Protonation-triggered conformational modulation of an N,N′-dialkylbispidine: first observation of the elusive boat–boat conformer

Norrehed, Sara; Erdélyi, Máté; Light, Mark E.; Gogoll, Adolf

doi:10.1039/c3ob41122b

Cited by 13 publications

(10 citation statements)

References 92 publications

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“…We believe that the protonation at the Pyr side of bispidine nitrogen changes the conformation of 1 from chairchair to boat-chair hence rendering it unsuitable for intramolecular complex formation (Scheme 2). 32 The fact that 1 is stable in the presence of 3.16 Â 10 À3 M [H + ] is amply evident by the mass spectroscopic data (Fig. S8, ESI †).…”

Section: Resultsmentioning

confidence: 97%

A tryptophan-containing fluorescent intramolecular complex as a designer peptidic proton sensor

Haridas

Yadav

Sharma

et al. 2016

Phys. Chem. Chem. Phys.

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Pyrene and tryptophan groups judiciously placed on a novel molecular scaffold, namely, bispidine exhibited fluorescence due to the formation of an unprecedented emissive intramolecular complex in polar solvents. Upon protonation, the emission signal from the pyrene unit enhances at the expense of the emission signal from the complex. The probe demonstrates good sensitivity, excellent selectivity, and adequate reversibility towards proton sensing. The present design based on the bispidine scaffold opens up newer opportunities for the design of novel bispidine-peptide sensors.

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Section: Resultsmentioning

confidence: 97%

A tryptophan-containing fluorescent intramolecular complex as a designer peptidic proton sensor

Haridas

Yadav

Sharma

et al. 2016

Phys. Chem. Chem. Phys.

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“…11 Besides its bioactive properties, the peculiar three-dimensional structure has attracted attention for use in the design of bicyclic scaffolds, which can interconvert between conformations. 9,[12][13][14][15] Bispidine derivatives can adopt three main conformations: the chair-chair (CC), chair-boat (CB), and boat-boat (BB) conformations, respectively (Scheme 1a). The bispidine skeleton mainly adopts the most thermodynamically feasible of the three conformations.…”

Section: Conformation Switches Based On Bispidine Derivativesmentioning

confidence: 99%

Ring-System-Based Conformational Switches and their Applications in Sensing and Liposomal Drug Delivery

Pedersen

2022

Synthesis

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In the past decades, a great number of stimuli-responsive systems have been developed to be used as drug-delivery systems with high sensitivity and selectivity in targeted therapy. Despite promising results, the current stimuli-responsive systems suffer from the complexity of preparation, as most novel stimuli-responsive systems are based on polymers. Small molecules have often been neglected as candidates for application for stimuli-responsive systems. Recently, structures based on six-membered ring molecules or bicyclic molecules have been developed into conformational switches working through conformational interconversion. These single conformational switches have significantly reduced the complexity of material preparation compared to polymers or copolymers. In this review, we focus on ring-system-based conformational switches that are involved in sensors and smart drug-delivery systems. We hope that this review will shed light on ring-system-based single conformational switches for use in the development of stimuli-responsive systems.1 Introduction2 Conformation Switches Based On Bispidine Derivatives3 Conformation Switches Based On Cycloalkanes4 Conformation Switches Based On Carbohydrates5 Conclusion

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“…[26] However, the boat-boat conformer seems too energetically unfavourable, a recent report by Norrehed et al claims the existence of a bispidine bicycle as a mixture of chair-boat and boat-boat conformation. [31] The presence of the bispidine scaffolds in quinolizidine alkaloids ( Figure 1) was discovered about more than a hundred and fifty years back but still several aspects and usefulness of this molecule has remained unexplored. Since the diamine form of the bispidine framework is resourceful in the biological forefront, considerable research has been conducted on the effect of substituents at N3 and N7 in particular.…”

Section: Introductionmentioning

confidence: 99%

“…However, the boat‐boat conformer seems too energetically un‐favourable, a recent report by Norrehed et al . claims the existence of a bispidine bicycle as a mixture of chair‐boat and boat‐boat conformation [31] …”

Section: Introductionmentioning

confidence: 99%

Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds

Mukherjee

Sastri

2020

Israel Journal of Chemistry

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Ligand framework in a metal complex has a pivotal role to play in orchestrating the spectroscopic and reactivity parameters. High-valent non-heme metal intermediates are known to be crucial species in the catalytic cycles of several metalloenzymes. Among the plethora of a variety of ligand frameworks employed in bioinorganic chemistry, the bispidine molecular scaffold is unique and privileged. In this review, we intend to discuss the overwhelming effects of the bispidine ligand scaffold in tuning the spectroscopic signatures and reactivity parameters of non-heme metal intermediates. The basic skeleton constituting a fused and rigid bicyclic diamine framework with its tentacles tethered to C2, C4, N3 and N7 provides tuneable features to both the primary and secondary coordination spheres. Therefore, the bispidine framework offers a handle to optimize the balance of rigidity and flexibility in a coordination molecule which is thereby important in understanding the rich but surprising results in the reactivity of metal intermediates contained in these scaffolds. Herein, we summarize the significant developments in different types of oxidation reactions of reactive metal intermediates stabilized in bispidine ligands and noted their mechanistic details.

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Protonation-triggered conformational modulation of an N,N′-dialkylbispidine: first observation of the elusive boat–boat conformer

Cited by 13 publications

References 92 publications

A tryptophan-containing fluorescent intramolecular complex as a designer peptidic proton sensor

A tryptophan-containing fluorescent intramolecular complex as a designer peptidic proton sensor

Ring-System-Based Conformational Switches and their Applications in Sensing and Liposomal Drug Delivery

Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds

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