Intramolecular alkyne–dithiolium cycloaddition: a joint experimental and DFT mechanistic study

Wang, Cheng; Flinn, Christopher G.; Zhao, Yuming

doi:10.1039/c7ra05087a

Cited by 6 publications

(9 citation statements)

References 69 publications

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“…In addition to oxidation, the DTF group has also been known to be susceptible to protonation, yielding an electron-withdrawing dithiolium cation as the product. , Figure compares the UV–vis absorption spectra of decyl-substituted DTF-TPPys ( 7b , 8b , and 9b ) before and after treatment with excess trifluoroacetic acid (TFA) in CH 2 Cl 2 . For p -DTF-substituted TPPy 7b , the low-energy π → π* absorption bands in the range of 310–430 nm are considerably attenuated, while a high-energy band at 298 nm is enhanced after protonation.…”

Section: Resultsmentioning

confidence: 99%

A Comparative Study of Redox-Active Dithiafulvenyl-Functionalized 1,3,6,8-Tetraphenylpyrene Derivatives

2021

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A series of 1,3,6,8-tetraphenylpyrene (TPPy) derivatives substituted with redox-active 1,4-dithiafulvenyl (DTF) groups was synthesized and characterized. The conformational properties of these DTF-TPPys and their TPPy precursors were assessed by X-ray single-crystal and nuclear magnetic resonance analyses. Their electronic and redox properties were examined by ultraviolet–visible absorption, fluorescence, and cyclic voltammetric analyses. The DTF substitution was found to strongly modify the absorption, emission, and electrochemical properties, while detailed effects can be linked to substitution patterns and alkyl side chains attached to the DTF groups. Furthermore, the DTF-TPPy derivatives showed sensitivity to acids; in particular, the vinylic proton of DTF group could undergo efficient proton/deuterium exchange with D2O in an acidic medium.

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Section: Resultsmentioning

confidence: 99%

A Comparative Study of Redox-Active Dithiafulvenyl-Functionalized 1,3,6,8-Tetraphenylpyrene Derivatives

2021

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“…[1][2][3][4] Modeling is exceptionally efficient in deciphering reaction mechanisms. [5][6][7][8][9][10][11][12][13][14] Isoxazole ring is a key structural moiety of valuable pharmaceutical substances (Figure 1). [15] Among them are antibiotics, [16][17][18][19] as cloxacillin, [16,18,20] dicloxacillin [16,18,[20][21][22] and flucloxacillin, [16,18,20,23,24] which were included in the WHO Model List of Essential Medicines and recommended for the treatment of a wide range of bacterial infections.…”

Section: Introductionmentioning

confidence: 99%

“…Concerted 1,3-dipolar cycloadditions are often studied with computational modeling. [5,7,[11][12][13][54][55][56][57][58] The cycloadditions to nitrile oxides of substituted alkenes and alkynes are no exception. [11,13,59,60] Most noticeable computational studies address regioselectivity of 1,3-dipolar cycloadditions.…”

Section: Introductionmentioning

confidence: 99%

“…Concerted 1,3‐dipolar cycloadditions are often studied with computational modeling [5,7,11–13,54–58] . The cycloadditions to nitrile oxides of substituted alkenes and alkynes are no exception [11,13,59,60] .…”

Section: Introductionmentioning

confidence: 99%

“…Methods of quantum chemical modeling implemented in modern software packages have potentially high accuracy and require relatively small hardware resources and researcher‘s time [1–4] . Modeling is exceptionally efficient in deciphering reaction mechanisms [5–14] …”

Section: Introductionmentioning

confidence: 99%

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Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

et al. 2022

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A tangible substituent effect may be perceived as a good feature in developing an organic reaction. This work demonstrates that, on the contrary, a zero-slope Hammet plot should be sought. The synthesis of isoxazoles by consecutive cycloaddition of nitrile oxides to vinyl ethers and alcohols elimination was studied computationally and experimentally. We performed a Hammett study in silico to demonstrate a negligible substituent effect (i. e., broad substrate scope) in the addition of benzyl vinyl ether to nitrile oxides. The modeling was performed at the ωB97X-V/def2-TZVP//PBE0-D4/def2-TZVP + SMD(benzene) level of theory within the RIJCOSX approximation. The experimental evaluation validated the computational model. A versatile methodology for synthesizing substituted isoxazolines and isoxazoles was proposed as the main result. We present this work as a successful example of how quantum chemical modeling can re-boost the classic Hammett approach to the optimization and design of organic synthetic methodologies. We anticipate further Hammett studies in silico, considering the current trend for data-driven chemical research.

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One‐Pot and Two‐Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D‐Labeled Derivatives

Ledovskaya

Polynski

Ananikov

2021

Chemistry An Asian Journal

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Acetylene surrogates are efficient tools in modern organic chemistry with largely unexplored potential in the construction of heterocyclic cores. Two novel synthetic paths to 3,6‐disubstituted pyridazines were proposed using readily available acetylene surrogates through flexible C2 unit installation procedures in a common reaction space mode (one‐pot) and distributed reaction space mode (two‐chamber): (1) an interaction of 1,2,4,5‐tetrazine and its acceptor‐functionalized derivatives with a CaC2−H2O mixture performed in a two‐chamber reactor led to the corresponding pyridazines in quantitative yields; (2) [4+2] cycloaddition of 1,2,4,5‐tetrazines to benzyl vinyl ether can be considered a universal synthetic path to a wide range of pyridazines. Replacing water with D2O and vinyl ether with its trideuterated analog in the developed procedures, a range of 4,5‐dideuteropyridazines of 95–99% deuteration degree was synthesized for the first time. Quantum chemical modeling allowed to quantify the substituent effect in both synthetic pathways.

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Intramolecular alkyne–dithiolium cycloaddition: a joint experimental and DFT mechanistic study

Abstract: The intramolecular alkyne–dithiolium cycloaddition reactions were found to occur through either a concerted or stepwise pathway, depending on the conjugation degree of the alkynyl unit.

Cited by 6 publications

References 69 publications

A Comparative Study of Redox-Active Dithiafulvenyl-Functionalized 1,3,6,8-Tetraphenylpyrene Derivatives

A Comparative Study of Redox-Active Dithiafulvenyl-Functionalized 1,3,6,8-Tetraphenylpyrene Derivatives

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

One‐Pot and Two‐Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D‐Labeled Derivatives

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