; Liu, Xueyuan; Liang, Yong‐Min

doi:10.1002/ange.201403383

Cited by 45 publications

(12 citation statements)

References 119 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Initially, the in situ -generated nitrogen-centred radical A added to the triple bond of alkyne (for example 6g ) regioselectively, providing a highly reactive vinyl radical B . Subsequently, sequential intramolecular 1,4-aryl migration via 5- ipso cyclization and desulfonylation would produce amidyl radical C 58 59 60 61 . This imidyl radical exists at an equilibrium with its resonance structure α-imino carbon radical D which could be stabilized by two aromatic rings and a C=N double bond.…”

Section: Resultsmentioning

confidence: 99%

Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

et al. 2015

View full text Add to dashboard Cite

Cascade reactions initiated by radical addition to alkynes are synthetically very attractive because they enable access to highly complex molecular skeletons in only few synthetic steps under usually mild conditions. Here we report a general radical cascade reaction of alkynes, N-fluoroarylsulfonimides and alcohols, enabling the efficient synthesis of important α-amino-α-aryl ketones from readily available starting materials via a single operation. During this process, the highly regioselective nitrogen-centred radical addition to internal and terminal alkynes generating vinyl radicals and the next explicit migration of aryl group from the nitrogen source lead the following efficient desulfonylation, oxygenation, and semi-pinacol rearrangement. In addition, the semi-pinacol rearrangement precursors, α-alkyloxyl-α,α-diaryl imines, could also be efficiently obtained under milder conditions. This methodology might open a new entry for designing intermolecular radical cascade reaction of alkynes.

show abstract

Section: Resultsmentioning

confidence: 99%

Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

et al. 2015

View full text Add to dashboard Cite

show abstract

“…[12] Very recently, we reported a copper-catalyzed trifluoromethylation/aryl migration/carbonyl formation with homopropargylic alcohols. [13] Inspired by these works, and based on our ongoing interest in the development of alkyne trifluoromethylation, we envisaged that a transition-metal-catalyzed difunctionalization of alkynes to introduce a CF 3 group Scheme 1. Transition-metal-catalyzed difunctionalization of alkenes or alkynes.…”

mentioning

confidence: 99%

Copper‐Catalyzed Difunctionalization of Activated Alkynes by Radical Oxidation–Tandem Cyclization/Dearomatization to Synthesize 3‐Trifluoromethyl Spiro[4.5]trienones

Hua

Qiu

et al. 2014

Chemistry A European J

Self Cite

129

View full text Add to dashboard Cite

A copper-catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO2CF3 or Langlois' reagent) has been developed incorporating a tandem cyclization/dearomatization process. This strategy affords a straightforward route to synthesis of 3-(trifluoromethyl)-spiro[4.5]trienones, and presents an example of difunctionalization of alkynes for simultaneous formation of two carbon-carbon single bonds and one carbon-oxygen double bond.

show abstract

“…Recently, HPA synthesis has been reported by using propargyl boronates or allenylboronates with carbonyl compounds as reactants. [10][11] The disadvantage of producing HPA through these synthetic routes is the difficulty in separating the catalyst from the products. Also, HPA synthesis requires the use of organic solvents, consequentially, this necessitates the use of extraction and chromatographic procedures to isolate and purify the product.…”

Section: Introductionmentioning

confidence: 99%

The Role of Bronsted and Lewis Acidity in the Green Synthesis of Homopropargyl Alcohols over HZSM-5

et al. 2018

View full text Add to dashboard Cite

A highly efficient and simple reaction under exceptionally mild conditions is shown for the synthesis of biologically and pharmaceutically active molecules of homopropargyl alcohol using HZSM-5 as the catalyst. Products analyzed by IR, 1H NMR, 13C NMR and GC-MS showed consistent yields of 98 % of the alcohol, even with respective recycles of the regenerated catalyst. The reaction was also carried out with selected mineral acids, acidic oxides and other acidic catalysts to compare reactivity and the influence of the type of acidity involved in the reaction. The results indicate that the presence of both Brønsted and Lewis acidity is beneficial for inducing a high rate of reaction when compared to systems having either predominantly Brønsted or Lewis acidity.

show abstract

Copper‐Catalyzed One‐Pot Trifluoromethylation/Aryl Migration/Carbonyl Formation with Homopropargylic Alcohols

Cited by 45 publications

References 119 publications

Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

Copper‐Catalyzed Difunctionalization of Activated Alkynes by Radical Oxidation–Tandem Cyclization/Dearomatization to Synthesize 3‐Trifluoromethyl Spiro[4.5]trienones

The Role of Bronsted and Lewis Acidity in the Green Synthesis of Homopropargyl Alcohols over HZSM-5

Contact Info

Product

Resources

About