Photostimulated nucleophilic aromatic substitution for halides with carbon nucleophiles. Preparative and mechanistic aspects

Semmelhack, M. F.; Bargar, Thomas M.

doi:10.1021/ja00546a021

Cited by 82 publications

(35 citation statements)

References 3 publications

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“…The results obtained for the photostimulated reaction of anion 3d with the aryl substrates are mechanistically interesting 51. In these reactions, the fragmentation step was the most favoured pathway.…”

Section: Resultsmentioning

confidence: 85%

Matrix Isolation and Spectroscopic Characterization of Perfluorinatedortho- andmeta-Benzyne

Wenk

Sander

2001

Chem. Eur. J.

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The matrix isolation and spectroscopic characterization of two C6F4 isomers, the perfluorinated o-benzyne 4 and the m-benzyne 5, is reported. UV photolysis of tetrafluorophthalic anhydride 6 in solid argon at 10 K results in the formation of CO, CO2, and 1,2-didehydro-3,4,5,6-tetrafluorobenzene (4) in a clean reaction. On subsequent 350 nm irradiation 4 is carbonylated to give the cyclopropenone 7. 1,3-Didehydro-2,4,5,6-tetrafluorobenzene (5) was synthesized by UV irradiation of 1,3-diiodo-2,4,5,6-tetrafluorobenzene (8) via 2,3,4,6-tetrafluoro-5-iodophenylradical 9. Photolysis of 8 in solid neon at 3 K produces good yields of both radical 9 and benzyne 5, while in argon at 10 K no reaction is observed. Thus, the photochemistry in neon at extremely low temperature markedly differs from the photochemistry in argon. The formation of 5 from 8 via 9 is reversible, and annealing the neon matrix at 8 K leads back to the starting material 8. The benzynes 4 and 5 and the radical 9 were characterized by comparison of their matrix IR spectra with density functional theory (DFT) calculations.

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Section: Resultsmentioning

confidence: 85%

Matrix Isolation and Spectroscopic Characterization of Perfluorinatedortho- andmeta-Benzyne

Wenk

Sander

2001

Chem. Eur. J.

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“…PET from a negatively charged center to the haloarene may be followed by a loss of halide ion and subsequent coupling of the two radical termini. Thus, medium-sized (six-to ten-membered) rings can be obtained by the photocyclization of enolate anions (Scheme 9.15) [23].…”

Section: Electron-deficient Aromatic Compounds As Electron Acceptorsmentioning

confidence: 99%

Formation of Six‐Membered (and Larger) Rings

Pérez‐Prieto

Miranda

2009

Handbook of Synthetic Photochemistry

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“…Chemical shifts (δ) were reported as part per million (ppm) in δ scale downfield from TMS. 13 C NMR spectra were referenced to CDCl 3 (δ 77.0 ppm, the middle peak). Coupling constants (J) were reported in Hertz (Hz).…”

Section: General Considerationsmentioning

confidence: 99%

“…Hz, 1H), 4.67 (s, 1H), 4.37 (q, J = 7.5 Hz, 2H) 4.27-4.17 (m, 4H), 1.39 (t, J = 7.0 Hz, 3H), 1.26 (t, J = 7.5 Hz, 6H); 13 1, entry 15). 5 Purified by column chromatography on silica gel using ethyl acetate/hexane (1:3) as eluent to obtain the title compound as an orange oil.…”

Section: General Procedures Cu-catalyzed α-Arylation Of Malonatesmentioning

confidence: 99%