Photoinduced molecular transformations. Part 133. New photoinduced deconjugation of steroidal α,β-unsaturated cyclic ketone oxime into the β,γ-unsaturated isomer involving stereospecific proton transfer

Suginome, Hiroshi; Ohki, Takashi; Nagaoka, Atsushi; Senboku, Hisanori

doi:10.1039/p19920001849

Cited by 7 publications

(1 citation statement)

References 10 publications

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“…The mono-oximes 4-6 were synthesized in 80, 90 and 82 % yields, respectively, (Scheme 1) by oximation of the corresponding para-benzoquinones 1-3 under standard conditions [10,11]. The mono-oxime derivatives 7-9 (Scheme 2) were obtained by standard alkylation and acylation reactions of compound 4.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Antidepressant Evaluation of Three para-Benzoquinone Mono-oximes and Their Oxy Derivatives

et al. 2006

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Section: Resultsmentioning

confidence: 99%

Synthesis and Antidepressant Evaluation of Three para-Benzoquinone Mono-oximes and Their Oxy Derivatives

et al. 2006

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Light‐Induced Chemistry of Oximes and Derivatives

Roth¹

2010

Patai's Chemistry of Functional Groups

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Photoreactions of oximes have been known for 120 years. The earliest recognized reaction was geometric isomerization, which is still the most prominent oxime photoreaction; it proceeds via a ππ* triplet state. More than sixty years later the intriguing photo‐Beckmann rearrangement came to light, a C–C=N–O to O=C–N–C conversion, generating, for example, ɛ‐caprolactam from cyclohexanone ξιμɛ. The rearrangement proceeds via a ππ* singlet state forming an oxazirane intermediate; the oxazirane ring usually opens in stereospecific fashion. Detailed insight into the stereo‐ and regiochemistry of the rearrangement was gained from steroidal oximes, the most thoroughly investigated class of oximes. Additional photoreactions of oximes or of their ethers and esters include: net loss of hydroxylamine generating carbonyl compounds; loss of water from aldoximes forming nitriles; conversion of ketoximes to nitriles by more complex mechanisms; photochemical O–H cleavage generating iminoxyl radicals, an interesting family of free radicals; N–O cleavage giving rise to iminyl radials, which undergo radical cyclizations. β,γ‐Unsaturated oximes undergo aza‐di‐π‐methane rearrangements, cyclize to oxazolines, and undergo further reorganizations. The palette of oxime reactions has been further enriched by triplet energy transfer or electron transfer sensitization; oximes serve as electron donors or acceptors.

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ChemInform Abstract: Photoinduced Molecular Transformations. Part 133. New Photoinduced Deconjugation of Steroidal α,β‐Unsaturated Cyclic Ketone Oxime into the β,γ‐Unsaturated Isomer Involving Stereospecific Proton Transfer.

et al. 1992

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Photoinduced molecular transformations. Part 133. New photoinduced deconjugation of steroidal α,β-unsaturated cyclic ketone oxime into the β,γ-unsaturated isomer involving stereospecific proton transfer

Cited by 7 publications

References 10 publications

Synthesis and Antidepressant Evaluation of Three para-Benzoquinone Mono-oximes and Their Oxy Derivatives

Synthesis and Antidepressant Evaluation of Three para-Benzoquinone Mono-oximes and Their Oxy Derivatives

Light‐Induced Chemistry of Oximes and Derivatives

ChemInform Abstract: Photoinduced Molecular Transformations. Part 133. New Photoinduced Deconjugation of Steroidal α,β‐Unsaturated Cyclic Ketone Oxime into the β,γ‐Unsaturated Isomer Involving Stereospecific Proton Transfer.

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