Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine‐based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius‐type Intermediate

Janes, Trevor; Diskin‐Posner, Yael; Milstein, David

doi:10.1002/ange.202000406

Cited by 10 publications

(1 citation statement)

References 87 publications

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“…[27,28] In fundamental terms, it is now evidently known that hydrogen bonds are formed in various X-HÁ Á ÁY systems, where the atoms X and Y are electronrich elements or more electronegative elements and Y possesses one or more lone pair, such as N, O, or F. [29][30][31][32][33] In line to this, specifically considering the interaction of water molecules with organic molecules, it is largely observed that hydrogen bonding interactions in pyridine, [34][35][36][37] pyrimidine, [38,39] and its derivatives play a significant role to drive their solvation dynamics and thus holds very high relevance in heterocyclic chemistry. [40,41] Large-scale industrial applicability of pyridine in the fine chemical [42,43] and pharmaceutical industries [44][45][46][47] as a solvent and reagent made its hydration properties a strong point of research interest among various researchers. In addition to this, a comprehensive understanding of hydrogen bonding interactions in pyridine is also essential for advances in the biochemical industries, ranging from designing receptors for basic amino acid side chain recognition [48] to chemometric probing of various biomolecules.…”

Section: Introductionmentioning

confidence: 99%

Origin of the blue‐shifted hydrogen bond in the vibrational Raman spectra of pyridine–water complexes: A density functional theory study

Sharma

Schlücker

Srivastava

2021

J Raman Spectroscopy

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Despite extensive scientific efforts to understand the exact nature of hydrogen bonding in Pyridine (Py) aqueous solutions, the exact mechanism causing the blue‐shift in Py ring breathing mode has remained unclear so far. The present study is an attempt to investigate the possible causes of the experimentally observed blue‐shifts using density functional theory (DFT) by computing the complexation‐induced electronic charge redistribution due to hydrogen bonding in distinct Py–water complexes. Electron density difference map (EDDM) calculations, natural population analysis (NPA), and natural bond orbital (NBO) analysis were used to explore the blue‐shift in Py ring breathing mode upon complexation with water. The combined NPA and NBO analysis yielded that interaction between the nitrogen lone pair in Py and hydrogen atom of W causes a net charge transfer from Py to W, which—through hyperconjugation—depopulates the σ* (C–C) orbitals. This finally leads to the strengthening of the local C–C force constants. The relative contributions of normal coordinates were obtained by potential energy distribution (PED) calculations. Our computation reveals that increasing contributions of C–C stretching motions to the Py ring breathing mode (ν1) are de facto causing a blue‐shift in the ν1 vibration upon water addition. Overall, this analysis suggests that complementary information from both (a) electronic charge redistribution and (b) potential energy distribution of normal coordinates is required to explain the blue‐shift in ν1 (Py) mode in aqueous solutions.

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Section: Introductionmentioning

confidence: 99%

Origin of the blue‐shifted hydrogen bond in the vibrational Raman spectra of pyridine–water complexes: A density functional theory study

Sharma

Schlücker

Srivastava

2021

J Raman Spectroscopy

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Co(II)‐Catalyzed Oxidation of N,N‐Dimethylaminoethanol: An Efficient Synthesis of Unsymmetrical (2,4‐) and Symmetrical (2,6‐) Diarylpyridines through Annulation of Aromatic Ketones with a Nitrogen Source

Qin

Zhang

et al. 2021

Asian J Org Chem

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An efficient and facile synthesis of 2,4‐ and 2,6‐diarylpyridines has been developed. It involves one‐pot [2+2+1+1] pseudo four‐component annulation of aromatic ketones, a nitrogen source and a carbon donor. N,N‐Dimethylaminoethanol is oxidized in the presence of Co(II) to provide a carbon synthon. Two C−C and two C−N bonds are formed during the oxidative annulation process. The products are strictly controlled due to the steric hindrance: 2,4‐diarylpyridines are afforded effectively with small ketones while 2,6‐diaryl analogues predominate when bulky ketones are employed.

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Blavatnik‐Nachwuchspreis: E. Levy / EuChemS‐Verdienstpreis: E. Keinan / Karl‐Ziegler‐Vorlesung: D. Milstein

2020

Angewandte Chemie

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Blavatnik-Nachwuchspreise sind eine finanzielle Unterstützung fürjunge Forscher,die schon frühin ihrer Karriere außergewçhnliche Leistungen vorweisen kçnnen. Fçrderprogramme gibt es fürd ie USA, Großbritannien und Israel. Emmanuel D. Levy (Weizmann-Institut, Rehovot) erhält 2020 den "Blavatnik Award for Young Scientists in Israel" auf dem Gebiet der Chemie.Levy studierte in Frankreich an der UniversitØ dÉvry,G Ønopôle, und der UniversitØ Paris VII und promovierte 2008 an der University of Cambridge (Großbritannien) unter Anleitung von Sarah Te ichmann in computerunterstützter Biologie.V on 2008 bis 2012 arbeitete er als Postdoktorand bei Stephen Michnick an der UniversitØ de MontrØal (Kanada) auf den Gebieten der Proteomik und Hefegenetik. Seit 2012 leitet er eine eigene Forschungsgruppe am Department fürS trukturbiologie des Weizmann-Instituts,w oe rdem Azrieli-Institut fürS ystembiologie angehçrt. Levy befasst sich mit den Grundlagen der Aggregation und Selbstorganisation von Proteinen. Seine Gruppe erarbeitet eigenständige Konzepte und Untersuchungsmethoden fürdie Organisation von Proteinen in lebenden Zellen. In einem Angewandte-Chemie-Aufsatz betrachteten Levy und Mitarbeiter infinite Ansammlungen gefalteter Proteine im Kontext von Evolution, Krankheiten und Proteinentwicklung. [1] In dieser Rubrik berichten wir über Auszeichnungen aller Art fürC hemiker/innen, die mit der Angewandten Chemie und ihren Schwesterzeitschriften als Autoren und Gutachter besonders eng verbunden sind.

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Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine‐based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius‐type Intermediate

Cited by 10 publications

References 87 publications

Origin of the blue‐shifted hydrogen bond in the vibrational Raman spectra of pyridine–water complexes: A density functional theory study

Origin of the blue‐shifted hydrogen bond in the vibrational Raman spectra of pyridine–water complexes: A density functional theory study

Co(II)‐Catalyzed Oxidation of N,N‐Dimethylaminoethanol: An Efficient Synthesis of Unsymmetrical (2,4‐) and Symmetrical (2,6‐) Diarylpyridines through Annulation of Aromatic Ketones with a Nitrogen Source

Blavatnik‐Nachwuchspreis: E. Levy / EuChemS‐Verdienstpreis: E. Keinan / Karl‐Ziegler‐Vorlesung: D. Milstein

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