Sigma‐assistance, an unrecognized factor in organic reactivity

Verhoeven, J. W.

doi:10.1002/recl.19800990412

Cited by 15 publications

(1 citation statement)

References 4 publications

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“…[146] Again, this effect is owed to the very small bridgehead-bridgehead distance within the BCP-radical of only 1.74 , [147] reflecting a large through-space contribution;t his is an otable difference in length when compared to the neutralB CP-species of 1.845 .I na ddition, three identicalp athways through the carbon-skeleton with an ideal trans-arrangement are available for an enhanced through-bond communication. [148] The triptycene radical on the other hand shows no interaction with the oppositeb ridgehead substituent. Even if af luorine atom is placed on the other bridgehead carbon atom, no measurable coupling is observed between the radical and the opposite atom.…”

Section: Bridgehead Radicalsmentioning

confidence: 99%

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Locke

Bernhard

Senge

2019

Chemistry A European J

189

143

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Nonconjugated hydrocarbons, like bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, triptycene, and cubane are a unique class of rigid linkers. Due to their similarity in size and shape they are useful mimics of classic benzene moieties in drugs, so‐called bioisosteres. Moreover, they also fulfill an important role in material sciences as linear linkers, in order to arrange various functionalities in a defined spatial manner. In this Review article, recent developments and usages of these special, rectilinear systems are discussed. Furthermore, we focus on covalently linked, nonconjugated linear arrangements and discuss the physical and chemical properties and differences of individual linkers, as well as their application in material and medicinal sciences.

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Section: Bridgehead Radicalsmentioning

confidence: 99%