Thiele's acid revisited: Isolation and characterization of two minor products formed by carbonation of cyclopentadienide anion

Marchand, Alan P.; Namboothiri, Irishi N. N.; Lewis, S. B.; Watson, William H.; Krawiec, Mariusz

doi:10.1016/s0040-4020(98)00770-4

Cited by 22 publications

(18 citation statements)

References 8 publications

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“…The conclusion that the cyclopentene CO 2 Me group in Thiele's ester thus is expected to be the more highly susceptible of the two ester functionalities toward base promoted ester hydrolysis is consistent with the experimentally observed preferential formation of 3a.…”

Section: Methodssupporting

confidence: 84%

“…Finally, the somewhat increased importance of the resonance contribution of the chargeseparated canonical form in the norbornene α,β-unsaturated ester moiety, i.e., 2b, is expected to reduce the C=O double bond character in the associated ester group, thereby rendering this CO 2 Me group more resistant to base promoted hydrolysis than the corresponding ester group in the cyclopentene α,β-unsaturated ester moiety. The conclusion that the cyclopentene CO 2 Me group in Thiele's ester thus is expected to be the more highly susceptible of the two ester functionalities toward base promoted ester hydrolysis is consistent with the experimentally observed preferential formation of 3a.…”

Section: Methodsmentioning

confidence: 99%

“…2 Recently, our attention has turned to Thiele's acid as a potentially useful intermediate in the synthesis of unusual polycarbocyclic systems. 2,3 In connection with ongoing research projects, it was necessary for us to prepare isomerically pure Thiele's acid in quantity. To this end, the crude mixture of carboxylic acids obtained via carbonation of sodium cyclopentadienide was esterified by using MeOH-H 2 SO 4 .…”

Section: Introductionmentioning

confidence: 99%

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Structure of a minor reaction product formed via base promoted hydrolysis of Thiele’s ester

Watson¹,

Marchand²,

Sivappa³

2003

Arkivoc

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Base promoted hydrolysis of dimethyl 3aα,4α,7α,7aα-tetrahydro-4,7-methano-lH-indene-2,5-dicarboxylate (i.e., "Thiele's ester", 2), performed by using KOH-MeOH, afforded after aqueous acidic workup the corresponding diacid (i.e., "Thiele's acid", 1) along with a minor reaction product, 3. Compound 3 has been shown to possess structure 3a via application of single crystal X-ray crystallographic techniques.

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Section: Methodssupporting

confidence: 84%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure of a minor reaction product formed via base promoted hydrolysis of Thiele’s ester

Watson¹,

Marchand²,

Sivappa³

2003

Arkivoc

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“…13 CHCl 3 ): 3016w, 2974w, 2929w, 1727s, 1600w, 1437w, 1369m, 1158s, 1088m, 1047m, 909w, 865w. (4) ]decane-1-carboxylic Acid (38). A soln.…”

Section: {5-[(benzyloxy)methyl]furan-2-yl}methyl (E)-3-(phenylsulfonymentioning

confidence: 99%

“…This simplified the preparation of the diacids 31 that were obtained (crude) in 75% yield. The corresponding di(tert-butyl) esters 32 were obtained (88%) by treating the diacids with oxalyl chloride and then with t-BuOK in Et 2 O. Thiele's acids 31 and the diesters 32 are mixtures of isomers [37] [38]. Considering that the esters 32 were thermolysed in the next step, we did not separate the isomers.…”

mentioning

confidence: 99%

7‐Oxanorbornane and Norbornane Mimics of a Distorted β‐D‐Mannopyranoside: Synthesis and Evaluation as β‐Mannosidase Inhibitors

Buser

Vasella

2005

Helvetica Chimica Acta

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The racemic 7-oxanorbornanyl and norbornanyl aminoalcohols 3, 4, 42, 45, and 46 were synthesized and tested as snail b-mannosidase inhibitors. The amino tetraol 3 was obtained from the known sulfonyl acrylate 9 and furan 10. Esterification provided 11 that underwent an intramolecular Diels-Alder reaction to the 7-oxanorbornene 12. Reduction of 12 to 13, desulfonylation, isopropylidenation, and cis-dihydroxylation gave 16. A second isopropylidenation to 17, followed by debenzylation and a Mitsunobu-Gabriel reaction provided 19 that was deprotected via 20 to 3. Diels-Alder cycloaddition of furfuryl acetate and maleic anhydride to 21, followed by alcoholysis of the anhydride, cis-dihydroxylation, isopropylidenation, and Barton decarboxylation gave the ester 25. Deacetylation to 26 and a Mitsunobu-Gabriel reaction led to 27 that was transformed into the NBoc analogue 29, reduced to the alcohol 30, and deprotected to 4. The 1-aminonorbornane 5 was obtained from Thiele's Acid 31. Diels-Alder cycloaddition of the cyclopentadiene obtained by thermolysis of the diester 32, methanolysis of the resulting anhydride 33, dihydroxylation, isopropylidenation, Barton decarboxylation, and Curtius degradation led to the benzyl carbamate 39 that was reduced to the alcohol 40, transformed into the N-Boc carbamate 41, and deprotected to 5. The alcohol 40 was also transformed into the benzylamine 42, aniline 45, and hydroxylamine 46. Snail b-mannosidase was hardly inhibited by 3, 4, 42, 45, and 46. Only the amino triol 5 proved a stronger inhibitor. The inhibition by 5 depends on the pH value (at pH 3.5: K i = 1900 mM; at pH 4.5: K i = 340 mM; at pH 5.5: K i = 110 mM). The results illustrate the strong dependence of the inhibition by bicyclic mimics upon the precise geometry and orientation of the amino group as determined by the scaffold. It is in keeping with the hypothesis that the reactive conformation imposed by snail b-mannosidase is close to aIntroduction. -The design, synthesis, and study of glycosidase inhibitors continue to attract interest, fuelled by the potential of strong and selective glycosidase inhibitors to act as drugs (e.g., against lysosomal storage disorders such as Gaucher's disease , and their use as tools in the elucidation of the mechanism of action of glycosidases on the basis of structure-activity relations, kinetic studies, and information provided by the structure determination of enzyme-inhibitor complexes [7]. Transition-state analogues promise to be most useful. Their design is based upon existent information about the mechanism of action, and particularly about the transition state of the rate-determining step, while their study may contribute to a more detailed understanding of the mechanisms of action as summarised in several reviews [8] [9]. Partial transition-state mimics may be thought of as being closer to a point of the reaction coordinate that either precedes, or follows the transition state of interest, and there are reasons to hypothesise that those preceding the rate-determining transition s...

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ChemInform Abstract: Thiele′s Acid Revisited: Isolation and Characterization of Two Minor Products Formed by Carbonation of Cyclopentadienide Anion.

1999

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Thiele's acid revisited: Isolation and characterization of two minor products formed by carbonation of cyclopentadienide anion

Cited by 22 publications

References 8 publications

Structure of a minor reaction product formed via base promoted hydrolysis of Thiele’s ester

Structure of a minor reaction product formed via base promoted hydrolysis of Thiele’s ester

7‐Oxanorbornane and Norbornane Mimics of a Distorted β‐D‐Mannopyranoside: Synthesis and Evaluation as β‐Mannosidase Inhibitors

ChemInform Abstract: Thiele′s Acid Revisited: Isolation and Characterization of Two Minor Products Formed by Carbonation of Cyclopentadienide Anion.

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