The stereochemistry of bicyclo[3.2.1]octane—XVIII
Identifieur interne : 003864 ( Istex/Curation ); précédent : 003863; suivant : 003865The stereochemistry of bicyclo[3.2.1]octane—XVIII
Auteurs : C. W. Jefford [États-Unis] ; W. Wojnarowski [États-Unis]Source :
- Tetrahedron [ 0040-4020 ] ; 1969.
English descriptors
- Teeft :
- Addition mode, Addition modes, Addition process, Adduct, Allylic, Aqueous acetone, Chem, Chemical shifts, Chlorine atom, Cyclopropane ring, Cyclopropyl, Deshielded cyclopropyl proton, Dispersion forces, Disrotatory rupture, Ether, Hydrogen chloride, Ibid, Jefford, Meli soln, Methyl group, Mild hydrolysis, Monochlorocarbene, Multiplet centred, Narrow triplet, Norbomene, Orbital symmetry, Other hand, Proton, Reaction mixture, Rearrangement, Ring opening, Several experiments, Solid trap, Soln, Spectral data, Stereochemistry, Tetrahedron, Tetrahedron letters, Torsional interactions, Transition state, Viii, Xvii.
Abstract
Abstract: Monochlorocarbene undergoes addition to bicyclo[2.2.2]octene-2 to give anti- and syn-3-chlorotricyclo[3.2.2.02,4]nonane in a ratio of 5:1. On warming the mixture, only the syn isomer rearranges to 2-chlorobicyclo[3.2.2]nonene-3. The addition of monochlorocarbene to 1-methylnorbomene-2 affords 1-methyl-anti-3-chloro-exo-tricyclo[3.2.1.02,4]octane. 1-methyl-exo-4-chlorobicyclo[3.2.1]octene-2 and 1-methyl-exo-2-chlorobicyclo[3.2.1]octene-3 in a ratio of 3:1:1. Similar addition to 2-methylnorbomene-2 gives 2-methyl-anti-3-chloro-exo-tricyclo[3.2.1.02,4]octane and 2-methylenebicyclo[3.2.1]octene-3 in a ratio of 10:1. The exo-anti tricyclic structures are stable to heat and aqueous silver ion. In contrast, the exo-syn adducts are remarkably labile and are assumed to be the precursors of the rearranged products. The factors which govern the stereochemistry of the addition and rearrangement processes are discussed.
Url:
DOI: 10.1016/S0040-4020(01)82760-5
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<term>Aqueous acetone</term>
<term>Chem</term>
<term>Chemical shifts</term>
<term>Chlorine atom</term>
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<term>Cyclopropyl</term>
<term>Deshielded cyclopropyl proton</term>
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<term>Disrotatory rupture</term>
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<term>Jefford</term>
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<term>Mild hydrolysis</term>
<term>Monochlorocarbene</term>
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<front><div type="abstract" xml:lang="en">Abstract: Monochlorocarbene undergoes addition to bicyclo[2.2.2]octene-2 to give anti- and syn-3-chlorotricyclo[3.2.2.02,4]nonane in a ratio of 5:1. On warming the mixture, only the syn isomer rearranges to 2-chlorobicyclo[3.2.2]nonene-3. The addition of monochlorocarbene to 1-methylnorbomene-2 affords 1-methyl-anti-3-chloro-exo-tricyclo[3.2.1.02,4]octane. 1-methyl-exo-4-chlorobicyclo[3.2.1]octene-2 and 1-methyl-exo-2-chlorobicyclo[3.2.1]octene-3 in a ratio of 3:1:1. Similar addition to 2-methylnorbomene-2 gives 2-methyl-anti-3-chloro-exo-tricyclo[3.2.1.02,4]octane and 2-methylenebicyclo[3.2.1]octene-3 in a ratio of 10:1. The exo-anti tricyclic structures are stable to heat and aqueous silver ion. In contrast, the exo-syn adducts are remarkably labile and are assumed to be the precursors of the rearranged products. The factors which govern the stereochemistry of the addition and rearrangement processes are discussed.</div>
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