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Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair
Dr. María Carmona Dr. Joaquina Ferrer Dr. Ricardo Rodríguez Dr. Vincenzo Passarelli Prof. Dr. Fernando J. Lahoz Dr. Pilar García-Orduña Dr. Laura Cañadillas-Delgado Prof. Dr. Daniel Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13665-13670
[Cp*Rh(κ3N,N′,P- L )][SbF6] (Cp*=C5Me5), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H2 and H2O in a reversible manner. When D2O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp3)−H bond activation. 相似文献
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Manuel G. Ricardo Dayma Llanes Ludger A. Wessjohann Daniel G. Rivera 《Angewandte Chemie (International ed. in English)》2019,58(9):2700-2704
For the first time, the Petasis (borono‐Mannich) reaction is employed for the multicomponent labeling and stapling of peptides. The report includes the solid‐phase derivatization of peptides at the N‐terminus, Lys, and N?‐MeLys side‐chains by an on‐resin Petasis reaction with variation of the carbonyl and boronic acid components. Peptides were simultaneously functionalized with aryl/vinyl substituents bearing fluorescent/affinity tags and oxo components such as dihydroxyacetone, glyceraldehyde, glyoxylic acid, and aldoses, thus encompassing a powerful complexity‐generating approach without changing the charge of the peptides. The multicomponent stapling was conducted in solution by linking N?‐MeLys or Orn side‐chains, positioned at i, i+7 and i, i+4, with aryl tethers, while hydroxy carbonyl moieties were introduced as exocyclic fragments. The good efficiency and diversity oriented character of these methods show prospects for peptide drug discovery and chemical biology. 相似文献
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An FTIR spectroscopic study of the elusive hydrogen-bonded methanol–ethene complex, the most elementary example for weak intermolecular alcohol hydrogen bonding to a π cloud, is presented. By isolating the complex in a supersonic jet, the rigorous comparability to high-level quantum chemical calculations is ensured. In stark contrast to classical hydrogen bonds, experimental overtone analysis reveals the harmonic oscillator approximation for the OH red shift to be accurate. Harmonic calculations up to explicitly correlated local coupled-cluster level are thus found to agree very well with experiment. The experimental OH values for the red shift (45 cm–1), the small change in diagonal anharmonicity (–3 cm–1) and the overtone intensity attenuation (2 × 102-fold) together with theoretical predictions for the preferred structural arrangement and the zero-point-corrected dissociation energy (8 kJ mol–1) may thus be regarded as definitive reference values for related systems and for more approximate computational methods. In particular, MP2 calculations are shown to fail for this kind of weak intermolecular interaction. 相似文献
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Fluorinated Musk Fragrances: The CF2 Group as a Conformational Bias Influencing the Odour of Civetone and (R)‐Muscone 下载免费PDF全文
Dr. Ricardo Callejo Dr. Michael J. Corr Mingyan Yang Prof. Mingan Wang Dr. David B. Cordes Prof. Alexandra M. Z. Slawin Prof. David O'Hagan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8137-8151
The difluoromethylene (CF2) group has a strong tendency to adopt corner over edge locations in aliphatic macrocycles. In this study, the CF2 group has been introduced into musk relevant macrocyclic ketones. Nine civetone and five muscone analogues have been prepared by synthesis for structure and odour comparisons. X‐ray studies indeed show that the CF2 groups influence ring structure and they give some insight into the preferred ring conformations, triggering a musk odour as determined in a professional perfumery environment. The historical conformational model of Bersuker and co‐workers for musk fragrance generally holds, and structures that become distorted from this consensus, by the particular placement of the CF2 groups, lose their musk fragrance and become less pleasant. 相似文献
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Josepha Yohanna de Jesus Eliane Santos de Carvalho Dantas Mairim Russo Serafini Paula dos Passos Menezes Juliana Cordeiro Cardoso Ricardo Luiz Cavalcanti Albuquerque-Jr Jivaldo do Rosário Matos Juliana Ferreira de Oliveira Irwin Rose Alencar de Menezes Francilene Amaral da Silva Adriano Antunes de Souza Araújo 《Journal of Thermal Analysis and Calorimetry》2016,123(3):2003-2012
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