Heptan-1,3,5,7-tetrol-diacetonides, flexible backbone segments with a marked conformational preference

Hoffmann, Reinhard W.; Kahrs, B. Colin

doi:10.1016/0040-4039(96)00863-5

Cited by 10 publications

(4 citation statements)

References 16 publications

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“…This led to our study of the bis(tetrahydropyranyl)methanes 28. [52,53] Our investigation at this stage were poorly focussed since we lacked information on problems for the solution of which conformation design would provide an essential element. In this situation, we resorted to writing a review before we had made any major contributions to the field.…”

Section: Conformation Design Of Open-chain Compoundsmentioning

confidence: 99%

“…This holds likewise for the corresponding acetonide 70. [53] When advancing to the corresponding trimer 71 and the pentamer 72 Trieselmann, one recognizes a small decrease in the diffences of the coupling constants. This attests to the lowering of conformational preferences in larger molecules (the given coupling constants in 71 or 72 represent the average over two backbone segments!).…”

Section: Dicyclohexylmethane Derivativesmentioning

confidence: 99%

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Conformation Design of Open-Chain Compounds

Hoffmann

2000

Angew. Chem. Int. Ed.

Self Cite

244

173

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At the brink of the 21st century, chemistry is increasingly concerned with the function that molecules fulfil as drugs, receptors, or—as ensemble of molecules—as materials. The capability of compounds to fulfil such functions cannot sufficiently be described by using only the terms composition and configuration. A decisive role is played in addition by the conformation of the molecules, which serves as the link between molecular composition and molecular function. Expressions such as “active conformation” or “competent conformation” allude to this aspect. Chemists have to develop an understanding how a flexible molecule adopts the conformation (a distinct shape) which is optimal for the function in question and how this process can be controlled. On the outset of such considerations, we may ask how nature succeeded in the process of evolution to endow flexible molecules with a preference to adopt the conformation which is optimal for the function it has to serve. In this review, I report on how we have reached a crude level of understanding of conformation design in nature with reference to the class of polyketide natural products, how we developed these insights into a conformation design of open‐chain compounds, and which applications are already in sight.

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Section: Conformation Design Of Open-chain Compoundsmentioning

confidence: 99%

Section: Dicyclohexylmethane Derivativesmentioning

confidence: 99%

Conformation Design of Open-Chain Compounds

Hoffmann

2000

Angew. Chem. Int. Ed.

Self Cite

244

173

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“…Finally, when the bis(dioxane) compound 12 29 was treated with LiBPh 4 in CD 3 NO 2 , only very small (< 0.5 ppm, but systematic) changes occurred in the 13 C NMR chemical shifts. These show that the complexation constants are only of the order of 1−2 L·mol −1 .…”

Section: Resultsmentioning

confidence: 95%

Conformation of Isobutyl, 2,2-Dibromoethyl, and 2-Methoxypropyl Side Chains on Cyclohexane and Tetrahydropyran Ring Systems

Hoffmann¹,

Kahrs²,

Reiß³

et al. 2001

Eur. J. Org. Chem.

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An isobutyl group placed equatorially in the 2‐position of a 1‐equatorially substituted cyclohexane adopts a preferred conformation (cf. 5). This also holds when it is placed in the 2‐position on a 3‐equatorially substituted tetrahydropyran (cf. 6). The same conformational preference is found for 2‐methoxypropyl residues in the 2‐position of 3‐substituted tetrahydropyrans (cf. 8 and 10). The latter compounds chelate lithium cations as analogues of 1,2‐dimethoxyethane. Through this complexation, it is possible to effect a change in the side chain conformation.

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“…Dies führte uns dann zur Untersuchung des Konformationsverhaltens von Bis(tetrahydropyranyl)methanen 28. [52,53] Doch waren unsere Untersuchungen in dieser Phase eher ziellos, weil Vorgaben fehlten, für welche Fragestellungen ein Konformationsdesign wirklich förderlich wäre.…”

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Konformationsdesign offenkettiger Verbindungen

Hoffmann

2000

Angewandte Chemie

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Am Übergang zum 21. Jahrhundert befasst sich die Chemie zunehmend mit der Funktion, die Molekülen als Wirkstoffen, Rezeptoren oder – im Molekülverband – als Materialien zukommt. Die Tauglichkeit einer Verbindung für eine molekulare Funktion können wir mit den Begriffen der Konstitution und Konfiguration allein nicht ausreichend beschreiben. Eine entscheidende Bedeutung kommt hier zusätzlich der Konformation der Einzelmoleküle als Mittler zwischen molekularer Konstitution und molekularer Funktion zu. Formulierungen wie „Aktivkonformation”︁ oder „kompetente Konformation”︁ lassen dies anklingen. Der Chemiker muss ein Verständnis dafür entwickeln, wie ein flexibles Molekül die für die jeweilige Funktion optimale Konformation (räumliche Gestalt) einnimmt und wie man dies beeinflussen kann. Am Anfang derartiger Überlegungen zu einem Konformationsdesign steht die Frage, wie es denn die Natur im Zuge der Evolution ihrer Funktionsmoleküle erreicht hat, dass flexible Verbindungen die für die jeweilige Funktion optimale Konformation einnehmen. Wir berichten in diesem Aufsatz, wie wir zu einem ansatzweisen Verständnis des „Konformationsdesigns”︁ der Natur im Bereich der Polyketid‐Naturstoffe gelangt sind, wie wir diese Erkenntnisse zu einem Konformationsdesign offenkettiger Moleküle weiterentwickelt haben und welche Anwendungsmöglichkeiten für diese Erkenntnisse sich jetzt schon abzeichnen.

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Heptan-1,3,5,7-tetrol-diacetonides, flexible backbone segments with a marked conformational preference

Cited by 10 publications

References 16 publications

Conformation Design of Open-Chain Compounds

Conformation Design of Open-Chain Compounds

Conformation of Isobutyl, 2,2-Dibromoethyl, and 2-Methoxypropyl Side Chains on Cyclohexane and Tetrahydropyran Ring Systems

Konformationsdesign offenkettiger Verbindungen

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