Studies on bicyclononanes. Part III. Chair–boat equilibria in bicyclo[3,3,1]nonanes

Appleton, R. A.; Egan, Sister C.; Evans, John; Graham, Steven M.; Dixon, John R.

doi:10.1039/j39680001110

Cited by 14 publications

(6 citation statements)

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“…Reduction of the latter with Raney nickel under equilibrating conditions (Marvell and Knutson, 1970) yielded a mixture of endo-6hydroxybicyclo[3.3.1]nonane-l,e«4o-3-dicarboxylic acid and exo-6-hydroxybicyclo[3.3.1 (nonane-1 ,e«4o-3-dicarboxylic acid. These were separated by gas-liquid chromatography as the dimethyl esters-Me3Si ethers and each one was epimerized at carbon 3 with sodium methoxide (Appleton et al, 1968), to give the remaining isomers: <?w/o-6-hydroxybicyclo[3.3.1 ]nonane-l,exo-3-dicarboxylic acid and exo-6-hydroxybicyclo[3.3.1]nonane-l,exo-3-dicarboxylic acid. Each of the four geometric isomers is a racemic mixture of two enantiomers but further resolution was not attempted.…”

Section: Methodsmentioning

confidence: 99%

Rearrangement of chorismate to prephenate. Use of chorismate mutase inhibitors to define the transition state structure

Andrews¹,

Cain²,

Rizzardo³

et al. 1977

Biochemistry

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The enzymically catalyzed conversion of chorismate to prephenate may proceed through either a chair-like or a boat-like transition state. To distinguish between these alternatives, we have prepared a series of structural analogues of the two possible transition state structures and tested them as inhibitors of chorismate mutase-prephenate dehydrogenase from Escherichia coli K12. The results indicate that the enzymically catalyzed reaction passes through a chair-like intermediate. None of the compounds studied is an ideal transition state analogue; it seems likely that the partial bond structure of the transition state precludes the corresponding orientation of the side chain in stable molecules. Nevertheless, the new inhibitors are stronger than any previously available, and the degree of inhibition is consistent with bacteriostatic activity recently observed in some of the compounds.

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Section: Methodsmentioning

confidence: 99%

Rearrangement of chorismate to prephenate. Use of chorismate mutase inhibitors to define the transition state structure

Andrews¹,

Cain²,

Rizzardo³

et al. 1977

Biochemistry

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“…Glpc analysis indicated only partial acetylation. An alternate process was carried out by stirring the crude product with acetyl chloride (7.5 ml)-triethyiamine (30)(31)(32)(33)(34)(35) ml)-benzene (75 ml) for 1.5 hr at room temperature. Samples of the endo and exo acetates were isolated by glpc.…”

Section: Methodsmentioning

confidence: 99%

Adamantanes and related compounds. XII. Diazotization of endo-7-aminomethylbicyclo[3.3.1]nonan-3-ols and endo-7-aminomethylbicyclo[3.3.1]non-2-ene

Wnuk¹,

Tonnis²,

Dolan³

et al. 1975

J. Org. Chem.

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Diazotization of endo-7-aminomethylbicyclo[3.3.1]nonan-exo-3-ol (3) with aqueous nitrous acid produced 3methylbicyclo[3.3.1]non-2-en-eio-7-ol (7), exo-7-methylbicyclo[3.3.1]nonan-3-one (8), and presumably exo-8-hydroxybicyclo[4.3.1]dec-2-ene (9) as major products. Exposure of endo-7-aminomethylbicyclo[3.3.1]nonan-endo-3-ol (2) to both protic (acetic acid or water) and aprotic (benzene) deamination resulted mainly in formation of 1methyl-2-oxaadamantane (19) and 4-oxahomoadamantane (20) in addition to a component tentatively identified as endo-8-hydroxybicyclo[4.3.1]dec-3-ene (21). Compound 2 yielded endo-7-aminomethylbicyclo[3,3.1]non-2-ene (4) with dilute sulfuric acid. Deamination of 4 under conditions used for 2 provided 2-adamantanol (28) and 2adamantyl acetate (29) as principal products. Elimination, transannular interactions, and apparently ring expansion comprise the dominant reaction routes. 7 gave 8 with sulfuric acid. The preparations of the isomeric 7-methylenebicyclo[3.3.l]nonan-3-ols (10) and endo-7-methylbicyclo[3.3.l]nonan-3-one (11) from reduction of 7-methylenebicyclo[3.3.l]nonan-3-one (12) are described. Endo alcohol 10b provided 19 under acidic conditions. Mechanistic aspects of the investigation are treated.

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“…In most cases the chair-chair conformation with slight ring flattening is favored. [137][138][139][140] In the twin-chair conformation the actual distance between the C-3 and C-7 carbons is 3.06 A while the ideal value is 2.52 A.…”

Section: R=ch2dtsmentioning

confidence: 99%

Chemistry of 3-azabicyclo[3.3.1]nonanes

Jeyaraman¹,

Avila²

1981

Chem. Rev.

200

113

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Studies on bicyclononanes. Part III. Chair–boat equilibria in bicyclo[3,3,1]nonanes

Cited by 14 publications

References 0 publications

Rearrangement of chorismate to prephenate. Use of chorismate mutase inhibitors to define the transition state structure

Rearrangement of chorismate to prephenate. Use of chorismate mutase inhibitors to define the transition state structure

Adamantanes and related compounds. XII. Diazotization of endo-7-aminomethylbicyclo[3.3.1]nonan-3-ols and endo-7-aminomethylbicyclo[3.3.1]non-2-ene

Chemistry of 3-azabicyclo[3.3.1]nonanes

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