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Back Cover: Breslow Intermediates from Aromatic N‐Heterocyclic Carbenes (Benzimidazolin‐2‐ylidenes,Thiazolin‐2‐ylidenes) (Angew. Chem. Int. Ed. 27/2018) 下载免费PDF全文
Dr. Mathias Paul Dr. Nils E. Schlörer Dr. Jörg‐M. Neudörfl Prof. Dr. Albrecht Berkessel 《Angewandte Chemie (International ed. in English)》2018,57(27):8332-8332
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Breslow Intermediates from Aromatic N‐Heterocyclic Carbenes (Benzimidazolin‐2‐ylidenes,Thiazolin‐2‐ylidenes) 下载免费PDF全文
Dr. Mathias Paul Dr. Nils E. Schlörer Dr. Jörg‐M. Neudörfl Prof. Dr. Albrecht Berkessel 《Angewandte Chemie (International ed. in English)》2018,57(27):8310-8315
We report the first generation and characterization of elusive Breslow intermediates derived from aromatic N‐heterocyclic carbenes (NHCs), namely benzimidazolin‐2‐ylidenes (NMR, X‐ray analysis) and thiazolin‐2‐ylidenes (NMR). In the former case, the diamino enols were generated by reaction of the free N,N‐bis(2,6‐diisopropylphenyl)‐ and N,N‐bis(mesityl)‐substituted benzimidazolin‐2‐ylidenes with aldehydes while the dimer of 3,4,5‐trimethylthiazolin‐2‐ylidene served as the starting material in the latter case. The unambiguous NMR identification of the first thiazolin‐2‐ylidene‐based Breslow intermediate rests on double 13C labeling of both the NHC and the aldehyde component. The acyl anion reactivity was confirmed by benzoin formation with excess aldehyde. 相似文献
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Dr. Suman De Sarkar Anup Biswas Ramesh C. Samanta Prof. Dr. Armido Studer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(15):4664-4678
This Concept article discusses the potential of oxidative carbene catalysis in synthesis and comprehensively covers pioneering studies as well as recent developments. Oxidative carbene catalysis can be conducted by using inorganic and organic oxidants. Applications in cascade processes, in enantioselective catalysis, and also in natural product synthesis are discussed. 相似文献
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Morgan Hans Prof. Johan Wouters Prof. Albert Demonceau Prof. Lionel Delaude 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9668-9676
Four zwitterions were prepared by treating 1,3‐dimesitylimidazolin‐2‐ylidene (SIMes) or 1,3‐dimesitylimidazol‐2‐ylidene (IMes) with either N‐tosyl benzaldimine or diphenylketene. They were isolated in high yields and characterized by IR and NMR spectroscopy. The molecular structures of three of them were determined by using X‐ray crystallography and their thermal stability was monitored by using thermogravimetric analysis. The imidazol(in)ium‐2‐amides were rather labile white solids that did not show any tendency to tautomerize into the corresponding 1,2,2‐triaminoethene derivatives. They displayed a mediocre catalytic activity in the Staudinger reaction of N‐tosyl benzaldimine with diphenylketene. In contrast, the imidazol(in)ium‐2‐enolates were orange‐red crystalline materials that remained stable over extended periods of time. Despite their greater stability, these zwitterions turned out to be efficient promoters for the model cycloaddition under scrutiny. As a matter of fact, their catalytic activity matched those recorded with the free carbenes. Altogether, these results provide strong experimental insight into the mechanism of the Staudinger reaction catalyzed by N‐heterocyclic carbenes. They also highlight the superior catalytic activity of the imidazole‐based carbene IMes compared with its saturated analogue SIMes in the reaction under consideration. 相似文献
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Probing the Diastereoselectivity of Staudinger Reactions Catalyzed by N‐Heterocyclic Carbenes 下载免费PDF全文
Morgan Hans Prof. Johan Wouters Prof. Albert Demonceau Prof. Lionel Delaude 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10870-10877
The reaction of ethylphenylketene with 1,3‐dimesitylimidazol‐2‐ylidene (IMes) or 1,3‐dimesitylimidazolin‐2‐ylidene (SIMes) afforded the corresponding azolium enolates in high yields. The two zwitterions were fully characterized by various analytical techniques. Their thermal stabilities were monitored by thermogravimetric analysis and the molecular structure of SIMes ? EtPhC?C?O was determined by means of X‐ray crystallography. A mechanism was proposed to account for the trans‐diastereoselectivity observed in the [2+2] cycloaddition of ketenes and N‐protected imines catalyzed by N‐heterocyclic carbenes and an extensive catalytic screening was performed to test its validity. The steric bulk of the NHC catalyst markedly affected the cis/trans ratio of the model β‐lactam product. The nature of the solvent used to carry out the Staudinger reaction also significantly influenced its diastereoselectivity. Conversely, the nature of the substituent on the N‐sulfonated imine reagent and the reaction temperature were less critical parameters. 相似文献
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Cover Picture: Long‐Lived Trifluoromethanide Anion: A Key Intermediate in Nucleophilic Trifluoromethylations (Angew. Chem. Int. Ed. 43/2014) 下载免费PDF全文
Prof. Dr. G. K. Surya Prakash Dr. Fang Wang Zhe Zhang Prof. Dr. Ralf Haiges Dr. Martin Rahm Prof. Dr. Karl O. Christe Dr. Thomas Mathew Prof. Dr. George A. Olah 《Angewandte Chemie (International ed. in English)》2014,53(43):11383-11383
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Matthew C. Leclerc Dr. Serge I. Gorelsky Bulat M. Gabidullin Ilia Korobkov Prof. R. Tom Baker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8063-8067
Selective reactions between nucleophilic N,N′‐diaryl‐heterocyclic carbenes (NHCs) and electrophilic fluorinated alkenes afford NHC fluoroalkenes in high yields. These stable compounds undergo efficient and selective fluoride abstraction with Lewis acids to give polyfluoroalkenyl imidazolium salts. These salts react at Cβ with pyrrolidine to give ammonium fluoride‐substituted salts, which give rise to conjugated imidazolium‐enamine salts through loss of HF. Alternatively, reaction with 4‐(dimethylamino)‐pyridine provides a Cα‐pyridinium‐substituted NHC fluoroalkene. These compounds were studied using multinuclear NMR spectroscopy, mass spectrometry, and X‐ray crystallography. Insight into their electronic structure and reactivity was gained through the use of DFT calculations. 相似文献
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Back Cover: A High‐Pressure NMR Probe for Aqueous Geochemistry (Angew. Chem. Int. Ed. 37/2014) 下载免费PDF全文
Dr. Brent G. Pautler Christopher A. Colla Dr. Rene L. Johnson Peter Klavins Dr. Stephen J. Harley Dr. C. André Ohlin Prof. Dimitri A. Sverjensky Dr. Jeffrey H. Walton Prof. William H. Casey 《Angewandte Chemie (International ed. in English)》2014,53(37):9962-9962