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Metal-catalyzed di-tert-butylsilylene transfer was developed as a mild, operationally simple, functional-group-tolerant method for silacyclopropane formation. Di-tert-butylsilylene was transferred from cyclohexene silacyclopropane 1 to an alkene through the use of a metal salt. Silacyclopropanation occurred at temperatures as low as -27 degrees C when AgOTf or AgOC(O)CF(3) were used as catalysts. Complex silacyclopropanes were formed stereospecifically and diastereoselectively from functionalized alkenes. Silacyclopropanes reacted with various carbonyl compounds, including aldehydes, ketones, formate esters, and formamides, in an overall process that efficiently converts alkenes into oxasilacyclopentanes with defined stereochemistry. 相似文献
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Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P)2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silylsilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a rho value of -0.62 +/- 0.02 using sigmap constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene. 相似文献
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We investigate the convergence of sequences of Padé approximants for power series
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Chimera Spectrum Diagnostics for Peptides Using Two-Dimensional Partial Covariance Mass Spectrometry
Taran Driver Nikhil Bachhawat Leszek J. Frasinski Jonathan P. Marangos Vitali Averbukh Marina Edelson-Averbukh 《Molecules (Basel, Switzerland)》2021,26(12)
The rate of successful identification of peptide sequences by tandem mass spectrometry (MS/MS) is adversely affected by the common occurrence of co-isolation and co-fragmentation of two or more isobaric or isomeric parent ions. This results in so-called `chimera spectra’, which feature peaks of the fragment ions from more than a single precursor ion. The totality of the fragment ion peaks in chimera spectra cannot be assigned to a single peptide sequence, which contradicts a fundamental assumption of the standard automated MS/MS spectra analysis tools, such as protein database search engines. This calls for a diagnostic method able to identify chimera spectra to single out the cases where this assumption is not valid. Here, we demonstrate that, within the recently developed two-dimensional partial covariance mass spectrometry (2D-PC-MS), it is possible to reliably identify chimera spectra directly from the two-dimensional fragment ion spectrum, irrespective of whether the co-isolated peptide ions are isobaric up to a finite mass accuracy or isomeric. We introduce ‘3-57 chimera tag’ technique for chimera spectrum diagnostics based on 2D-PC-MS and perform numerical simulations to examine its efficiency. We experimentally demonstrate the detection of a mixture of two isomeric parent ions, even under conditions when one isomeric peptide is at one five-hundredth of the molar concentration of the second isomer. 相似文献
8.
Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field‐Effect Transistors
![]() Crystalann Jones Dr. Damien Boudinet Dr. Yu Xia Mitch Denti Adita Das Dr. Antonio Facchetti Prof. Dr. Tom G. Driver 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5938-5945
A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition‐metal‐catalyzed C?H‐bond functionalization. In addition to modifying the substituents present on the end‐pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution‐state properties and field‐effect‐transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λmax value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin‐film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm2 V?1 s?1 and the Ion/Ioff value is greater than 106. 相似文献
9.
S.M. Driver 《Surface science》2007,601(2):510-517
We have used a novel fibre-optic low-energy electron diffraction (FO-LEED) instrument, capable of low flux measurements that minimise electron beam damage to surface overlayers, to study methanethiolate (CH3-S-) structural phases formed on Cu{1 1 1} at temperatures between 110 and 300 K. Three structural phases were seen: a (√3 × √3)R30° phase that forms at 110-140 K; a (4 × 4) phase which was observed transiently at 110 K; and a pseudo-{1 0 0} reconstructed phase which forms at room temperature. We discuss these in the context of previous studies of this system, and demonstrate the ability of the FO-LEED instrument to record high-quality LEED patterns and intensity data from a strongly beam-sensitive surface. 相似文献
10.
We introduce a class of non-commutative Heisenberg-like infinite-dimensional Lie groups based on an abstract Wiener space. The Ricci curvature tensor for these groups is computed and shown to be bounded. Brownian motion and the corresponding heat kernel measures, {νt}t>0, are also studied. We show that these heat kernel measures admit: (1) Gaussian like upper bounds, (2) Cameron-Martin type quasi-invariance results, (3) good Lp-bounds on the corresponding Radon-Nikodym derivatives, (4) integration by parts formulas, and (5) logarithmic Sobolev inequalities. The last three results heavily rely on the boundedness of the Ricci tensor. 相似文献
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