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1.
Amyes TL Diver ST Richard JP Rivas FM Toth K 《Journal of the American Chemical Society》2004,126(13):4366-4374
We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes. 相似文献
2.
The Grubbs 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene-substituted ruthenium complex 1 catalyzed ethylene-alkyne cross-metathesis and was shown to tolerate free hydroxyl groups and coordinating functionality at the propargylic and homopropargylic positions. Hindered and enantiomerically enriched 1-substituted alkynes also react efficiently under the reported conditions. 相似文献
3.
[Reaction: see text] The intermolecular enyne metathesis between alkynes and styrene derivatives was developed to study electronic effects in enyne metathesis. A Hammett plot for the overall reaction, catalyst initiation and vinyl carbene turnover was determined with the second generation Grubbs ruthenium carbene catalyst. 相似文献
4.
[reaction: see text]. A new method to produce benzimidazolium salts based on a successive Buchwald-Hartwig amination and ring closure is reported. A variety of different benzimidazolium salts can be prepared using this procedure. Amines that bear an alpha-chiral group undergo the reaction to furnish chiral benzimidazolium salts. The salts that lack a C2 substituent on the heterocycle are readily deprotonated to give nucleophilic carbenes. 相似文献
5.
Ene–yne cross metathesis was assessed for use as a key fragment coupling in a planned total synthesis of amphidinolide P. A terminal alkyne containing a β,γ-epoxide was synthesized and employed as the alkyne partner in an intermolecular ene–yne metathesis. In the alkene substrate, optimal functionality and reaction conditions were determined. An unprotected allyl alcohol was found to be critical for both high yield and high E-selectivity. Fewer equivalents of the alkene resulted in incomplete reaction and side reactions consumed the terminal alkyne. The best ruthenium carbene precatalysts were found to be the Hoveyda–Grubbs carbene complexes. 相似文献
6.
[reaction: see text] New affinity reagents were synthesized using alkene metathesis to directly modify the MeBmt side chain of cyclosporin A. The reagents were used to detect novel cyclophilins from cellular extracts. 相似文献
7.
8.
An efficient method for calculating the Lagrange multipliers and the analytical gradients of one state included in a state average MCSCF wave function is presented. It is demonstrated that the state average energy of an ‘equal-weight’ scheme is invariant to rotations within the state average subspace and that the corresponding rotations should be eliminated from the Lagrangian equations. Finally, a diagnostic is presented, which gauges the energy difference between a state defined by a state average calculation and the corresponding fully variational multi-configurational SCF state. 相似文献
9.
ChemInform Abstract: X-Ray Structural Studies of the Polymorphic Elpasolites K2LiAlF6 and Rb2LiGaF6.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献
10.
F. S. Diver D. Littlejohn T. D. B. Lyon G. S. Fell 《Fresenius' Journal of Analytical Chemistry》1988,332(6):627-629
Summary An investigation through interlaboratory comparison using different analytical techniques has been carried out in order to assess the suitability of a plasma protein solution as a source for a trace element reference material in clinical analysis. Reasonable agreement was obtained for a number of elements from the range studied: Al, Ba, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Se, Sr, V and Zn. The techniques used included flame and furnace atomic absorption spectrometry (FAAS and ETA-AAS), furnace atomic emission spectrometry (ETA-AES), inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), and simultaneous multi-element atomic absorption spectrometry (SIMAAC). Results indicated that this plasma protein solution may prove useful as a source for a reference material covering trace element levels outwith the range found in normal human plasma.
Humanalbumin als Referenzmaterial für Spurenelemente相似文献