<b>On the Photochemical Cyclization of Saturated Ketones and Aldehydes to Cyclobutanols</b>

Orbán, István; Schaffner, Kurt; Jeger, O.

doi:10.1021/ja00902a042

Cited by 48 publications

(12 citation statements)

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“…Soc., 90, 6607 (1968). (15) L. E. Sutton, Ed., "Tables of Interatomic Distances and Configurations in Molecules and Ions," Special Publication No. 11, The Chemical Society, London, 1958. (16) R. Hoffmann, J. Chem.…”

Section: Resultsmentioning

confidence: 99%

Molecular orbital approach to the mechanism of electrophilic additions to olefins

Bach¹,

Henneike²

1970

J. Am. Chem. Soc.

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The nature of the intermediate formed by the electrophilic addition of H+, F+, Cl+, Br+, +SR, +HgX, or Ag+ to ethylene has been studied by extended Hiickel molecular orbital calculations. The trends observed in these calculations are shown to correlate well with experimental data and chemical intuition. Overlap populations, self-consistent charge distributions, and relative energy differences for these ions are given. Total energy differences for two of the charged species are compared by CNDO/2 calculations. The overall mechanism of electrophilic additions to olefins is discussed in light of these calculations. The relative stability of the intermediates involved in these reactions is determined by the extent of perturbation of the olefin by the attacking electrophile. The mode of addition is influenced by the amount of energy required to convert the symmetrical onium ion II to its unsymmetrical form IV.

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Section: Resultsmentioning

confidence: 99%

Molecular orbital approach to the mechanism of electrophilic additions to olefins

Bach¹,

Henneike²

1970

J. Am. Chem. Soc.

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“…C 68,38 H 10.59% Gef. C 68,92 H 10,66% (6 -4-(4'-methyZ-pentyZ)-butyroZacton (7). 630 2-(3'-Methyl-butyl)-3-hydroxy-3-methyl-te~~~hydro~yran (8).…”

Section: Behandlung Vonmentioning

confidence: 99%

“…Discussion des rhsuitats. Pour montrer qu'on peut accorder foi aux valeurs des pressions d'kquilibre dktermin6es B. l'aide du dispositif expkrimental d6crit , nous avons comparC nos valeurs de A% = AHTm = 38,7 (6) Kcal . mole-l e t d S = AS,, = + 113 cal .…”

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Die Oxydation von (+)‐(4R)‐4, 8‐Dimethyl‐nonanol‐(1) mit Blei (IV)‐ acetat

Hauser

Schaffner

Jeger

1964

Helvetica Chimica Acta

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The lead tetraacetate oxidation of the optically active aliphatic alcohol 1 in benzene afforded the tetrahydrofurane derivative 3 and the 3‐acetoxy‐tetrahydro‐pyranes 4–6 as major products. The formation of the expected compound 3 in racemic form is interpreted by the stepwise sequence a → b → c → d1–3 → e. The appearance of a carbonium ion of type d3 in the conversion 1 → 3 is in contrast to the direct oxydative ring closure (cf. c → e) which had been postulated previously for cases involving alicyclic educts with sterically fixed reaction centres. The same carbonium ion d3 is considered as a possible intermediate in the formation of compounds 4–6 (cf. f → g → h). The latter process represents a novel type of reaction of monohydric alcohols with lead tetraacetate.

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“…The phenomenon was already reported by Seebach and Wasmuth in the alkylation of di-tert-butyl N-formylaspartate involving a sp 2 -hybridized enolate intermediate [2] and by Leuchs [3] and Marquet as well as coworkers [4,5] in the halogenation of chiral 2-benzylated-indan-1-ones involving an enol intermediate. Other examples in the field of diradical chemistry were discovered early by Jones in the thermal and by Rinehard and van Auken in the light induced decomposition of pyrazolines leading to cyclopropane [6,7], as well as by Jeger and coworkers during the photochemical formation of cyclobutanols from saturated ketones [8]. Nowadays, examples of MoC involving enolates [9], carbenium ions [10], radicals [11], radical cations [12], and diradicals [6] are known.…”

Section: Introductionmentioning

confidence: 99%

Memory of chirality in reactions involving monoradicals

Gloor

Dénès

Renaud

2016

Free Radical Research

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The effects of memory of chirality (MoC) in reactions involving monoradical species are reviewed here. Reactions involving a nonracemic chiral starting material bearing a single stereogenic element such as a chiral center or chiral axis directly involved in the new bond formation are discussed. These reactions lead to a nonracemic product via an intermediate susceptible to rapid racemization. Memory of chirality has been observed in cyclic radicals, aryl, ester/amide substituted acyclic radicals, and benzylic radicals at temperatures up to 130 °C.

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On the Photochemical Cyclization of Saturated Ketones and Aldehydes to Cyclobutanols

Cited by 48 publications

References 0 publications

Molecular orbital approach to the mechanism of electrophilic additions to olefins

Molecular orbital approach to the mechanism of electrophilic additions to olefins

Die Oxydation von (+)‐(4R)‐4, 8‐Dimethyl‐nonanol‐(1) mit Blei (IV)‐ acetat

Memory of chirality in reactions involving monoradicals

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