Reaction of perfluoroalkanesulfinates with allyl and propargyl halides. A convenient synthesis of 3-(perfluoroalkyl)prop-1-enes and 3-(perfluoroalkyl)allenes

胡昌明,; 卿凤翎,; 黄维垣,

doi:10.1021/jo00008a041

Cited by 39 publications

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“…The product was almost pure but contains about 1% of impurity, which could not be separated; bp 82 °C. The spectroscopic data were in agreement with the reported data …”

Section: Methodssupporting

confidence: 92%

Alternating Copolymerization of Fluoroalkenes with Carbon Monoxide

et al. 2006

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The palladium-catalyzed alternating copolymerization of fluoroalkenes, represented as CH(2)=CH-CH(2)-C(n)F(2n+1), with CO was performed using (R,S)-BINAPHOS (2e) as a ligand. The CH(2)-C(n)F(2n+1) group is the most electronegative substituent ever reported for the copolymerization (Taft's sigma value of 0.90 for CH(2)CF(3)). The copolymer obtained from CH(2)=CH-CH(2)-C(8)F(17) (1a) existed as a mixture of polyspiroketal and polyketone, while that from CH(2)=CH-CH(2)-C(4)F(9) (1b) was a pure polyspiroketal, as was revealed by infrared and (13)C-CP/MAS NMR spectroscopies. The terminal structure of the polymer from 1b was confirmed by MALDI-TOF MS spectrometry. Detailed NMR studies suggested that the much higher reactivity with (R,S)-BINAPHOS (2e) than that with the conventional ligand DPPP (2a) can be attributed to the unique 1,2-insertion of the fluoroalkene into acylpalladium species. The existence of an electronegative substituent on the alpha-carbon of the palladium center is successfully avoided in the 1,2-insertion mechanism.

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“…The product was almost pure but contains about 1% of impurity, which could not be separated; bp 82 °C. The spectroscopic data were in agreement with the reported data …”

Section: Methodssupporting

confidence: 92%

Alternating Copolymerization of Fluoroalkenes with Carbon Monoxide

et al. 2006

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“…1c,f However, in comparison with the well-developed methods for the synthesis of di-or trisubstituted difluoroalkyl allenes, the synthetic strategies for accessing tetrasubstituted difluoroalkyl allenes have been much less exploited. 3 In 2019, Wang and coworkers developed a Ni-catalyzed 1,4-carbofluoroalkylation of 1,3-enynes to access tetrasubstituted difluoroalkyl allenes using difluoroalkyl halides (Scheme 1a). 4 In 2020, Bao and coworkers reported a metal-free synthesis of tetrasubstituted difluoromethyl allenes via the 1,1,4-trifunctionalization of 1,3enynes with N-fluorobenzenesulfonimide (NFSI) as the fluorination source (Scheme 1b).…”

mentioning

confidence: 99%

HFIP-Catalyzed Difluoroalkylation of Propargylic Alcohols to Access Tetrasubstituted Difluoroalkyl Allenes

Liu

et al. 2021

Org. Lett.

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A hexafluoroisopropanol (HFIP)-catalyzed difluoroalkylation of propargylic alcohols with difluoroenoxysilanes to access structurally diverse tetrasubstituted difluoroalkyl allenes has been developed. This convenient procedure enables the rapid construction of highly functionalized multisubstituted fluorinated allenes in a mild and straightforward way. Furthermore, the synthetic potential of this methodology has been demonstrated by the facile synthesis of various structurally interesting fluorinecontaining molecules such as gem-difluorosubstituted dihydropyran, tetrasubstituted CF 2 H-allene, and multisubstituted fluorinated cyclopentanone derivatives.

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“…radical and the stoichiometric oxidant K 2 S 2 O 8 regenerates the Cu(II) from the Cu(I) formed in the latter step. The latter trifluoromethyl radical may also be generated by the direct oxidation of the Langlois reagent by K 2 S 2 O 8 , [30,31] although relatively poor yields of the trifluoromethylated products were obtained in the absence of the Cu(II) catalysis (Table 1, entry 15). The CF 3 .…”

Section: Resultsmentioning

confidence: 99%

Cu‐Catalyzed C(sp²−H)‐Trifluoromethylation of Aldehyde Hydrazones with Langlois Reagent

2021

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The C(sp 2 À H)-trifluoromethylation of hydrazones would give access to the α-trifluoromethylated hydrazones that can serve as intermediates in the synthesis of pharmaceutically interesting fluorinated compounds. Herein, we demonstrate the Cu-catalyzed C(sp 2 À H)-trifluoromethylation of the aldehyde hydrazones using the readily available and cost effective Langlois reagent (sodium trifluoromethanesulfinate). This reaction is broadly applicable to a series of aromatic aldehyde N-aminomorpholine hydrazones to give the corresponding C(sp 2 )-trifluoromethyl hydrazones in moderate to high yields. The reaction generally tolerates a series of electron-releasing as well as electronwithdrawing substituents on the aromatic ring.

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Reaction of perfluoroalkanesulfinates with allyl and propargyl halides. A convenient synthesis of 3-(perfluoroalkyl)prop-1-enes and 3-(perfluoroalkyl)allenes

Cited by 39 publications

References 0 publications

Alternating Copolymerization of Fluoroalkenes with Carbon Monoxide

Alternating Copolymerization of Fluoroalkenes with Carbon Monoxide

HFIP-Catalyzed Difluoroalkylation of Propargylic Alcohols to Access Tetrasubstituted Difluoroalkyl Allenes

Cu‐Catalyzed C(sp²−H)‐Trifluoromethylation of Aldehyde Hydrazones with Langlois Reagent

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Reaction of perfluoroalkanesulfinates with allyl and propargyl halides. A convenient synthesis of 3-(perfluoroalkyl)prop-1-enes and 3-(perfluoroalkyl)allenes

Cited by 39 publications

References 0 publications

Alternating Copolymerization of Fluoroalkenes with Carbon Monoxide

Alternating Copolymerization of Fluoroalkenes with Carbon Monoxide

HFIP-Catalyzed Difluoroalkylation of Propargylic Alcohols to Access Tetrasubstituted Difluoroalkyl Allenes

Cu‐Catalyzed C(sp2−H)‐Trifluoromethylation of Aldehyde Hydrazones with Langlois Reagent

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Cu‐Catalyzed C(sp²−H)‐Trifluoromethylation of Aldehyde Hydrazones with Langlois Reagent