Azide⋅⋅⋅Oxygen Interaction: A Crystal Engineering Tool for Conformational Locking

Madhusudhanan, Mithun C.; Balan, Haripriya; Werz, Daniel B.; Sureshan, Kana M.

doi:10.1002/anie.202106614

Cited by 29 publications

(18 citation statements)

References 102 publications

(24 reference statements)

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“…The inositol ring adopts a chair conformation. The azide moiety is involved in azide‐oxygen interaction [17] . As expected, molecules of 1 form hydrogen‐bonded layers in the ac plane (Figure 2b, shown using a blue dotted line).…”

Section: Figuresupporting

confidence: 68%

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne

2022

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Here we report the synthesis of a trisubstituted-1,2,3-triazole-linked polymer using a topochemical azide-alkyne cycloaddition (TAAC) reaction. A cyclitolderived monomer having an azide and an internal alkyne group was designed. The four hydroxy groups present in this monomer dictate its crystal packing such that the monomer molecules are arranged head-to-tail, thereby placing the internal alkyne and the azide units of adjacent molecules proximally. Although the alignment of the reactive groups in the monomer crystal is not favourable for a topochemical reaction, a reactive orientation can be achieved by the rotation of the reactive groups. Upon heating the crystals, the monomer underwent topochemical polymerization to yield the trisubstituted-1,2,3-triazole-linked-polycyclitol. This study demonstrates a new synthetic strategy for cycloaddition reaction between non-polarized internal alkynes and azides to yield trisubstituted triazoles.

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Section: Figuresupporting

confidence: 68%

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne

2022

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“…The azide moiety is involved in azide-oxygen interaction. [17] As expected, molecules of 1 form hydrogen-bonded layers in the ac plane…”

supporting

confidence: 66%

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne

2022

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Here we report the synthesis of a trisubstituted‐1,2,3‐triazole‐linked polymer using a topochemical azide‐alkyne cycloaddition (TAAC) reaction. A cyclitol‐derived monomer having an azide and an internal alkyne group was designed. The four hydroxy groups present in this monomer dictate its crystal packing such that the monomer molecules are arranged head‐to‐tail, thereby placing the internal alkyne and the azide units of adjacent molecules proximally. Although the alignment of the reactive groups in the monomer crystal is not favourable for a topochemical reaction, a reactive orientation can be achieved by the rotation of the reactive groups. Upon heating the crystals, the monomer underwent topochemical polymerization to yield the trisubstituted‐1,2,3‐triazole‐linked‐polycyclitol. This study demonstrates a new synthetic strategy for cycloaddition reaction between non‐polarized internal alkynes and azides to yield trisubstituted triazoles.

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“…Turning to N π-holes, the C end of a CO molecule approaches the central N of NNO in the gas phase, as do several π-electron donors such as HCCH . A very recent examination of a number of crystals verified that the π-hole above the central N of an NNN azide group can indeed engage in an intramolecular pnicogen bond, in these cases with an O atom from another segment of the molecule. The calculated π-hole depths in these molecules were considerably shallower than the NNNF and NNNCN molecules described here, but the bond critical point densities were comparable.…”

Section: Discussionmentioning

confidence: 99%

“…However, there have been some indications of possible N-participation via quantum calculations under special circumstances, − particularly in the context of the NO 2 group. − On an encouraging note, recent gas phase and matrix spectra , have verified the earlier computational indications that the π-hole above the NO 2 group can accept electron density from an amine in the context of a N···N pnicogen bond. A very recent study of crystals has provided structural and electron density evidence that the central N of a NNN azide group can engage in an intramolecular pnicogen bond with an O atom.…”

Section: Introductionmentioning

confidence: 99%

On the Ability of Nitrogen to Serve as an Electron Acceptor in a Pnicogen Bond

Scheiner

2021

J. Phys. Chem. A

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Whereas pnicogen atoms like P and As have been shown repeatedly to act as electron acceptors in pnicogen bonds, the same is not true of the more electronegative first-row N atom. Quantum calculations assess whether N can serve in this capacity in such bonds and under what conditions. There is a positive π-hole belt that surrounds the central N atom in the linear arrangement of NNNF, NNN-CN, and NNO, which can engage a NH3 base to form a pnicogen bond with binding energy between 3 and 5 kcal/mol. Within the context of a planar arrangement, the π-hole above the N in NO2OF, N(CN)3, and CF3NO2 is also capable of forming a pnicogen bond, the strongest of which amounts to 11 kcal/mol with NMe3 as base. In their pyramidal geometry, NF3 and N(NO2)3 engage with a base through the σ-hole on the central N, with variable binding energies between 2 and 9 kcal/mol. AIM and NBO provide somewhat different interpretations of the secondary interactions that occur in some of these complexes.

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Azide⋅⋅⋅Oxygen Interaction: A Crystal Engineering Tool for Conformational Locking

Cited by 29 publications

References 102 publications

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne

On the Ability of Nitrogen to Serve as an Electron Acceptor in a Pnicogen Bond

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