Facile access to the 2,2-difluoro-2,3-dihydrofuran skeleton without extra additives: DMF-promoted difluorocarbene formation of ClCF<sub>2</sub>CO<sub>2</sub>Na

Chen, Zunsheng; Xie, Xin; Chen, Wei-Ming; Luo, Nianhua; Li, Xiaoning; Yu, Fuchao; Huang, Jiuzhong

doi:10.1039/d2ob01542k

Cited by 12 publications

(7 citation statements)

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“…Thus, combining the above-mentioned results and previous relevant literature reports on the HFIP catalytic mechanism 6,37,38 and the synthesis of chromones from o -hydroxyaryl enamamines, 34,39–42 a plausible mechanism of the HFIP-promoted tandem cyclization reaction from o -hydroxyaryl enaminones was proposed (Scheme 3). In this conversion, HFIP not only acted as a solvent, but also as a Brønsted acid to promote the reaction.…”

Section: Resultsmentioning

confidence: 56%

“…Furthermore, chromone 3a′ reacted with 2a under the standard conditions, without providing product 3a (Scheme 2b), indicating that the reaction process might not involve the formation of 3a′, but rather proceed first through hydroxydifluoromethylation and then annulation to afford 3a. Thus, combining the above-mentioned results and previous relevant literature reports on the HFIP catalytic mechanism 6,37,38 and the synthesis of chromones from o-hydroxyaryl enamamines, 34,[39][40][41][42] a plausible mechanism of the HFIP-promoted tandem cyclization reaction from o-hydroxyaryl enaminones was proposed (Scheme 3). In this conversion, HFIP not only acted as a solvent, but also as a Brønsted acid to promote the reaction.…”

Section: Papermentioning

confidence: 70%

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Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones via tandem cyclization of o-hydroxyaryl enaminones

Wu,

Liu,

Liu

et al. 2023

Org. Biomol. Chem.

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Section: Resultsmentioning

confidence: 56%

Section: Papermentioning

confidence: 70%

Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones via tandem cyclization of o-hydroxyaryl enaminones

Wu,

Liu,

Liu

et al. 2023

Org. Biomol. Chem.

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“…These results now are undergoing in our group and will be reported on due course. In the same year, Wan, 41 Song 42 and Huang 43 consequently reported the results on constructing gem-fluorinated 2H-furans by enaminones and difluoride reagents.…”

Section: Cleavage Of Enamine C-c Double Bonds and Cyclized To 2h-furansmentioning

confidence: 99%

Reassembly of Unsaturated C–C Bonds by a Cutting/Insertion Cascade

Zhao

et al. 2022

Synlett

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Reassembling of unsaturated C-C bonds has attracted wide attentions by synthetic chemists due to advantages of unique reactivity, easy-handling, high atom and step economies. We recently explored a "cutting/insertion" cascade to introduce a new C1 source and construct functionalized 1,4-ketoaldehyde and 2H-furan derivatives through cyclopropanation of enamines with different carbene precursors and consequently ring-opening reactions in situ. Aminocyclopropanes are believed to be involved as key intermediates in these transformations. This Synpact article outlines our recent contributions in this arising research area.

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“…The current synthetic method is suitable for the preparation of diverse 2,2‐difluoro‐2,3‐dihydrofuran‐3‐amine derivatives, including 4,5‐disubstituted and cycloalkano[ d ] fused 2,2‐difluoro‐2,3‐dihydrofuran‐3‐amine derivatives (Scheme 13). [30] …”

Section: Synthesis Of Gem‐difluoroheterocyclesmentioning

confidence: 99%

Difluorocarbene in Cycloadditions and Annulations for the Synthesis of gem‐Difluorocarbocycles and gem‐Difluoroheterocycles

