Mechanistic and kinetic insights of reduction of indophenol by sodium borohydride: A theoretical study to explore the effect of solvent and counter ion

Patel, Priyanka; Lingayat, Sudheer; Gulvi, Nitin R.; Badani, Purav M.

doi:10.1016/j.chemphys.2018.02.021

Cited by 11 publications

(2 citation statements)

References 33 publications

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“…The observed anti-addition between the Diels–Alder components (diene and dienophile) is against the expected cis-addition as per basic principles of concerted pericyclic pathways . A similar result of the anti-addition was reported for the reaction of bis-dialine with oxygen yielding the formation of anti-endoperoxides, with the proposed stepwise mechanism due to steric reasons.…”

Section: Resultsmentioning

confidence: 99%

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Benzyne-Mediated Nonconcerted Pathway toward Synthesis of Sterically Crowded [5]- and [7]Oxahelicenoids, Stereochemical and Theoretical Studies, and Optical Resolution of Helicenoids

et al. 2018

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Synthesis of [5]- and [7]oxahelicenoids via Diels–Alder reaction of sterically crowded bichromenes with benzyne is presented. Studies carried out on Diels–Alder addition product establish the unusual preference for a stepwise mechanism over the concerted reaction pathway. This high yielding general synthetic protocol affords unexpected anti cycloadducts [5]- and [7]oxahelicenoids, as confirmed by crystallographic analysis. To rationalize these intriguing antiaddition products, the reaction mechanism was elucidated by means of DFT analysis. Additionally, hydroxy-functionalized [7]oxahelicenoid has been resolved in its optically pure forms.

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Section: Resultsmentioning

confidence: 99%

“…Therefore, it was reasonably assumed that the reaction between benzyne and chromene starts in the s-trans forms of the bichromenes. Furthermore, the DFT calculations 31 carried out for 12 demonstrated that the interconversion of s-trans to s-cis form is prevented due to the high energy barrier of ∼50 kJ mol −1 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Benzyne-Mediated Nonconcerted Pathway toward Synthesis of Sterically Crowded [5]- and [7]Oxahelicenoids, Stereochemical and Theoretical Studies, and Optical Resolution of Helicenoids

et al. 2018

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Oxidation and Reduction

Banerji

2021

Organic Reaction Mechanisms Series

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Origin and turnaround of enantioselectivity in a chiral organocatalysed Diels‐Alder reaction: A mechanistic study

Maliekal

Gulvi

Karnik

et al. 2020

J of Physical Organic Chem

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The present work comprises exploring the efficacies of the chiral organocatalysts employed in the classic Diels‐Alder reaction between anthrone and maleimide in generating an enantioselective product. The complete mechanism of the reaction has been figured out by performing the electronic structure calculations at the density functional theory (DFT) level. Our calculations suggest that the reaction commences with the abstraction of acidic proton of anthrone instigated by organocatalysts, (S)‐(‐)‐N‐(methyl‐2′‐pyridyl)‐2‐(α‐hydroxyethyl)benzimidazole[Pyr‐HEB]and (S)‐(‐)‐N‐(methyl‐1′‐benzotriazolyl)‐2‐(α‐hydroxyethyl)benzimidazole[Btz‐HEB]. Subsequently, N‐methyl maleimide interacts with the nucleophilic carbon of anthrone in a stepwise pathway, either from left‐hand side or right‐hand side, resulting in the generation of an enantioselective chiral product. A unique feature in the above reaction was thatPyr‐HEBandBtz‐HEBfavoured the formation of SS‐product and RR‐product, respectively, with high enantioselectivity. The turnaround of enantioselectivity upon changing the catalyst has been attributed to the noncovalent interaction and steric orientation in the molecule during the intermediate reaction steps. An estimated value of degree of enantioselectivity, for both the catalysts, was obtained in accordance with the experimental findings.

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Mechanistic and kinetic insights of reduction of indophenol by sodium borohydride: A theoretical study to explore the effect of solvent and counter ion

Cited by 11 publications

References 33 publications

Benzyne-Mediated Nonconcerted Pathway toward Synthesis of Sterically Crowded [5]- and [7]Oxahelicenoids, Stereochemical and Theoretical Studies, and Optical Resolution of Helicenoids

Benzyne-Mediated Nonconcerted Pathway toward Synthesis of Sterically Crowded [5]- and [7]Oxahelicenoids, Stereochemical and Theoretical Studies, and Optical Resolution of Helicenoids

Oxidation and Reduction

Origin and turnaround of enantioselectivity in a chiral organocatalysed Diels‐Alder reaction: A mechanistic study

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