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171.
Synthesis of 1‐silacyclopent‐2‐ene derivatives using 1,2‐hydroboration, 1,1‐organoboration and protodeborylation
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The reaction of di(alkyn‐1‐yl)vinylsilanes R1(H2C═CH)Si(C≡C―R)2 (R1 = Me ( 1 ), Ph ( 2 ); R = Bu (a), Ph (b), Me2HSi (c)) at 25°C with 1 equiv. of 9‐borabicyclo[3.3.1]nonane (9‐BBN) affords 1‐silacyclopent‐2‐ene derivatives ( 3a , 3b , 3c , 4a , 4b ), bearing one Si―C≡C―R function readily available for further transformations. These compounds are formed by consecutive 1,2‐hydroboration followed by intramolecular 1,1‐carboboration. Treated with a further equivalent of 9‐BBN in benzene they are converted at relatively high temperature (80–100°C) into 1‐alkenyl‐1‐silacyclopent‐2‐ene derivatives ( 5a , 5b 6a , 6b ) as a result of 1,2‐hydroboration of the Si―C≡C―R function. Protodeborylation of the 9‐BBN‐substituted 1‐silacyclopent‐2‐ene derivatives 3 , 4 , 5 , 6 , using acetic acid in excess, proceeds smoothly to give the novel 1‐silacyclopent‐2‐ene ( 7 , 8 , 9 , 10 ). The solution‐state structural assignment of all new compounds, i.e. di(alkyn‐1‐yl)vinylsilanes and 1‐silacyclopent‐2‐ene derivatives, was carried out using multinuclear magnetic resonance techniques (1H, 13C, 11B, 29Si NMR). The gas phase structures of some examples were calculated and optimized by density functional theory methods (B3LYP/6‐311+G/(d,p) level of theory), and 29Si NMR parameters were calculated (chemical shifts δ29Si and coupling constants nJ(29Si,13C)). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
172.
Thies Dirksmeyer Paul Stahl Dr. Cecilia Vallet Prof. Dr. Shirley Knauer Prof. Dr. Michael Giese Prof. Dr. Carsten Schmuck Dr. Christoph Hirschhäuser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202104618
A transfection vector that can home in on tumors is reported. Whereas previous vectors that allow moderately cell selective gene transfection used larger systems, this small-molecule approach paved the way for precise structure-activity relationship optimization. For this, biotin, which mediates cell selectivity, was combined with the potent DNA-binding motif tetralysine-guanidinocarbonypyrrol via a hydrophilic linker, thus enabling SAR-based optimization. The new vector mediated biotin receptor (BR)-selective transfection of cell lines with different BR expression levels. Computer-based analyses of microscopy images revealed a preference of one order of magnitude for the BR-positive cell lines over the BR-negative controls. 相似文献
173.
Jan Maier Marian Deutsch Dr. Julia Merz Prof. Dr. Qing Ye Oliver Diamond Maja-Tessa Schilling Dr. Alexandra Friedrich Prof. Dr. Bernd Engels Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15989-16000
We have investigated the cannibalistic self-trapping reaction of an ortho-benzyne derivative generated from 1,11-bis(p-tolyl)undeca-1,3,8,10-tetrayne in an HDDA reaction. Without adding any specific trapping agent, the highly reactive benzyne is trapped by another bisdiyne molecule in at least three different modes. We have isolated and characterized the resulting products and performed high-level calculations concerning the reaction mechanism. During the cannibalistic self-trapping process, either a C≡C triple bond or an sp–sp3 C−C single bond is cleaved. Up to seven rings and nine C−C bonds are formed starting from two 1,11-bis(p-tolyl)undeca-1,3,8,10-tetrayne molecules. Our experiments and calculations provide considerable insight into the variety of reaction pathways which the ortho-benzyne derivative, generated from a bisdiyne, can take when reacting with another bisdiyne molecule. 相似文献
174.
175.
Triggering the Directional Selectivity of a Ring‐Closure Reaction Leads to Pyridoazacarbazoles with Anticancer Properties
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Tamara N. Steinhauer Daniel S. Längle Dr. Christopher Meier Dr. Ulrich Girreser Dr. Lars Stenzel Prof. Dr. Dieter Heber Prof. Dr. Bernd Clement 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6668-6672
We herein describe a facile and versatile synthetic route to the tetracyclic system of 6‐substituted 5,6‐dihydro‐11H‐pyrido[3,2‐i]‐1‐azacarbazoles with promising anticancer properties. These derivatives are built up by an elegant one‐step base‐catalyzed synthetic procedure from commercially available building blocks. One additional step provides the corresponding skeleton hitherto unknown in the literature. The possibility to synthesize a large library of compounds with various substitution patterns utilizing this method underlines the importance of this synthetic procedure. 相似文献
176.
Ceren Kütahya Nicolai Meckbach Prof. Dr. Veronika Strehmel Prof. Dr. Jochen S. Gutmann Prof. Dr. Bernd Strehmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10444-10451
NIR exposure at 790 nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [CuII/(TPMA)]Br2 (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol. 相似文献
177.
The LiRh-type crystal structure of the equiatomic intermetallic compound IrZn turns out to be a competitor to the otherwise energetically favored CsCl-type structures of congeneric transition metal zinc phases, thus enlightening the structural impact of element-specific factors beyond the Hume-Rothery concept. 相似文献
178.
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
179.