Xu,

Sun

2023

Eur J Org Chem

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Difluorocarbene is a simple, readily prepared, and versatile difluoriinated one‐carbon synthon. It can be applied as both the difluoromethylating reagent in the carbene insertion and the difluoromethylenating reagent in various cycloadditions and annulations. This concept article provides an account of applications of difluorocarbene in cycloadditions and annulations for synthesis of gem‐difluorocarbocycles and gem‐difluoroheterocycles. The synthesized gem‐difluorocarbocycles include 2,2‐difluorobicyclo[1.1.1]pentanes, 4,4‐/5,5‐difluoro‐cyclopentenes, 2,2‐difluorocyclopentanones, and 5,5‐difluorocyclopent‐2‐enones via tandem [2 + 1] cycloaddition and ring‐expansion or [4 + 1] annulations. The prepared gem‐difluoroheterocycles involve 2,2‐/3,3‐difluoro‐2,3‐dihydrofurans, 2,2‐difluoro‐2,3‐dihydrobenzofurans, 2,2‐difluoro‐2,3‐dihydrobenzothiophenes, 2,2‐difluorobenzofuran‐3(2H)‐ones, 2,2‐difluorobenzothiophen‐3(2H)‐ones, 2,2‐difluoro‐2,3‐dihydrothie‐no[2,3‐b]pyridines, 2,2‐difluorothieno[2,3‐b]pyridine‐3(2H)‐ones, 5,5‐difluorooxazolines and thiazolines, and spirocyclic 2,2‐difluorobenzo [d][1,3]aza/phosphaborol‐1‐ium‐3‐yliums via [4 + 1] annulations, 1,1‐difluoro‐1,9a‐dihydropyrido[2,1‐c][1,4]thiazines and 3,3‐difluorobenzo[e][1,4,2] oxaza/phosphaborinin‐4‐ium‐2‐uides via [5 + 1] annulations, 9,9‐difluoro‐8‐azabicyclo[5.2.0]nona‐2,4,6‐trienes via [8 + 1] annulation, 4,4‐difluorooxazolidines and 3,3‐difluoropyrrolidines via [1 + 2 + 2] annulations. Difluorocarbene generated from different readily available precursors proceeds these cycloadditions and annulations well. The substrate scopes, proposed mechanisms, selected product examples and their applications are discussed.

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Facile access to the 2,2-difluoro-2,3-dihydrofuran skeleton without extra additives: DMF-promoted difluorocarbene formation of ClCF₂CO₂Na

Abstract: The practical and facile difluorocarbene-triggered cycloaddition reaction of enaminones was developed, that delivered 2,2-difluoro-2,3-dihydrofurans with broad substrates scope. Notably, the reaction proceeded smoothly without any extra additive. The readily available...

Cited by 12 publications

References 52 publications

Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones via tandem cyclization of o-hydroxyaryl enaminones

Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones via tandem cyclization of o-hydroxyaryl enaminones

Reassembly of Unsaturated C–C Bonds by a Cutting/Insertion Cascade

Difluorocarbene in Cycloadditions and Annulations for the Synthesis of gem‐Difluorocarbocycles and gem‐Difluoroheterocycles

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Facile access to the 2,2-difluoro-2,3-dihydrofuran skeleton without extra additives: DMF-promoted difluorocarbene formation of ClCF2CO2Na

Abstract: The practical and facile difluorocarbene-triggered cycloaddition reaction of enaminones was developed, that delivered 2,2-difluoro-2,3-dihydrofurans with broad substrates scope. Notably, the reaction proceeded smoothly without any extra additive. The readily available...

Cited by 12 publications

References 52 publications

Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones via tandem cyclization of o-hydroxyaryl enaminones

Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones via tandem cyclization of o-hydroxyaryl enaminones

Reassembly of Unsaturated C–C Bonds by a Cutting/Insertion Cascade

Difluorocarbene in Cycloadditions and Annulations for the Synthesis of gem‐Difluorocarbocycles and gem‐Difluoroheterocycles

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Facile access to the 2,2-difluoro-2,3-dihydrofuran skeleton without extra additives: DMF-promoted difluorocarbene formation of ClCF₂CO₂Na