Unusual DBU-catalyzed decarboxylative formation of allylic thioethers from vinyl cyclic carbonates and thiols

Ni, Jixiang; Lanzi, Matteo; Kleij, Arjan W.

doi:10.1039/d2qo01511k

Cited by 5 publications

(3 citation statements)

References 39 publications

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“…Among organic bases (e.g., 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, and 1,5-diazabicyclo[4.3.0]non-5-ene), DBU, having a p K a value of 12, was selected to replace corrosive KOH because of its high proton-abstracting capability of adjacent nitrogen atoms and efficient catalysis for many chemical reactions such as esterification, , etherification, , and condensation . As shown in Figure A and Figure S1, different biomasses ( i.e ., wood pump, tunicate, shrink shells, squid pen, silk fibers, and spider silk dragline) were first incubated in DMSO containing DBU (20 wt %) at 65 °C for 24 h under mechanic stirring.…”

Section: Resultsmentioning

confidence: 99%

Versatile Deprotonation-Induced Exfoliation and Functionalization of Biological Nanofibrils for Actuation and Fluorescence

Zhang,

Wang,

et al. 2024

ACS Appl. Mater. Interfaces

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Biological nanofibrils not only are characteristic of many species of biomasses but also serve as a promising type of sustainable nanomaterials for various applications. However, their production has long relied on an invasive and energyconsuming mechanical shear. A noninvasive and versatile approach remains challenging to exfoliate different types of biomasses into nanofibrils. In this study, we showed a versatile and nonaggressive intercalative deprotonation agent of organic base, which could efficiently deprotonate various biomasses for energy-saving exfoliation and functionalization, including cellulose, chitin, and silk. Both carboxylic nanofibrils and nanofibrils with pristine chemical structures could be produced in high yields through manual shaking or sonication. By further grafting photoresponsive groups via transesterification, intelligent NFs were generated featuring ultraviolet-responsive fluorescence and hydrophilicity. These responsive fluorescence and actuation behaviors promised their potential as green encryption and anticounterfeiting nanomaterials.

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Section: Resultsmentioning

confidence: 99%

Versatile Deprotonation-Induced Exfoliation and Functionalization of Biological Nanofibrils for Actuation and Fluorescence

Zhang,

Wang,

et al. 2024

ACS Appl. Mater. Interfaces

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“…APCs can be conveniently synthesized by ring opening polymerization (ROP) of six-membered cyclic carbonates that typically provide polymers with precise molar mass and narrow dispersity. [3][4][5][6][7][8] A number of catalytic systems 9 have been developed for the living ROP of trimethylene carbonate (TMC). [10][11][12][13][14][15][16][17][18][19][20][21] Despite this advantage, the low glass transition temperatures (T g = À20 C) of poly(TMC) has been one of its limitations.…”

Section: Introductionmentioning

confidence: 99%

“…(Vide Infra). APCs can be conveniently synthesized by ring opening polymerization (ROP) of six‐membered cyclic carbonates that typically provide polymers with precise molar mass and narrow dispersity 3–8 . A number of catalytic systems 9 have been developed for the living ROP of trimethylene carbonate (TMC) 10–21 .…”

Section: Introductionmentioning

confidence: 99%

Tuning the structure of pendant groups in poly(α‐arylTMC)s: A pathway to high glass transition temperature

Patra,

Yadav,

Anbarasu

et al. 2024

Journal of Polymer Science

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Aliphatic polycarbonates have been explored as environmentally benign alternatives to aromatic polycarbonates. Improvements to the glass transition temperature (Tg) of aliphatic polycarbonates have been pursued by several groups. We recently showed that attaching a pendant aromatic group to poly(TMC) can enhance the Tg. Also, we have shown that para substituents on the pendant group have an impact on the Tg. Here, we have explored the role of bulky pendant groups and the effect of substituent position on the pendant aromatic ring. We prepared novel naphthalene‐derived poly(TMC)s as well as 2‐Br‐substituted poly(PhTMC). The 2‐bromophenyl derivative showed a Tg of 69.5 °C which represents a nominal increase in comparison to the 4‐bromo derivative that we reported earlier. This suggests that the position of the substituent does not have a critical impact on Tg. With naphthalene derivatives, the increase in steric bulk led to an increase in Tg. Increase of chain length beyond fifty monomer units had a minimal impact on Tg. Finally, when 4‐bromonaphthyl moiety was the pendant group, we observed a Tg of 97 °C. This demonstrates that Tg can be varied significantly by modifying the pendant groups. We have also shown that the 1,3‐diols used in our polymer are non‐cytotoxic.

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Chemo‐, Regio‐ and Stereoselective Preparation of (Z)‐2‐Butene‐1,4‐Diol Monoesters via Pd‐Catalyzed Decarboxylative Acyloxylation

Cheng,

Zhao,

Zhang

et al. 2024

Chemistry A European J

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(Z)‐alkenes are useful synthons but thermodynamically less stable than their (E)‐isomers and typically more difficult to prepare. The synthesis of 1,4‐hetero‐bifunctionalized (Z)‐alkenes is particularly challenging due to the inherent regio‐ and stereoselectivity issues. Herein we demonstrate a general, chemoselective and direct synthesis of (Z)‐2‐butene‐1,4‐diol monoesters. The protocol operates within a Pd‐catalyzed decarboxylative acyloxylation regime involving vinyl ethylene carbonates (VECs) and various carboxylic acids as the reaction partners under mild and operationally attractive conditions. The newly developed process allows access to a structurally diverse pool of (Z)‐2‐butene‐1,4‐diol monoesters in good yields and with excellent regio‐ and stereoselectivity. Various synthetic transformations of the obtained (Z)‐2‐butene‐1,4‐diol monoesters demonstrate how these synthons are of great use to rapidly diversify the portfolio of these formal desymmetrized (Z)‐alkenes.

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Unusual DBU-catalyzed decarboxylative formation of allylic thioethers from vinyl cyclic carbonates and thiols

Abstract: An unanticipated exo-cyclic nucleophilic attack of thiol reagents onto vinyl cyclic carbonates is described under DBU catalysis. The process allows to produce allylic thioethers under moderately mild conditions following a...

Cited by 5 publications

References 39 publications

Versatile Deprotonation-Induced Exfoliation and Functionalization of Biological Nanofibrils for Actuation and Fluorescence

Versatile Deprotonation-Induced Exfoliation and Functionalization of Biological Nanofibrils for Actuation and Fluorescence

Tuning the structure of pendant groups in poly(α‐arylTMC)s: A pathway to high glass transition temperature

Chemo‐, Regio‐ and Stereoselective Preparation of (Z)‐2‐Butene‐1,4‐Diol Monoesters via Pd‐Catalyzed Decarboxylative Acyloxylation

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