.alpha.'-Functionalization of .beta.,.gamma.-unsaturated cyclohexenones. Utilization of silyl enol ethers produced from the lithium/ammonia reduction of silyl aryl ethers

Donaldson, R. E.; Fuchs, P. L.

doi:10.1021/jo00431a055

Cited by 23 publications

(6 citation statements)

References 3 publications

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“…Compound 11 : colorless oil; 1 HNMR (CDCl 3 ): δ = 0.45 (s, 6 H), 1.15 (s, 9 H), 2.5 (s, 6 H), 6.65 (t, 2 H, J =7 Hz), 7.00 (d, 1 H, J =7 Hz); further characteristics as reported 30. Data of compound 13 in accordance with literature 31…”

Section: Methodssupporting

confidence: 77%

Aryl Cation and Carbene Intermediates in the Photodehalogenation of Chlorophenols

Manet

Monti

Fagnoni

et al. 2004

Chemistry A European J

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The photochemistry of 2,6-dimethyl-4-chlorophenol (6) has been studied in methanol and trifluoroethanol (TFE) through product studies and transient absorption spectroscopy. Chloride loss from triplet 6 gave triplet hydroxyphenyl cation 14, which equilibrated with triplet oxocyclohexadienylydene 15 within a few tens of nanoseconds; the cation can, however, be selectively trapped by allyltrimethylsilane (k(ad) = 10(8)-10(9) m(-1) s(-1)) to give a phenonium ion and the allylated phenol. In neat alcohols, 14 and 15 are reduced through different mechanisms, namely by hydrogen transfer through radical cation 17 and via phenoxyl radical 16, respectively. The mechanistic rationalization has been substantiated by the parallel study of an O-silylated derivative. The work shows that the chemistry of the highly (but selectively) reactive phenyl cation 14 can not only be discriminated from that of the likewise highly reactive carbene 15, but also exploited for synthetically useful reactions, as in this case with alkenes. Photolysis of electron-donating substituted halobenzenes may be the method of choice for the mild generation of some classes of phenyl cations.

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Section: Methodssupporting

confidence: 77%

Aryl Cation and Carbene Intermediates in the Photodehalogenation of Chlorophenols

Manet

Monti

Fagnoni

et al. 2004

Chemistry A European J

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“…It was also apparent that the cyclohexenones could be converted into the corresponding alcohol ( 5 ) and the dienol acylates (6). These have been shown by Johnson and by Harding to be good precursors for the allylic ions (7) and ( 8) which, in turn, are efficient initiators of cyclisation. This flexibility offered by the 3-methylcyclohex-2-enone unit suggested facile synthetic routes provided that the cyclohexenones could be prepared in high yield.…”

Section: Chemistry Department the Victoria University Of Manchester M...mentioning

confidence: 93%

3-Methylcyclohex-2-enone derivatives as initiators of cyclisation. Part 1. Introduction and synthesis of 2-substituted 3-methylcyclohex-2-enones

Amupitan¹,

Mellor²,

Scovell³

et al. 1983

J. Chem. Soc., Perkin Trans. 1

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“…in the syntheses of steroids,2 terpenoids 6 and alkaloids. Compounds (23) to (26), for example, have only been reduced by employing massive excesses (200-600 equiv.) 5 (22) M/ROH/NH 3 Scheme 3 The Birch reduction of aromatic hydrocarbons and ethers to the 2,5-dihydro derivatives proceeds most satisfactorily when the substitution pattern allows the addition of hydrogen to two unsubstituted positions in a para relationship.…”

Section: Benzenoid Hydrocarbons and Ethersmentioning

confidence: 99%

Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods

Mander

1991

Comprehensive Organic Synthesis

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.alpha.'-Functionalization of .beta.,.gamma.-unsaturated cyclohexenones. Utilization of silyl enol ethers produced from the lithium/ammonia reduction of silyl aryl ethers

Cited by 23 publications

References 3 publications

Aryl Cation and Carbene Intermediates in the Photodehalogenation of Chlorophenols

Aryl Cation and Carbene Intermediates in the Photodehalogenation of Chlorophenols

3-Methylcyclohex-2-enone derivatives as initiators of cyclisation. Part 1. Introduction and synthesis of 2-substituted 3-methylcyclohex-2-enones

Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods

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