Physico‐Chemical Properties of Organosuperbases

Margetić, Davor

doi:10.1002/9780470740859.ch2

Cited by 28 publications

(28 citation statements)

References 93 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…9 We observed complete conversion, even at −20 °C (entry 10) . Lower temperatures were necessary to avoid TMG addition to the perfluoroarenes (not shown) .…”

mentioning

confidence: 85%

Polyfluoroarylation of oxazolones: access to non-natural fluorinated amino acids

Teegardin

Weaver

2017

Chem. Commun.

View full text Add to dashboard Cite

Herein, conditions are provided for the formation and use of the oxazolone enolate for the nucleophilic substitution of highly fluorinated (hetero) arenes, which after unmasking yield highly fluorinated non-natural amino acids and derivatives. In addition, the properties and chemical behavior of this new class of amino acids are explored. The utility is demonstrated in the one pot synthesis of medicinally relevant 2-aminohydantoins.

show abstract

“…9 We observed complete conversion, even at −20 °C (entry 10) . Lower temperatures were necessary to avoid TMG addition to the perfluoroarenes (not shown) .…”

mentioning

confidence: 85%

Polyfluoroarylation of oxazolones: access to non-natural fluorinated amino acids

Teegardin

Weaver

2017

Chem. Commun.

View full text Add to dashboard Cite

show abstract

“…The pK a value of the superbase btmgn [1,8-bis(tetramethylguanidino)naphthalene] in CH 3 CN was estimated to be 25.1 (experimentally derived estimate) [21] or 25.4 (calculated with the help of IPCM-B3LYP/6-311+G**//HF/6-31G* calculations and an empirical formula, IPCM = isodensity polarized continuum model), being thus higher than that of guanidine (24.1 in CH 3 CN according to the calculations). [22,23] The calculated pK a value in CH 3 CN is lower for the related 1,8-bis(N,NЈ-dimethylethyleneguanidino)naphthalene. We expect pK a values in a similar range for the three GFA molecules.…”

Section: Synthesis and Characterization Of 1245-tetrakis(nnј-dimementioning

confidence: 96%

The First Cyanomethyl Complex of Gold, Synthesized by Reaction of a Au^I Complex with Acetonitrile in the Presence of a New Guanidine N‐Superbase

et al. 2010

View full text Add to dashboard Cite

Herein we report on the synthesis of the new strong N‐base and electron donor tdmegb [1,2,4,5‐tetrakis(N,N′‐dimethylethyleneguanidino)benzene]. Compared to the previously synthesized ttmgb [1,2,4,5‐tetrakis(tetramethylguanidino)benzene], this compound turned out to be a slightly better electron donor and a slightly weaker base. In experiments in which [AuCl(PPH3)] was dissolved in CH3CN together with tdmegb, we observed the formation of the first cyanomethyl complex of Au, namely [Au(CH2CN)(PPh3)] in good yield. This reaction does not take place for ttmgb. Moreover, in CH2Cl2 solutions containing the three components [AuCl(PPh3)], tdmegb and a nitrile (in large excess), only AuI reduction leading to a [Au11Cl3(PPh3)7] cluster is observed. Possible reaction mechanisms for this unusual reaction are discussed.

show abstract

“…Incorporation of guanidino fragments within polycyclic and/or cage structures as linkers has been explored by Singh and Ganguly () and Margetic et al (Margetic, ; Margetic et al, ; Margetic, Ishikava, & Kumamoto, ). Some illustrative examples are shown in Scheme .…”

Section: Guanidinesmentioning

confidence: 99%

“…The term "hyperbasicity" has been recently introduced to characterize bases with GB close or over $1200 kJ/mol (Despotovic, Kovacevic, & Maksic, 2007). Several specific reviews devoted to these super-and hyper-basic molecules recently appeared (Margetic, 2009;Maksic, Kovacevic, & Vianello, 2012;Leito et al, 2015) and may complete the reader's information.…”

Section: Introductionmentioning

confidence: 99%

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp² nitrogen containing compounds

Bouchoux

Eckert‐Maksić

2016

Mass Spectrometry Reviews

View full text Add to dashboard Cite

This paper constitutes the fifth part of a general review of the gas-phase protonation thermochemistry of polyfunctional molecules (Part 1: Theory and methods, Mass Spectrom Rev 2007, 26:775-835, Part 2: Saturated basic sites, Mass Spectrom Rev 2012, 31:353-390, Part 3: Amino acids, Mass Spectrom Rev 2012, 31:391-435, Part 4: Carbonyl as basic site, Mass Spectrom Rev 2015, 34:493-534). This part is devoted to non-aromatic molecules characterized by a lone pair located on a sp nitrogen atom, it embraces functional groups such as imines, amidines, guanidines, diazenes, hydrazines, oximes, and phosphazenes. Specific examples are examined under five major chapters. In the first one, aliphatic and unsaturated (conjugated and cyclic) imines, hydrazones, and oximes are considered. A second chapter describes the protonation energetic of aliphatic, conjugated, or cyclic amidines. Guanidines, polyguanides, and biomolecules containing guanidine were examined in the third chapter. A fourth chapter describes the particular case of the phosphazene molecules. Finally, diazenes and azides were considered in the last chapter. Experimental data were re-evaluated according to the presently adopted basicity scale, i.e., PA(NH ) = 853.6 kJ/mol, GB (NH ) = 819 kJ/mol. Structural and energetic information given by G4MP2 quantum chemistry computations on typical systems are presented. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:139-170, 2018.

show abstract

Physico‐Chemical Properties of Organosuperbases

Cited by 28 publications

References 93 publications

Polyfluoroarylation of oxazolones: access to non-natural fluorinated amino acids

Polyfluoroarylation of oxazolones: access to non-natural fluorinated amino acids

The First Cyanomethyl Complex of Gold, Synthesized by Reaction of a Au^I Complex with Acetonitrile in the Presence of a New Guanidine N‐Superbase

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp² nitrogen containing compounds

Contact Info

Product

Resources

About

Physico‐Chemical Properties of Organosuperbases

Cited by 28 publications

References 93 publications

Polyfluoroarylation of oxazolones: access to non-natural fluorinated amino acids

Polyfluoroarylation of oxazolones: access to non-natural fluorinated amino acids

The First Cyanomethyl Complex of Gold, Synthesized by Reaction of a AuI Complex with Acetonitrile in the Presence of a New Guanidine N‐Superbase

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp2 nitrogen containing compounds

Contact Info

Product

Resources

About

The First Cyanomethyl Complex of Gold, Synthesized by Reaction of a Au^I Complex with Acetonitrile in the Presence of a New Guanidine N‐Superbase

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp² nitrogen containing compounds