2800-87-5Relevant academic research and scientific papers
TMTHSI, a superior 7-membered ring alkyne containing reagent for strain-promoted azide-alkyne cycloaddition reactions
Hadavi, Darya,Honing, Maarten,Ippel, Hans,Liskamp, Rob M. J.,Meulemans, Tommi,Rijcken, Cristianne J. F.,Timmers, Matt,Veldhuis, Harald,Weterings, Jimmy
, p. 9011 - 9016 (2020/10/15)
We describe the development of TMTH-SulfoxImine (TMTHSI) as a superior click reagent. This reagent combines a great reactivity, with small size and low hydrophobicity and compares outstandingly with existing click reagents. TMTHSI can be conveniently func
Thiacycloalkynes for copper-free click chemistry
De Almeida, Gabriela,Sletten, Ellen M.,Nakamura, Hitomi,Palaniappan, Krishnan K.,Bertozzi, Carolyn R.
supporting information; experimental part, p. 2443 - 2447 (2012/04/23)
The heteroatom helps! The introduction of an endocyclic sulfur atom enables fine-tuning of the reactivity and stability of thiacycloalkynes for copper-free click chemistry. The stabilizing effect of the endocyclic sulfur atom allows the use of highly activated seven-membered rings as reagents for bioorthogonal copper-free click chemistry. Copyright
New tetramethylthiepinium (TMTI) for copper-free click chemistry
King, Mathias,Baati, Rachid,Wagner, Alain
supporting information; scheme or table, p. 9308 - 9309 (2012/09/25)
A new derivative of the strained 3,3,6,6-tetramethylthiacycloheptyne (TMTH) bearing a functional handle is reported. Following an optimized synthesis, the handle was introduced by mild alkylation of the sulphur atom. The resulting functionalized strained 4,5-didehydro-3,3,6,6-tetramethyl-2,3,6,7- tetrahydrothiepinium (TMTI) proved to be stable and underwent extremely fast [3+2] cycloaddition reaction with benzyl azide in both organic and aqueous solvents. The reaction was equally efficient in cell lysate and serum and therefore opens interesting prospects for chemical-biology applications.
Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: The effect of alkyl substitution on extraction properties and implications for ligand design
Lewis, Frank W.,Harwood, Laurence M.,Hudson, Michael J.,Distler, Petr,John, Jan,Stamberg, Karel,Nunez, Ana,Galan, Hitos,Espartero, Amparo G.
, p. 1509 - 1519 (2012/04/23)
Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.
Synthesis with perfect atom economy: Generation of diazo ketones by 1,3-dipolar cycloaddition of nitrous oxide at cyclic alkynes under mild conditions
Banert, Klaus,Plefka, Oliver
supporting information; scheme or table, p. 6171 - 6174 (2011/09/13)
A cascade of five steps, transforms cyclooctynes in the presence of nucleophiles NuH and nitrous oxide, into the depicted products (see scheme). In another example, nitrous oxide was added at a cycloalkyne at -25 °C to generate the corresponding diazo ket
Hydrogen Transfer Reactions, 21. - On the Pericyclic Hydrogen Transfer from 1,2-Dihydroarenes to a Cycloheptyne
Gerres, Thomas,Heesing, Albert
, p. 1439 - 1448 (2007/10/02)
The aromatization of 1,2-dihydroarenes by thiacycloheptyne 1 takes place by a pericyclic process.This mechanism is supported by the dependence of the reactivity on the ? system, absence of both substituent and solvent effects, a strong negative entropy of activation, high stereoselectivity of hydrogen abstraction, as well as size and consistency of primary isotope effects and semiempirical calculations of the transition state.Key Words: Hydrogen transfer, pericyclic / Aromatization / Isotope effects / Ring strain
