La deshalogenation par le zinc des bis(bromomethyl)-2,2 cyclanones.

Conia, J. M.; Leriverend, Pierre; Bouket, Jean-Louis

doi:10.1016/0040-4039(64)83132-4

Cited by 2 publications

(2 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…provided pure spiro[2.5]octan-4-one ( 18 ): uncorrected bp 85−86 °C/26 mmHg [lit . bp 82−84 °C/24 mmHg] (98%+, GC); GC/MS, 1 H and 13 C NMR characteristics consistent with the given structure and with reported literature data. , Conversion of 18 into the corresponding 2,4-dinitrophenylhydrazone provided a light-orange crystalline derivative: mp 158−159 °C …”

Section: Methodssupporting

confidence: 77%

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties¹

et al. 2003

View full text Add to dashboard Cite

The powerful methyl(trifluoromethyl)dioxirane (1b) was employed to achieve the direct oxyfunctionalization of 2,4-didehydroadamantane (5), spiro[cyclopropane-1,2'-adamantane] (9), spiro[2.5]octane (17), and bicyclo[6.1.0]nonane (19). The results are compared with those attained in the analogous oxidation of two alkylcyclopropanes, i.e., n-butylcyclopropane (11) and (3-methyl-butyl)-cyclopropane (14). The product distributions observed for 11 and 14 show that cyclopropyl activation of alpha-C-H bonds largely prevails when no tertiary C-H are present in the open chain in the tether; however, in the oxyfunctionalixation of 14 cyclopropyl activation competes only mildly with hydroxylation at the tertiary C-H. The application of dioxirane 1b to polycyclic alkanes possessing a sufficiently rigid framework (such as 5 and 9) demonstrates the relevance of relative orientation of the cyclopropane moiety with respect to the proximal C-H undergoing oxidation. At one extreme, as observed in the oxidation of rigid spiro compound 9, even bridgehead tertiary C-H's become deactivated by the proximal cyclopropyl moiety laying in the unfavorable "eclipsed" (perpendicular) orientation; at the other end, a cyclopropane moiety constrained in a favorable "bisected" orientation (as for didehydroadamantane 5) can activate an "alpha" methylene CH2 to compete effectively with dioxirane O-insertion into tertiary C-H bonds. Comparison with literature reports describing similar oxidations by dimethyldioxirane (1a) demonstrate that methyl(trifluoromethyl)dioxirane (1b) presents similar selectivity and remarkably superior reactivity.

show abstract

Section: Methodssupporting

confidence: 77%

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties¹

et al. 2003

View full text Add to dashboard Cite

show abstract

“…J. H. Treiber u. S. R. Dowd, J. Amer. chem.entsteht, mit Mesityloxid(34) in sehr guter Ausbeute zum Dichlordimethylcyclopropyl-methylketon(35) 1231.Die Reaktion nach SimntottsCHzJ2 -1 Zn/Cu -1. Olefin + Cyclopropanverhindung ist auch auf ungesattigte Verbindungen mit funktionellen Gruppen wie -OH, -OAc, ~ COOR und ebenfalls auf cr,rJ-ungesattigte Ketone anwendbar'35.361.…”

unclassified

Synthesen von Cyclopropylcarbonylverbindungen

Conia

1968

Angewandte Chemie

View full text Add to dashboard Cite

Es gibt drei wichtige direkte Wege zu Cyclopropylcarbonylverbindungen: 1. Die Cyclisierung von Ketten aus drei Kohlenstoffatomen, von denen das erste oder dritte einem Carbonyl‐ oder potentiellen Carbonylkohlenstoffatom benachbart ist (hierzu gehören die Synthesen durch intramolekulare Alkylierung von γ‐Halogenketonen oder verwandten Verbindungen in alkalischem Milieu); 2. die Insertion einer Methylengruppe oder substituierten Methylengruppe in die olefinische Doppelbindung einer α,β‐ungesättigten Carbonylverbindung sowie 3. die Einführung einer Acetonylgruppe in die Doppelbindung eines Olefins. Cyclopropylcarbonylverbindungen können aber außerdem auch durch Ringverengung aus 1,2‐Epoxycyclobutan‐ und aus 2‐Bromcyclobutanon‐Derivaten gewonnen werden. Eine weitere Möglichkeit ist die Enthalogenierung von α,α‐Bis(brommethyl)‐cycloalkanonen. Alle diese Synthesewege sind hier zusammengestellt.

show abstract

La deshalogenation par le zinc des bis(bromomethyl)-2,2 cyclanones.

Cited by 2 publications

References 6 publications

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties¹

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties¹

Synthesen von Cyclopropylcarbonylverbindungen

Contact Info

Product

Resources

About

La deshalogenation par le zinc des bis(bromomethyl)-2,2 cyclanones.

Cited by 2 publications

References 6 publications

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties1

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties1

Synthesen von Cyclopropylcarbonylverbindungen

Contact Info

Product

Resources

About

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties¹

Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 5. Selective Oxidation of Hydrocarbons Bearing Cyclopropyl Moieties¹