Photochemcial Rearrangement of N-Chloroimides to 4-Chloroimides. A New Synthesis of γ-Lactones

Petterson, R. C.; Wambsgans, Anthony

doi:10.1021/ja01062a048

Cited by 50 publications

(27 citation statements)

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“…Mori's research interests particularly focused on strategies to convert the C4-acid subunit directly into lactones as present in various members of the entkaurene diterpenoids, such as gibberellin A 15 , 54 7β-hydroxykaurenolide, 55 sciadinone, 56 tripterifordin (53) and neotripterifordin (52). In 1968, Mori and coworkers reported the successful application of a photochemical lactonization reaction developed by Barton 57 and Petterson 58 to the synthesis of C4 lactones of the kaurene natural products. The search for novel potent anti-AIDS agents led to the isolation of tripterifordin (53) in 1992 from the ethanolic extracts of the roots of Trypterygium wilfordii, 59 a poison liana plant occurring in southern China.…”

Section: Synthesis Of (±)-Kaurene and (±)-Atiserene (1966)mentioning

confidence: 99%

New avenues for the synthesis of ent-kaurene diterpenoids

et al. 2015

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Section: Synthesis Of (±)-Kaurene and (±)-Atiserene (1966)mentioning

confidence: 99%

New avenues for the synthesis of ent-kaurene diterpenoids

et al. 2015

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“…The internal selectivity in the NBS bromination of l-bromobutane under exemplary conditions (No. 2 and 3 in Table I [42]; obviously imidyl radicals 5 are formed and undergo specific intramolecular hydrogen abstraction from the'y-position. Benzoyl peroxide or lightinitiated NIS oxidation of l-phenylethanol is shown to be a succinimidyl radical mediated chain reaction giving excellent yields of acetophenone [43].…”

Section: The Recognition Of the Succinimidyl Radicalmentioning

confidence: 99%

Recent controversy on imidyl radical chemistry

Chow

Naguib

1984

Reviews of Chemical Intermediates

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“…That an amidyl free radical does not intramolecularly abstract a &hydrogen atom of the acyl chain was also confirmed by other groups (5, 6). Interestingly, in the photolysis of N-haloamides (1,3,4), varied extents of &-hydrogen abstraction from the acyl side chain took place depending on the type of halogen substitution and the type of N-alkyl group. Two plausible explanations, based on the stereochemistry of the transition state, have been postulated, one by us in our brief communication (7) and the other by Kuhn et al (6).…”

Section: Formation Of C-nitroso Compoundsmentioning

confidence: 99%

“…Recent studies (1)(2)(3)(4)(5)(6) have established that amidyl radicals can abstract a hydrogen atom from a saturated carbon center. We, as well as other groups,' have been studying the photolysis of nitrosamides aiming to unravel the reactions of transient amidyl radicals.…”

mentioning

confidence: 99%

Photochemistry of nitroso compounds in solution. X. The reaction pattern of photo-excited nitrosamides

Chow¹,

Tam²,

Lee³

1969

Can. J. Chem.

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The initial step in photolysis of alkyl N-nitrosamides 1 and 2 has been shown to be homolysis of the N-N bond, giving amidyl radicals and nitric oxide. Under the reaction conditions nitric oxide disproportionated, in part, to NO, and NO, radicals. The amidyl radicals abstracted hydrogen atoms intermolecularly from the solvent as well as intrarnolecularly from the 6-carbon of the alkyl chain, but not from that of the acyl chain. The combined pathways lead to the observed products .as shown in Schemes 1 and 2. By this photolysis, the functionalization at the unactivated 6-carbon site of the alkyl chain could be achieved in 55 % yield.Canadian Journal of Chemistry, 47, 2441 (1969) Recent studies (1-6) have established that amidyl radicals can abstract a hydrogen atom from a saturated carbon center. We, as well as other groups,' have been studying the photolysis of nitrosamides aiming to unravel the reactions of transient amidyl radicals. We now amplify the preliminary report (7) to describe the detailed reaction pattern of nitrosamide photolysis. In particular we were concerned with intramolecular reaction of acyclic amidyl radicals. Since photolysis of nitrosamides in protic solvent gave complicated mixtures (S), the present work concentrated on reactions in hydrocarbon solvents.Results Owing to thermal lability of nitrosamides (9), all the preparations and photolyses of these compounds were carried out at a temperature near or below ambient. The crude nitrosamides 1 and 2 were not ~urified further and exhibited the expected physical properties as summarized in Table I. The apparatus and procedure of the irradiation were described in detail in Experimental. The photodecompositions of the nitrosamides were shown to follow zero-order kinetics up to 75 % completion.

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Photochemcial Rearrangement of N-Chloroimides to 4-Chloroimides. A New Synthesis of γ-Lactones

Cited by 50 publications

References 0 publications

New avenues for the synthesis of ent-kaurene diterpenoids

New avenues for the synthesis of ent-kaurene diterpenoids

Recent controversy on imidyl radical chemistry

Photochemistry of nitroso compounds in solution. X. The reaction pattern of photo-excited nitrosamides

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