Chalcogen bonding andlatest application

M1 ZHAI
2021/10/21
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Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donors
in Catalysis◇ Summary2

Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donors
in Catalysis◇ Summary3Chalcogen bonding
Chalcogen bonding (ChB) is defined as the interaction between apositively polarized chalcogen atom and a Lewis base (LB) .

Early example of chalcogen bonding.

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Chalcogen bonding：σ-hole
The term “σ-hole” originally referred to the electron-deficient outer lobe of a half-filled p (ornearly p) orbital involved in forming a covalent bond.
A region of positive electrostatic potential which can interact attractively (noncovalently) withnegative sites on other molecules (σ-hole bonding).

Two views of the calculated electrostatic potential on the 0.001 au molecular surface of SiCl4.
Jane S. Murrary et al, J Mol Model, 2009, 723, 15

5Chalcogen bonding

Chalcogen bonding

Electrostatics Charge-transfer

anisotropic
distribution ofelectron density

electrondonation

Dispersion(particularlyrelevant for
weakcomplexes)

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Chalcogen bonding

The strength of a chalcogen bonddepends on:
1. the Lewis basicity of the interacting partner
2. the nature of the chalcogen atom (Te > Se> O > S)
3. the polarization of the chalcogen atom
4. the R-Ch···LB interaction angle: strong
ChBs require angles close to 180°

De Silva et al., Molecules, 2021, 26, 4125

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Chalcogen bonding
ChB vs HB:
1. Hydrogen bonding is limited to one atom, several alternatives areavailable for ChB, with Se and Te certainly being the most promising
candidates for strong ChBs.
2. Hydrogen bonding is markedly less directional than chalcogenbonding, with much stronger deviations of the R-H···LB angle from180° being tolerated.

De Silva et al., Molecules, 2021, 26, 4125

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Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donorsin Catalysis◇ Summary9Chalcogen Bonding in Crystal Engineering

Crystal structure of Ebselen highlighting
the short chalcogen bonda) Supramolecular assembly of iso-tellurazoleoxides (2); b) linear assembly ofchalcogenodicyanides 3; c) intramolecularchalcogen bond in a 1-chalcogeno-8-halogenonaphthalene 4.
10Applications of Chalcogen-Bonded StructuresCrystal structure of nanotubes formed bycyclic hexaselenides, , which incorporate
mesitylene molecules as guests.

Columnar structure of 1,6,12,17tetrathiacyclodocosa-2,4,13,15tetrayne in thesolid state with included toluene guest molecules.
H atoms are omitted for the sake of clarity.

C. Bleiholder, D. B. Werz, H. Koppel, R. Gleiter, J. Am. Chem.Soc. 2006, 128, 266611

Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donorsin Catalysis◇ Summary

12Anion Binding with Chalcogen Bonds• Chalcogen-Bonding-Based Anion Recognition• Chalcogen-Bond-Based Anion Transport

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Chalcogen-Bonding-Based Anion Recognition
Chalcogen bonding
anion-receptors froma) Gabba and Zhao,b) Taylor et al.
c) Beer et al.

H. Y. Zhao, F. P. Gabbai, Nat. Chem., 2010, 2, 984

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Chalcogen-Bond-Based Anion Transport

Anion transporters 10 and 11 by Matile et al.

S. Benz et al., J. Am. Chem. Soc, 2016, 138, 9093
M. Macchione et al., Helv. Chim. Acta, 2018, 101, e1800014
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Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donors
in Catalysis◇ Summary16

Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis• Organochalcogen Compounds as Lewis Bases and Transient
Chalcogen Bonding• Intramolecular Chalcogen Bonding in Synthesis: Rigidification ofChiral Structures• Intermolecular Chalcogen Bonding in Synthesis andOrganocatalysis

17Organochalcogen Compounds as Lewis Bases and Transient
Chalcogen Bonding

Organochalcogens 12 and 13 as Lewis basicorganocatalysts

D. W. Tay et al, Org. Lett., 2013, 15, 1310.
X. Liu et al., J. Am. Chem. Soc.,2018, 140, 4782

Selenenylation of alkenes 14 involving
transient chalcogen bonding
M. G. Edwards et al., J. Org. Chem., 2006, 71, 7293
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Intramolecular Chalcogen Bonding in Synthesis: Rigidificationof Chiral Structures

Intramolecular chalcogen bonding as a tool to rigidify and stabilizeK. Srivastava et al., Dalton Trans., 2011, 40, 4489

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Intermolecular Chalcogen Bonding in Synthesis andOrganocatalysis

S. Benz et al., J. Am. Chem. Soc, 2016, 138, 9093

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Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donorsin Catalysis◇ Summary21

Bis-selenonium Cations as Bidentate Chalcogen BondDonors in Catalysis

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Bis-selenonium Cations as Bidentate Chalcogen Bond
Donors in Catalysis

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Analysis of the bis-selenonium catalyst in aza-Diels−Alderreaction

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Analysis of the bis-selenonium catalyst in aza-Diels−Alderreaction

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Analysis of the bis-selenonium catalyst in aza-Diels−Alderreaction

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Analysis of the bis-selenonium catalyst in Diels−Alderreaction

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Analysis of the bis-selenonium catalyst in Diels−Alderreaction

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Analysis of the bis-selenonium catalyst in bromination
reactions

Xinxin H.; Xinyan W. et al., ACS Catal., 2021, 11, 12632

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Contents◇ Introduction of chalcogen bonding◇ Chalcogen Bonding in Crystal Engineering◇ Anion Binding with Chalcogen Bonds◇ Chalcogen Bonding in Organic Synthesis and Noncovalent
Organocatalysis◇ Bis-selenonium Cations as Bidentate Chalcogen Bond Donors
in Catalysis◇ Summary30

Summary• Rational applications of chalcogen bonding have mostly only
started to appear in the last two decades or so.
• Chalcogen bonding has by now been used very successfully forthe construction of nanoscale materials.
• Chalcogen bonding has been proven to be a powerful tool torigidify reagents or intermediates and thus to enable highly
stereoselective reactions.
• Different monodentate or bidentate neutral or cationicchalcogen-bond donors have now been applied in anion
recognition and transport as well as in organic synthesis.
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