cis,cis-1,5-Cyclooctadiene diepoxide

Cope, Arthur C.; Fisher, B. S.; Funke, Wolfgang; McIntosh, John M.; McKervey, M. Anthony

doi:10.1021/jo01259a046

Cited by 22 publications

(8 citation statements)

References 5 publications

(12 reference statements)

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“…Wood and Wiggins (2) observed that hydrolysis of 1,2,5,6-diepoxyhexane with boiling water yields a tetrahydrofuran derivative as the major product (65%) but none of the expected tetrahydroxyhexane. Similar results were obtained by Ross (3) Cope and coworkers (4) showed that 1,2,5,6-diepoxycyclooctane gives bicyclic ethers in 100% yield on treatment with aqueous sulfuric acid but no tetrols.…”

Section: Ho Osupporting

confidence: 83%

Improved preparation of 9,10,12,13‐tetrahydroxystearic acids fromanti‐cis,cis‐9,10,12,13‐diepoxystearic acid

Khuddus

Usui

Swern

1973

J Americ Oil Chem Soc

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A mixture of isomeric 9,10,12,13-tetrahydroxystearic acids (threo, threo, threo and threo, erythro, threo) can be prepared from anti-cis, cis-9,10,12,13-di-epoxystearic acid in over 80% yield by way of the intermediate di(hydroxy-alkoxysulfonium) salts and in ca. 68% yield by way of the intermediate di(hydroxy-formate) esters obtained by acid-catalyzed epoxide ring opening with dimethyl sulfoxide and formic acid, respectively. Mechanisms and stereochemistry of formation of the two isomers are discussed. Factors that influence the formation of cyclic products in competition with tetrahydroxystearic acids also are described. The key to the greatly improved yield of tetrahydroxystearic acids over prior literature procedures is avoiding water during ring opening of the protonated epoxide, as even small quantities of water cause marked reduction in yields of tetrahydroxystearic acids.

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Section: Ho Osupporting

confidence: 83%

Improved preparation of 9,10,12,13‐tetrahydroxystearic acids fromanti‐cis,cis‐9,10,12,13‐diepoxystearic acid

Khuddus

Usui

Swern

1973

J Americ Oil Chem Soc

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“…In order to prepare 9-oxabicyclo[4.2.1]nona-2,4diene, an interesting 1,3-diene (Cope, McKervey & Weinshenker, 1969), using endo,endo-2,5-dihydroxy- Siemens, 1990) plot of compound (I) with the atomic numbering scheme (50% probability ellipsoids).…”

Section: Commentmentioning

confidence: 99%

Three 2,5-Disubstituted 9-Oxabicyclo[4.2.1]nonanes. Transannular O-Heterocyclization Products of Cycloocta-1,5-diene

Hegemann¹,

Haufe²,

Fröhlich³

et al. 1997

Acta Crystallogr C

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“…The n.m.r. spectrum of the crude product showed peaks in the region 6 Base Treatment of the Bis-P-hydroxyphosphine Oxides (1 1) and ( 12): General Method.-In the following series of ' g.1.c.scale ' experiments, the bis-p-hydroxyphosphine oxides (1 1) or a mixture of ( 11) and (12) in the ratio 66 : 34 or 35 : 65 (mixtures A and B respectively) (28 mg, 0.05 mmol) were treated with a range of solvent (2 m1)-base (in excess) combinations. Generally, after 2 h at 18 "C water (4 ml) was added and the aqueous solution extracted with light petroleum (3 x 3 ml).…”

Section: Ciscis-cyclonona-l5-diene'3-to a Stirred Refluxing Deepmentioning

confidence: 99%

“…The high regioselectivity in the epoxide opening is noteworthy. Epoxidation of the unsaturated hydroxyphosphine oxide, essentially (4), gave two epoxides (6) and (7) in the ratio 4 : 6. The major epoxide (7) deteriorated on standing or attempted recrystallisation owing to formation of a transannular ether (which attested to the trans-relationship of the OH group to the epoxide ring) and this approach was therefore abandoned.…”

mentioning

confidence: 99%

trans-Cycloalkenes. Part 12. trans,trans- and cis,trans-Cyclonona-1,5-diene

CONNELL¹,

Whitham²

1983

J. Chem. Soc., Perkin Trans. 1

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Possible synthetic routes to trans,trans-cyclonona-l,5-diene from the cis,cis-isomer have been investigated using the phydroxyphosphine oxide olefin inversion procedure. A stepwise approach via the epoxytrans-cyclononene (1 0) failed. However consecutive double elimination involving the bis-phydroxyphosphine oxides (1 1 ) and (1 2) gave cisand trans-l,2-divinylcyclopentane which are believed to have been obtained by rapid Cope rearrangement of first formed ' parallel ' and ' crossed ' tramtrans-cyclonona- 1,5-diene (IA) and (1 6) respectively. Arising out of our experiences with trans-cyclonona-l,2,6triene described in the previous paper in this series, we decided to attempt the preparation of trans,trMs-cyclonona-1,s-diene. An additional incentive was provided by a recent statement in the literature that the latter ' should be more stable than the known cis,trans-isomer.' This statement was based on examination of molecular models. It is supported by early forcefield calculations but not by more recent ones." rrms,trans-Cyclonona-l,5-diene might be expected to exist in two diastereoisomeric forms or at least two conformational isomers with a relatively high energy barrier between them. These two forms are the parallel and crossed structures (1A) and (1B) respectively. In designing routes to these, it was decided to utilise the P-hydroxyphosphine oxide elimination since this olefin inversion procedure was known to proceed with high stereospecificity in suitable cases, and by appropriate choice of precursors it might be possible to direct formation of either (1A) or (1B).Clearly one can adopt either a stepwise approach in which the trans-double bonds are introduced one at a time or a simultaneous one in which they are introduced together in a

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cis,cis-1,5-Cyclooctadiene diepoxide

Cited by 22 publications

References 5 publications

Improved preparation of 9,10,12,13‐tetrahydroxystearic acids fromanti‐cis,cis‐9,10,12,13‐diepoxystearic acid

Improved preparation of 9,10,12,13‐tetrahydroxystearic acids fromanti‐cis,cis‐9,10,12,13‐diepoxystearic acid

Three 2,5-Disubstituted 9-Oxabicyclo[4.2.1]nonanes. Transannular O-Heterocyclization Products of Cycloocta-1,5-diene

trans-Cycloalkenes. Part 12. trans,trans- and cis,trans-Cyclonona-1,5-diene

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