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1.
Peter Bellotti Maximilian Koy Christian Gutheil Steffen Heuvel Frank Glorius 《Chemical science》2021,12(5):1810
A highly modular radical cascade strategy based upon radical cyclisation/allylic substitution sequence between alkyl/aryl bromides, 1,3-dienes and nucleophiles ranging from sulfinates to amines, phenols and 1,3-dicarbonyls is described (>80 examples). Palladium phosphine complexes – which merge properties of photo- and cross coupling-catalysts – allow to forge three bonds with complete 1,4-selectivity and stereocontrol, delivering highly value added carbocyclic and heterocyclic motifs that can feature – inter alia – vicinal quaternary centers, free protic groups, gem-difluoro motifs and strained rings. Furthermore, a flow chemistry approach was for the first time applied in palladium–photocatalysed endeavors involving radicals.Highly modular three-bond three-component cascade featuring palladium as dual photoredox/cross coupling catalyst. 相似文献
2.
D. Thao Nguyen Matthias Freitag Christian Gutheil Dr. Kai Sotthewes Dr. Bonnie J. Tyler Dr. Marcus Böckmann Mowpriya Das Friederike Schlüter Prof. Dr. Nikos L. Doltsinis Prof. Dr. Heinrich F. Arlinghaus Prof. Dr. Bart Jan Ravoo Prof. Dr. Frank Glorius 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13754-13759
3.
D. Thao Nguyen Matthias Freitag Christian Gutheil Kai Sotthewes Bonnie J. Tyler Marcus Bckmann Mowpriya Das Friederike Schlüter Nikos L. Doltsinis Heinrich F. Arlinghaus Bart Jan Ravoo Frank Glorius 《Angewandte Chemie (International ed. in English)》2020,59(32):13651-13656
A novel photoresponsive and fully conjugated N‐heterocyclic carbene (NHC) has been synthesized that combines the excellent photophysical properties of arylazopyrazoles (AAPs) with an NHC that acts as a robust surface anchor (AAP‐BIMe). The formation of self‐assembled monolayers (SAMs) on gold was proven by ToF‐SIMS and XPS, and the organic film displayed a very high stability at elevated temperatures. This stability was also reflected in a high desorption energy, which was determined by temperature‐programmed SIMS measurements. E‐/Z‐AAP‐BIMe@Au photoisomerization resulted in reversible alterations of the surface energy (i.e. wettability), the surface potential (i.e. work function), and the conductance (i.e. resistance). The effects could be explained by the difference in the dipole moment of the isomers. Furthermore, sequential application of a dummy ligand by microcontact printing and subsequent backfilling with AAP‐BIMe allowed its patterning on gold. To the best of our knowledge, this is the first example of a photoswitchable NHC on a gold surface. These properties of AAP‐BIMe@Au illustrate its suitability as a molecular switch for electronic devices. 相似文献
4.
Solid-phase peptide synthesis in the N-to-C direction, opposite to the classical C-to-N direction of peptide synthesis, provides the synthetically versatile C-terminal carboxyl group for further modification into C-terminally modified peptide mimetics. These are of general interest as potential bioactive agents, particularly as protease inhibitors. Elaboration of peptide mimetics on the solid-phase would facilitate synthesis of peptide mimetic combinatorial libraries. This report describes an effective strategy for solid-phase inverse peptide synthesis based on readily available amino acid tert-butyl esters. The potential of this approach for peptide mimetic synthesis is demonstrated by the solid-phase synthesis of two peptide trifluoromethylketones. 相似文献
5.
H. -D. Dörfler G. Brezesinski P. Nuhn B. Dobner M. Gutheil 《Colloid and polymer science》1983,261(12):1033-1037
- By means of differential scanning calorimetry the phase transition temperatures (T u) and phase transition enthalpies (ΔH u) ofα- andβ-branched lecithins were determined. The lecithin samples contained 50% water per weight.
- The occurrence of the pre-transition was dependent on the position of the methyl group in the acid residue as well as on the length of the carbon chains. TheΔH u values of the pre-transition were about 2.5 kJ·mol?1.
- The hydration number (HZ) (number of water molecules per lecithin headgroup) was independent on the position of the methyl group and the length of the acyl group. The average HZ-values for all the lecithins studied is about HZ=14+-1.
- The influence of the chain length of theα- andβ- branched acyl groups affects the thermodynamical parameters of the main transitions (gel→L α). TheΔH m andT m-values increased as the chain length increases.
6.
OK Yoon WG Hwang JC Choe MS Kim 《Rapid communications in mass spectrometry : RCM》1999,13(14):1515-1521
A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
7.
