Supramolecular Catalysis of a Catalysis-Resistant Diels–Alder Reaction: Almost Theoretical Acceleration of Cyclopentadiene Dimerization inside Cucurbit[7]uril

Tehrani, Foad N.; Assaf, Khaleel I.; Hein, Robert; Jensen, Casper M. E.; Nugent, Thomas C.; Nau, Werner M.

doi:10.1021/acscatal.1c05659

Cited by 29 publications

(25 citation statements)

References 109 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[5][6][7][8][9][10][11][12][13][14][15] Among the macrocyclic hosts used in supramolecular catalysis, cucurbit[n]urils (Q[n]s or CB[n]s) distinguish themselves by their rigid pumpkin-shaped cavities and superior substrate recognition properties with high binding ability in aqueous media. [16][17][18][19][20][21][22][23][24] For example, Mock and co-workers revealed in the early 1980s that the 1,3-dipolar Huisgen cycloaddition achieved inside the Q [6] cavity can selectively produce the 1,4-substituted triazole product [25] similar to that observed in the copper-catalyzed "click" reaction reported by Sharpless et al in 2001. [26] In particular, the cycloaddition reaction inside the Q [6] cavity was found to be accelerated 5.5 × 10 4 -fold.…”

Section: Introductionmentioning

confidence: 79%

Cucurbit[7]uril‐Encapsulation‐Controlled Supramolecular Photoproduct and Radical Fluorescence Emission

Peng

Luo

Rao

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

Herein, a host-guest interaction-controlled photoproduct created by using cucurbit[7]uril (Q[7])-based pseudorotaxane structures is reported. The assembly exhibited controlled behavior towards the reduction of the ethylene (C=C) bond in the tetrakis(pyridin-4-yl)ethylene (TPyE) guest molecule under UV light irradiation. This can be attributed to the Q[7] encapsulation masking the four pyridinium arms of the guest, which inhibits planarization of the TPyE core to form the cyclization product. In particular, the strong affinity of Q[7] for the butyl-substituted guest (TPyE-4C) led to an unusual radical fluorescence emission of the photoirradiationtriggered intermediate of the guest molecule being observed in aqueous solution. This work provides a valuable paradigm and new insight for macrocycle-based host À guest interactions in supramolecular catalysis and luminescent radical materials.

show abstract

Section: Introductionmentioning

confidence: 79%

Cucurbit[7]uril‐Encapsulation‐Controlled Supramolecular Photoproduct and Radical Fluorescence Emission

Peng

Luo

Rao

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“… a L1 = MPW1PW91/6-31+G(d) in ref ; L2 = MP3/6-31G*//6-31G* in ref ; L3 = CBS-QB3 in ref ; L4 = ωB97X-D/6-31G* in ref and ωB97X-D/def2-TZVP; L5 = DLPNO-CCSD(T)/cc-pQVZ//L4. *This work. …”

Section: Resultsmentioning

confidence: 99%

Probative Evidence and Quantitative Energetics for the Unimolecular Mechanism of the 1,5-Sigmatropic Hydrogen Shift of Cyclopentadiene

2022

View full text Add to dashboard Cite

While the 1,5-sigmatropic hydrogen shift in cyclopentadiene is generally thought to be a unimolecular pericyclic reaction, Yamabe proposed a more complex bimolecular mechanism proceeding through the exo dimer of cyclopentadiene. DFT computations by Yamabe were claimed to show that the bimolecular mechanism was kinetically more favorable than the unimolecular mechanism. Reinvestigation of the unimolecular concerted mechanism and Yamabe's bimolecular mechanism with ωB97X-D and DLPNO-CCSD(T) calculations demonstrates a 25 kcal/mol preference for the unimolecular mechanism relative to the bimolecular mechanism. While Yamabe's calculations were performed with the less accurate B3LYP functional, the incorrect conclusion was the result of a different error discovered here. We have also computed corrections for tunneling that result in computed activation barriers within 1.5 kcal/mol of the experimental values.

show abstract

“…3,4 These properties allow them to be used to treat the channelopathies, in supramolecular chemistry, anion sensing and catalysis. 5 Imidazoldidine-2-thiones were shown to act as ligands for transition metals. 6 In addition, the DHIT is an effective inhibitor of acid corrosion.…”

Section: Figure 1 Dhit Synthesis Reactionmentioning

confidence: 99%

Reaction Pathway and Kinetic Study of 4,5-Dihydroxyimidazolidine-2-thione Synthesis by HPLC and NMR

Kalichkina¹,

Новиков²,

Kotelnikov³

et al. 2022

HETEROCYCLES

View full text Add to dashboard Cite

Process of 4,5-dihydroxyimidazolidine-2-thione (DHIT) synthesis from thiourea and glyoxal is studied. Formation of 1,3-dihydro-2H-imidazole-2-thione and 4,5-dihydroxyimidazolidin-2-one as byproducts is confirmed by NMR. The kinetics of the scalable DHIT synthesis process is studied by HPLC, and the kinetic parameters of the model based on the proposed reaction scheme are calculated. The model correctly describes the kinetics of the DHIT formation and thiourea consumption.

show abstract

Supramolecular Catalysis of a Catalysis-Resistant Diels–Alder Reaction: Almost Theoretical Acceleration of Cyclopentadiene Dimerization inside Cucurbit[7]uril

Cited by 29 publications

References 109 publications

Cucurbit[7]uril‐Encapsulation‐Controlled Supramolecular Photoproduct and Radical Fluorescence Emission

Cucurbit[7]uril‐Encapsulation‐Controlled Supramolecular Photoproduct and Radical Fluorescence Emission

Probative Evidence and Quantitative Energetics for the Unimolecular Mechanism of the 1,5-Sigmatropic Hydrogen Shift of Cyclopentadiene

Reaction Pathway and Kinetic Study of 4,5-Dihydroxyimidazolidine-2-thione Synthesis by HPLC and NMR

Contact Info

Product

Resources

About