Journal ArticleDOI
On the Structure of [K(crypt-222)]+ CF3−
R. L. Harlow,Jordi Benet-Buchholz,Fedor M. Miloserdov,Andrey I. Konovalov,William J. Marshall,Eduardo C. Escudero-Adán,Eddy Martin,Anton Lishchynskyi,Vladimir V. Grushin +8 more
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This article is published in Helvetica Chimica Acta.The article was published on 2018-04-01. It has received 9 citations till now. The article focuses on the topics: Crypt & Cryptand.read more
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Journal ArticleDOI
Anion-Initiated Trifluoromethylation by TMSCF3: Deconvolution of the Siliconate-Carbanion Dichotomy by Stopped-Flow NMR/IR.
Craig P. Johnston,Thomas H. West,Ruth E. Dooley,Marc Reid,Ariana B. Jones,Edward J. King,Andrew G. Leach,Guy C. Lloyd-Jones +7 more
TL;DR: The overarching mechanism for trifluoromethylation by R3SiCF3, in which pentacoordinate siliconate intermediates are unable to directly transfer CF3– as a nucleophile or base, rationalizes why the turnover rate depends on the initial concentration (but not identity) of X–, the identity of the R3 SiCF3 reagent, and the carbonyl/R3Si CF3 ratio.
Journal ArticleDOI
Difluorocarbene Generation from TMSCF3: Kinetics and Mechanism of NaI-Mediated and Si-Induced Anionic Chain Reactions.
Andrés García-Domínguez,Thomas H. West,Johann J. Primozic,Katie M. Grant,Craig P. Johnston,Grant G. Cumming,Andrew G. Leach,Guy C. Lloyd-Jones +7 more
TL;DR: An overarching mech- anism involving direct and indirect fluoride transfer from a CF3-anionoid to TMSCF3 has been elucidated, allowing rationalization of why the NaI-mediated process is more effective for less reactive alkenes and alkynes, and why slow-addition protocols can be of benefit.
Journal ArticleDOI
Direct nucleophilic trifluoromethylation of carbonyl compounds by potent greenhouse gas, fluoroform: Improving the reactivity of anionoid trifluoromethyl species in glymes.
TL;DR: Experimental results and DFT calculations suggest that the beneficial effect deals with glyme coordination to the K+ to produce [K(polyether)n]+ whose diminished Lewis acidity renders the reactive anionoid CF3 counterion species more ‘naked’, thereby slowing down its undesirable decomposition to CF2 and F− and simultaneously increasing its reactivity towards the organic substrate.
Journal ArticleDOI
Synthesis of trifluoromethyl ketones by nucleophilic trifluoromethylation of esters under a fluoroform/KHMDS/triglyme system.
TL;DR: A straightforward method that enables the formation of biologically attractive trifluoromethyl ketones from readily available methyl esters using the potent greenhouse gas fluoroform (HCF3, HFC-23) was developed in this article.
Journal ArticleDOI
Mechanism of Anion-Catalyzed C–H Silylation Using TMSCF3: Kinetically-Controlled CF3-Anionoid Partitioning As a Key Parameter
Andrés García-Domínguez,Pedro H. Helou de Oliveira,Gilian T. Thomas,Arnau R. Sugranyes,Guy C. Lloyd-Jones +4 more
TL;DR: The mechanism of anion-catalyzed C-H silylation by R3SiCF3 reagents has been investigated using homogeneous TBAT-initiation, in situ and stopped-flow 19F NMR spectroscopy 2H-KIE, LFER, deuterium-la...
References
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Equilibrium Acidities in Dimethyl Sulfoxide Solution
TL;DR: The first acidity scale to be established in a pure solvent other than water was the result of the pioneering work of Conant, Wheland, and McEwen in ether or ben~ene.
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Intermolecular Nonbonded Contact Distances in Organic Crystal Structures: Comparison with Distances Expected from van der Waals Radii
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Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond.
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Defining the hydrogen bond: An account (IUPAC Technical Report)
Elangannan Arunan,Gautam R. Desiraju,Roger A. Klein,Joanna Sadlej,Steve Scheiner,Ibon Alkorta,David C. Clary,Robert H. Crabtree,J. J. Dannenberg,Pavel Hobza,Henrik G. Kjaergaard,Anthony C. Legon,Benedetta Mennucci,David J. Nesbitt +13 more
TL;DR: In this paper, a new definition of the hydrogen bond is proposed, which emphasizes the need for evidence, and a list of criteria has been provided, and these can be used as evidence for hydrogen bond formation.
Journal ArticleDOI
Equilibrium acidities of carbon acids. VI. Establishment of an absolute scale of acidities in dimethyl sulfoxide solution
Walter S. Matthews,Joseph E. Bares,John E. Bartmess,Frederick G. Bordwell,Frederick J. Cornforth,George E. Drucker,Zafra Margolin,Robert J. McCallum,Gregory J. Mccollum,Noel R. Vanier +9 more
TL;DR: An accurate spectrophotometric method of determining relative equilibrium acidities of carbon acids in DMSO has been developed as discussed by the authors, and the pK of fluorene, formerly arbitrarily taken as 20.5, has been raised to an absolute value of 22.6.