I. Düwel H.-W. Ge H. Kronemayer R. Dibble E. Gutheil C. Schulz J. Wolfrum 《Proceedings of the Combustion Institute》2007,31(2):2247-2255
A turbulent ethanol spray flame is characterized through quantitative experiments using laser-based imaging techniques. The data set is used to validate a numerical code for the simulation of spray combustion. The spray burner has been designed to generate a stable flame without the use of a bluff body or a pilot flame facilitating numerical simulations. The experiments include spatially-resolved measurements of droplet sizes (Mie/LIF-dropsizing and PDA), droplet velocity (PDA), liquid-phase temperature (2-color LIF temperature imaging with Rhodamine B) and gas-phase temperature (multi-line NO-LIF temperature imaging). The measurements close to the nozzle exit are used to determine the initial conditions for numerical simulations. An Eulerian–Lagrangian model including spray flamelet modeling is applied to calculate the development of the spray. Good agreement with the experimental data is found. The experimental data set and the numerical results will be published on a website to allow other groups to evaluate their experimental and/or numerical data. 相似文献
8.
Peptide mimetics are of considerable interest as bioactive agents and drugs. C-terminally modified peptide mimetics are of particular interest given the synthetic versatility of the carboxyl group and its derivatives. A general approach to C-terminally modified peptide mimetics, based on a urethane attachment strategy and amino acid t-butyl ester-based N-to-C peptide synthesis, is described. This approach is compatible with the reaction conditions generally employed for solution-phase peptide mimetic synthesis. To develop and demonstrate this approach, it was employed for the solid-phase synthesis of peptide trifluoromethyl ketones, peptide boronic acids, and peptide hydroxamic acids. The development of a versatile general approach to C-terminally modified peptides using readily available starting materials provides a basis for the combinatorial and parallel solid-phase synthesis of these peptide mimetic classes for bioactive agent screening and also provides a basis for the further development of solid-phase C-terminal functional group elaboration strategies. 相似文献
9.
von der Schulenburg WG Hopf H Walsh R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(11):1963-1979
The pyrolyses of two isomeric pairs of alkylcyclopropenes, namely 1,3-dimethyl-(15) and 1-ethyl-cyclopropene (16), and 1,3,3-trimethyl-(5) and 1-isopropyl-cyclopropene (17), have been studied in the gas phase. Complete product analyses at various conversions up to 95% were obtained for the decomposition of each compound at five temperatures over a 40 degrees C range. The time-evolution data showed that the isomerisation reactions 15<==>16 and 5<==>17 were occurring. Kinetic modelling of each system allowed the determination of rate constants for these and all other decomposition processes. Tests confirmed that all reactions were unimolecular and homogeneous. Arrhenius parameters are reported for overall reactions and individual product pathways. Further kinetic analysis allowed us to extract the propensities (at 500 K) for 1,3-C-H insertion of the dialkylvinylidene intermediates involved in the rearrangements as follows: k(prim):k(sec): k(tert)= 1:16.5:46.4. Additional experiments with 13C-labelled cyclopropenes yielded alkyl group migration aptitudes for the dialkylvinylidenes (from the pattern of 13C in the alkyne products) as follows: Me:Et:iPr=1:3.1:1.5. Explanations for these trends are given. Another important finding is that of the dramatic rate enhancements for 1,3-diene product formation from the 1-alkylcyclopropenes; this can be explained by either hyperconjugative stabilisation of the vinylcarbene intermediates involved in this pathway, or their differing propensities to 1,2 H-shift. The observed large variations in product distribution amongst these four cyclopropenes is interpreted in terms of these specific effects on individual pathways. 相似文献
10.
Hai-Wen Ge Min-Ming Zhu Yi-Liang Chen Eva Gutheil 《Flow, Turbulence and Combustion》2007,78(2):91-109
A hybrid unsteady Reynolds-averaged numerical simulation (U-RANS) and probability density function (PDF) method is developed
for turbulent non-reactive and reactive flows. The resulting modeled equations are solved by a consistent hybrid finite volume
and Lagrangian Monte-Carlo particle method. Both turbulent non-reactive and reactive flows in a rectangular channel containing
a triangular-shaped bluff-body are simulated. One-step and two-step mechanisms for propane/air combustion are used for the
reactive case. The time-averaged results are compared with both experimental data and numerical results from the literature
using large eddy simulation (LES) and steady RANS. The results of the present method are in good agreement with the experimental
data, and they improve the numerical results available in the literature. 相似文献