Stereoselective Anti‐Markovnikov Geminal Diamination and Dioxy­gena­tion of Vinylarenes Mediated by the Bromonium Ion

Balaji, Pandur Venkatesan; Chandrasekaran, Srinivasan

doi:10.1002/ejoc.201600203

Cited by 10 publications

(8 citation statements)

References 66 publications

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“…The detector temperature was 260 °C. The quantification of the G‐C2‐acetal was based on a calibration curve performed using G‐C2‐acetal synthetized and purified using a modified reported procedure versus an internal standard (octadecane). The calibration curve was used as follows:

true m_{normalG - normalC 2 - normala normalc normale normalt normala normall} = (\frac{{A r e a}_{normalG - normalC 2 - normala normalc normale normalt normala normall}}{{A r e a}_{normalo normalc normalt normala normald normale normalc normala normaln normale}} \times 2.5386) \times m_{normalo normalc normalt normala normald normale normalc normala normaln normale}

…”

Section: Methodsmentioning

confidence: 99%

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Lignin‐First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate and Ethylene Glycol Organosolv Process

et al. 2020

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A mild lignin‐first acidolysis process (140 °C, 40 min) was developed using the benign solvent dimethyl carbonate (DMC) and ethylene glycol (EG) as a stabilization agent/solvent to produce a high yield of aromatic monophenols directly from softwood lignocellulose (pine, spruce, cedar, and Douglas fir) with a depolymerization efficiency of 77–98 %. Under the optimized conditions (140 °C, 40 min, 400 wt % EG and 2 wt % H2SO4 to pinewood), up to 9 wt % of the aromatic monophenol was produced, reaching a degree of delignification in pinewood of 77 %. Cellulose was also preserved, as evidenced by a 85 % glucose yield after enzymatic digestion. An in‐depth analysis of the depolymerization oil was conducted by using GC‐MS, HPLC, 2 D‐NMR, and size‐exclusion chromatography, which provided structural insights into lignin‐derived dimers and oligomers and the composition of the sugars and derived molecules. Mass balance evaluation was performed.

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true m_{normalG - normalC 2 - normala normalc normale normalt normala normall} = (\frac{{A r e a}_{normalG - normalC 2 - normala normalc normale normalt normala normall}}{{A r e a}_{normalo normalc normalt normala normald normale normalc normala normaln normale}} \times 2.5386) \times m_{normalo normalc normalt normala normald normale normalc normala normaln normale}

…”

Section: Methodsmentioning

confidence: 99%

“…The detector temperature was 260 8C. The quantification of the G-C2-acetal was based on ac alibration curve performed using G-C2-acetal synthetized and purified using am odified reported procedure [59] versus an internal standard (octadecane). The calibration curve was used as follows:…”

Section: Volatile Products Analysis and Characterizationmentioning

confidence: 99%

Lignin‐First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate and Ethylene Glycol Organosolv Process

et al. 2020

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“…Detector temperature was 260 °C. The quantification of C2-acetal was based on a calibration curve performed with C2-acetal synthetized and purified via a modified reported procedure [35] versus an internal standard (octadecane). C2-acetal yield was calculated as follows:…”

Section: Volatile Products Analysis and Characterizationmentioning

confidence: 99%

Effective Lignin-First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate Organosolv Process

Santi¹,

Galkin²,

Lahive³

et al. 2019

Preprint

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Large-scale biorefineries converting lignocellulosic biomass into chemicals, fuels, and energy require a cost-effective pretreatment process that can effectively fractionate all main lignocellulose constituents. A mild organosolv process has been developed using a system of dimethyl carbonate (DMC) and ethylene glycol (EG) as solvent. Softwood biomass (pine, spruce, cedar, and Douglas fir) was fractionated using mild conditions: 140 °C, 40 min, DMC-EG, and sulfuric acid. Organosolv pulping of the softwood biomass usually leads to poor delignification hampering enzymatic cellulose hydrolysis. However, for the developed system, effective pretreatment and subsequent enzymatic cellulose hydrolysis into glucose (up to 84.7%) was observed in combination with a high yield of monomeric hemicellulose sugars and monophenolic compounds from lignin (up to 98% compared to theoretical monomer yield). In sum, effective fractionation and in situ lignin depolymerization was demonstrated for various softwood feedstock combined with limited solvent loss at mild conditions and low reactor pressure.<br>

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“…Although an aerobic anti‐Markovnikov acetalization of styrene using a PdCl 2 (MeCN) 2 /CuCl catalyst system has been reported, only one example (with 1,3‐propanediol) has been shown previously . If we consider that the formation of arylacetaldehydes from vinylarenes (such as anti‐Markovnikov Wacker‐type oxidation and Fe‐ or Ru‐catalyzed epoxidation–isomerization) is still rare, the accessible aerobic synthesis of the corresponding terminal acetals can be an attractive alternative …”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π‐Acceptor Ligands

et al. 2017

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What prompted you to investigate this topic? We have recently found that the addition of electron-deficient cyclic alkenes, such as maleimide, accelerates ap alladium-cata-lyzed anti-Markovnikov Wacker-type oxidation of vinylarenest o arylacetaldehydes using O 2 .W ee xpected that this method could be applied to other reactions related to the anti-Markov-nikov Wacker-type oxidation, such as the one presented in this paper.The electron-deficient cyclic alkenesw ould operate as li-gands for palladium to accelerate the reactiona sw ella ss tabi-lize the in situ formed Pd 0 species, suppressing deactivation.

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Stereoselective Anti‐Markovnikov Geminal Diamination and Dioxygenation of Vinylarenes Mediated by the Bromonium Ion

Cited by 10 publications

References 66 publications

Lignin‐First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate and Ethylene Glycol Organosolv Process

Lignin‐First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate and Ethylene Glycol Organosolv Process

Effective Lignin-First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate Organosolv Process

Palladium‐Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π‐Acceptor Ligands

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Stereoselective Anti‐Markovnikov Geminal Diamination and Dioxy­gena­tion of Vinylarenes Mediated by the Bromonium Ion

Cited by 10 publications

References 66 publications

Lignin‐First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate and Ethylene Glycol Organosolv Process

Lignin‐First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate and Ethylene Glycol Organosolv Process

Effective Lignin-First Fractionation of Softwood Lignocellulose Using a Mild Dimethyl Carbonate Organosolv Process

Palladium‐Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π‐Acceptor Ligands

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Resources

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Stereoselective Anti‐Markovnikov Geminal Diamination and Dioxygenation of Vinylarenes Mediated by the Bromonium Ion