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91.
Prof. Peter A. Beckmann Prof. Paul R. Rablen Dr. Jason Schmink Dr. Steven T. Szewczyk Prof. Arnold L. Rheingold 《Chemphyschem》2019,20(21):2887-2894
We investigate the relationship between structure (crystal and molecular) and tert-butyl and methyl group dynamics in 2-(tert-butyl)-9-(4-(tert-butyl)phenyl)anthracene. Powder and single-crystal X-ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X-ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert-butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments support the powder and single-crystal X-ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert-butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert-butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations. 相似文献
92.
Dr. Nikolay A. Pushkarevsky Elena A. Chulanova Prof. Dr. Leonid A. Shundrin Dr. Anton I. Smolentsev Dr. Georgy E. Salnikov Dr. Elena A. Pritchina Dr. Alexander M. Genaev Dr. Irina G. Irtegova Prof. Dr. Irina Yu. Bagryanskaya Prof. Dr. Sergey N. Konchenko Prof. Dr. Nina P. Gritsan Prof. Dr. Jens Beckmann Prof. Dr. Andrey V. Zibarev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):806-816
By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron-acceptor ability of 2,1,3-benzochalcogenadiazoles 1 – 3 (chalcogen: S, Se, and Te, respectively) increases with increasing atomic number of the chalcogen. This trend is nontrivial, since it contradicts the electronegativity and atomic electron affinity of the chalcogens. In contrast to radical anions (RAs) [ 1 ].− and [ 2 ].−, RA [ 3 ].− was not detected by EPR spectroscopy under CV conditions. Chemical reduction of 1 – 3 was performed and new thermally stable RA salts [K(THF)]+[ 2 ].− ( 8 ) and [K(18-crown-6)]+[ 2 ].− ( 9 ) were isolated in addition to known salt [K(THF)]+[ 1 ].− ( 7 ). On contact with air, RAs [ 1 ].− and [ 2 ].− underwent fast decomposition in solution with the formation of anions [ECN]−, which were isolated in the form of salts [K(18-crown-6)]+[ECN]− ( 10 , E=S; 11 , E=Se). In the case of 3 , RA [ 3 ].− was detected by EPR spectroscopy as the first representative of tellurium–nitrogen π-heterocyclic RAs but not isolated. Instead, salt [K(18-crown-6)]+2[ 3 -Te2]2− ( 12 ) featuring a new anionic complex with coordinate Te−Te bond was obtained. On contact with air, salt 12 transformed into salt [K(18-crown-6)]+2[ 3 -Te4- 3 ]2− ( 13 ) containing an anionic complex with two coordinate Te−Te bonds. The structures of 8 – 13 were confirmed by XRD, and the nature of the Te−Te coordinate bond in [ 3 -Te2]2− and [ 3 -Te4- 3 ]2− was studied by DFT calculations and QTAIM analysis. 相似文献
93.
Matthew J. Stark Douglas T. Tang Nigam P. Rath Eike B. Bauer 《Tetrahedron letters》2018,59(10):873-877
A new ruthenium 2,6-diacetylpyridine complex was synthesized and applied in the atom-economic synthesis of enol esters through Markovnikov-directed addition of carboxylic acids to terminal alkynes. The ruthenium complex [RuCl(dap)(PPh3)2]+BArF? was synthesized from [RuCl2(PPh3)2] and the corresponding ligand 2,6-diacetylpyridine (dap). The complex was characterized structurally. The new ruthenium complex was utilized under ambient conditions as a catalyst in the Markovnikov addition of carboxylic acids to terminal alkynes to afford the corresponding enol esters in 93% to 52% isolated yields (85?°C, 16?h reaction time, 1?mol% catalyst loading). 相似文献
94.
Karl Gatterdam Eike F. Joest Dr. Marina S. Dietz Prof. Dr. Mike Heilemann Prof. Dr. Robert Tampé 《Angewandte Chemie (International ed. in English)》2018,57(20):5620-5625
Live‐cell labeling, super‐resolution microscopy, single‐molecule applications, protein localization, or chemically induced assembly are emerging approaches, which require specific and very small interaction pairs. The minimal disturbance of protein function is essential to derive unbiased insights into cellular processes. Herein, we define a new class of hexavalent N‐nitrilotriacetic acid (hexaNTA) chelators, displaying the highest affinity and stability of all NTA‐based small interaction pairs described so far. Coupled to bright organic fluorophores with fine‐tuned photophysical properties, the super‐chelator probes were delivered into human cells by chemically gated nanopores. These super‐chelators permit kinetic profiling, multiplexed labeling of His6‐ and His12‐tagged proteins as well as single‐molecule‐based super‐resolution imaging. 相似文献
95.
