Beiträge zur Konstellationsanalyse, VII. (Solvolyse von Toluolsulfonsäureestern, IX) Konkurrenzreaktionen bei der Alkoholyse

Methodology is described for the annulation of five-membered carboxylic rings onto cycloalkanones, using an intramolecular sulfur ylide reaction. Epoxybicyclo[x.3.0]alkanes (x = 3, 4, 5, 6) were obtained from cycloalkanones via the corresponding 2-[3-(phenylthio)propyl]cycloalkanones (2a-d, 7, 11), which were reacted successively with triethyloxonium tetrafluoroborate and potassium fert-butylate. An analogous annulation to give a six-membered ring epoxide from 14 also proceeds smoothly, whereas attempted seven-membered ring formation from 17 was unsuccessful. The stereochemistry of the various annulations was determined and compared with the stereochemistry of the epoxidations of the corresponding olefins (33a-d, 35, 38, 40). These olefins were obtained by intramolecular Wittig reactions. Mechanisms for the ylide cyclizations are discussed.

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“…2-(3-Bromopropyl)-4-tert-butylcyclohexanone (34). In a similar fashion to the preceding experiment, 6 yielded 8.69 g (61%)…”

Section: Methodssupporting

confidence: 58%

Intramolecular sulfur ylide additions to ketones

Crandall¹,

MAGAHA²,

Henderson³

et al. 1982

J. Org. Chem.

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“…Materials 100-Decal-50-01 (la) This alcohol, mp 52-56"C, was prepared as described by Huckel et al (6).…”

Section: Methodsmentioning

confidence: 99%

¹³C nuclear magnetic resonance studies. 81. Conformational inversion barriers of some cis-decalins determined by ¹³C nuclear magnetic resonance

Browne¹,

Klinck²,

Stothers³

1979

Can. J. Chem.

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. Can. J. Chem. 57,803 (1979). The 13Cmr spectra of 5P,lOp-dimethyldecalin, lop-decal-5p-01, and lop-methyldecal-5p-01 have been examined as a function of temperature to determine the barriers to conformational inversion. Lineshape fitting was employed to extract rate data from which the thermodynamic parameters governing the inversion processes were extracted. Comparison of these results with those obtained by molec~~lar mechanics calculations indicates that the barrier for chair-twist to twist-twist interconversion dominates the conformational inversion profile.LOIS M. BROWNE, R. E. KLINCK et J. B. STOTHERS. Can. J. Chem. 57,803 (1979). On a dktermink les spectres rmn I3C des dimtthyl-5[3,10P dkcaline, 10~-d6calol-5p et methyl-lop d&calol-5[3 en fonction de la tempkrature dans le but d'kvaluer les barrikres a l'inversion conformationnelle. On a utilisk la technique de la superposition des formes des pics pour en tirer les donnees a partir desquelles on a pu Cvaluer les parametres thermodynamiques qui gouvernent les processus d'inversion. Une comparaison de ces rksultats avec ceux obtenus gr2ce a des calculs de mkcanique molkculaire indique que la barriere a I'interconversion chaise-croiske a croisee-croiske domine le profil de l'inversion conformationnelle.[Traduit par le journal]

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“…2-Methyl-2-nitrosopropane yielded 2-methyl-2-iodopropane in high yield in a reaction analogous to the reaction of 2-methyl-2-nitropropane (eq 5). 2Me3SiI (Me)3CNO-Me3CI + Me3SiOSiMe3 (5) ^0SiMe3 :N\ + ^0.…”

Section: Me3cnmentioning

confidence: 99%

Synthetic methods and reactions. 113. Reactions of nitro- and nitrosoalkanes with iodotrimethylsilane

Oláh¹,

Narang²,

Field³

et al. 1983

J. Org. Chem.

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Beiträge zur Konstellationsanalyse, VII. (Solvolyse von Toluolsulfonsäureestern, IX) Konkurrenzreaktionen bei der Alkoholyse

Cited by 30 publications

References 37 publications

Intramolecular sulfur ylide additions to ketones

Intramolecular sulfur ylide additions to ketones

¹³C nuclear magnetic resonance studies. 81. Conformational inversion barriers of some cis-decalins determined by ¹³C nuclear magnetic resonance

Synthetic methods and reactions. 113. Reactions of nitro- and nitrosoalkanes with iodotrimethylsilane

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Beiträge zur Konstellationsanalyse, VII. (Solvolyse von Toluolsulfonsäureestern, IX) Konkurrenzreaktionen bei der Alkoholyse

Cited by 30 publications

References 37 publications

Intramolecular sulfur ylide additions to ketones

Intramolecular sulfur ylide additions to ketones

13C nuclear magnetic resonance studies. 81. Conformational inversion barriers of some cis-decalins determined by 13C nuclear magnetic resonance

Synthetic methods and reactions. 113. Reactions of nitro- and nitrosoalkanes with iodotrimethylsilane

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¹³C nuclear magnetic resonance studies. 81. Conformational inversion barriers of some cis-decalins determined by ¹³C nuclear magnetic resonance