96.
E. H. Riesenfeld H. E. Wohlers Lockyer Beckmann und Rupp 《Fresenius' Journal of Analytical Chemistry》1907,46(2-3):167-169
Ohne Zusammenfassung 相似文献
97.
98.
The synthesis of five natural products (3, 6, 7, 10, and 14), isolated from the Indian neem tree Azadirachta indica, is reported from a common intermediate (2). The judicious choice of transacetalization conditions allows efficient access to both the azadirachtinin (9 and 10) and the azadirachtin (3, 6, 7, and 14) skeletons. 相似文献
99.
Xiao SH Reagan JD Lee PH Fu A Schwandner R Zhao X Knop J Beckmann H Young SW 《Combinatorial chemistry & high throughput screening》2008,11(3):195-215
GPCRs had significant representation in the drug discovery portfolios of most major commercial drug discovery organizations for many years. This is due in part to the diverse biological roles mediated by GPCRs as a class, as well as the empirical discovery that they have proven relatively tractable to the development of small molecule therapeutics. Publication of the human genome sequence in 2001 confirmed GPCRs as the largest single gene superfamily with more than 700 members, furthering the already strong appeal of addressing this target class using efficient and highly parallelized platform approaches. The GPCR research platform implemented at Amgen is used as a case study to review the evolution and implementation of available assays and technologies applicable to GPCR drug discovery. The strengths, weaknesses, and applications of assay technologies applicable to G alpha s, G alpha i and G alpha q-coupled receptors are described and their relative merits evaluated. Particular consideration is made of the role and practice of "de-orphaning" and signaling pathway characterization as a pre-requisite to establishing effective screens. In silico and in vitro methodology developed for rapid, parallel high throughput hit characterization and prioritization is also discussed extensively. 相似文献
100.
William P. Freeman Yi Joon Ahn J. Andrew Whitaker Ramel J. Rubio Eike B. Bauer Fook S. Tham 《Journal of organometallic chemistry》2008,693(14):2415-2423
Four new phosphazirconocenes, [(4,5,6-trihydro-1-phosphapentalenyl)2ZrCl2] (8), [(4,5,6,7-tetrahydro-1-phosphindolyl)2ZrCl2] (9), [(4,5,6,7,8-pentahydro-1-phosphazulenyl)2ZrCl2] (10), (2,4-dimethylphospholyl)2ZrCl2 (11), were prepared and characterized. A crystal structure of [(4,5,6,7-tetrahydro-1-phosphindolyl)2ZrCl2] (9), was obtained that revealed disorder (rac and meso isomers in the same crystal) and demonstrates unambiguously the meso configuration in the bent early transition metal phosphametallocenes. Lacking a spectroscopic probe of the rotational dynamics in phosphametallocenes, propylene polymerization was chosen to provide a record of the stereoselective insertions and by inference insight into the phosphametallocene dynamics. Phosphazirconocenes 8-11 were evaluated, and the rac/meso mixture of [(4,5,6,7-tetrahydro-1-phosphindolyl)2ZrCl2] (9) was found to produce a mixture of isotactic (iPP) and atactic (aPP) polypropylenes. 13C NMR spectral analysis of the stereo-errors contained in the iPP fraction indicated enantiomorphic site control as the source of the stereoselectivity. The rotational dynamics of the η5-phospholyl ligand of the parent phosphazirconocene, [(C4H4P)2ZrCl2], was examined as a first order surrogate of reasonable computing complexity for the catalytically active species. The phosphazirconocene was examined using a restricted Hartree-Fock method with a split basis set of 6-311+G(d,p) for C, H, Cl, P and of LANL2DZ for Zr. The rotational potential energy surface was found to be unsymmetrical with a maximum barrier of 8.8 kcal mol−1, which is about an order of magnitude greater than that reported for Cp2ZrCl2. The projection of the calculated rotational dynamics onto a 1-phosphatetrahydroindenyl system is illustrated. This model leads to an interpretation of the polymerization results and the rotational dynamics in phosphametallocenes. 相似文献