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71.
[reaction: see text] Glucuronyl iodide 1 has been studied in detail as a "disarmed" glycosyl donor. In a model reaction, using N-iodosuccinimide (NIS) as a promoter and 2-phenylethanol as acceptor, best results were obtained using NIS with I(2), followed by trimethylsilyltrifluoromethanesulfonate (TMSOTf). When a series of primary and secondary alcohols was glycosylated using these conditions, yields of 60-83% of beta-glucuronides were obtained. Various "nonheavy" metal salts also effectively catalyzed the model reaction but led to significant amounts of alpha-product with less reactive secondary alcohols. 相似文献
72.
Weronika Gruszka Anna Lykkeberg Gary S. Nichol Michael P. Shaver Antoine Buchard Jennifer A. Garden 《Chemical science》2020,11(43):11785
Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver “best of both” in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (kobs = 1.7 × 10−2 s−1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.Cooperative heterotrimetallic Na/Zn2 and K/Zn2 complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation. 相似文献
73.
Yongzheng Cong Khatereh Motamedchaboki Santosh A. Misal Yiran Liang Amanda J. Guise Thy Truong Romain Huguet Edward D. Plowey Ying Zhu Daniel Lopez-Ferrer Ryan T. Kelly 《Chemical science》2021,12(3):1001
We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling. 相似文献
74.
Tynan E Jensen P Kelly NR Kruger PE Lees AC Moubaraki B Murray KS 《Dalton transactions (Cambridge, England : 2003)》2004,(21):3440-3447
We report herein the single crystal structures of four metal-organic framework complexes incorporating the 4,4'-dicarboxy-2,2'-bipyridine ligand, H(2)dcbp: alpha-[Co(dcbp)(H(2)O)(2)], 1; beta-[Co(dcbp)(H(2)O)(2)], 2, [Ni(dcbp)(H(2)O)(2)], and [[Mn(dcbp)].1/2DEF], 4 (DEF = diethylformamide). In each complex the ligand is deprotonated giving neutral species with 1:1 stoichiometry that form three-dimensional coordination polymers. Supramolecular isomerism (polymorphism) in 1 and 2 arises from the different ligand connectivity around the octahedral Co(II) centres. The two coordinated water molecules in 1 occupy cis positions, which are trans to the chelating bipyridine nitrogen atoms, leaving the carboxylate oxygen atoms in axial trans positions. In 2 all like donors occupy cis positions. Different modes of carboxylate coordination in 1 and 2 give dissimilar network topologies. A rare example of two interpenetrating 6(4)8(2)-b (quartz-like) chiral networks in 1 results from both dcbp carboxylate groups coordinating in a monodentate fashion to adjacent Co(II) centres, whereas in 2 only one carboxylate group bridges between adjacent Co(II) centres giving rise to a single chiral (10,3)-a net. In 1 and 2 the coordinated water molecules hydrogen bond to the non-coordinated carboxylate oxygen atoms. These interactions give rise to water-carboxylate double helices in , and support the coordination network in 2. Strikingly for a pair of dimorphs the crystal densities of 1 and 2 differ by ca. 0.3 g cm(-3)(1.654 vs. 1.940 g cm(-3), respectively). Compound 3 is isomorphous with 1 and likewise features two chiral interpenetrating nets of quartz topology. In 4, chelating bipyridine nitrogen atoms and four carboxylate oxygen atoms from a total of five adjacent dcbp ligands provide distorted octahedral geometry around Mn(II). The carboxylate groups bridge adjacent Mn(II) centres to produce bis-carboxylato chains which cross-link and generate a 3D network that is perforated with channels. The channels are occupied with disordered DEF molecules. The network topology in 4 is quite different to 1-3 and has a (4.6(2))(4(2).6)(4(3).6(6).8(6)) Schlafli notation. Magnetic susceptibility studies performed on 1, 2, [[Mn(dcbp)].1/2DMF] 5 (DMF = dimethylformamide) and [[Mn(dcbp)].2H(2)O] 6 reveal very weak antiferromagnetic coupling between the metal centres in each case. 相似文献
75.
Edwards KW Ogg M Bellerive A Britton DI Hyatt ER MacFarlane DB Patel PM Spaan B Sadoff AJ Ammar R Baringer P Bean A Besson D Coppage D Copty N Davis R Hancock N Kelly M Kotov S Kravchenko I Kwak N Lam H Kubota Y Lattery M Momayezi M Nelson JK Patton S Poling R Savinov V Schrenk S Wang R Alam MS Kim IJ Ling Z Mahmood AH O'Neill JJ Severini H Sun CR Wappler F Crawford G Daubenmier CM Fulton R Fujino D Gan KK Honscheid K Kagan H Kass R Lee J Sung M White C Wolf A Zoeller MM Butler F Fu X Nemati B 《Physical review letters》1995,74(17):3331-3335
76.
Jeffrey Axten Jennifer Troy Peter Jiang Mendel Trachtman Charles W. Bock 《Structural chemistry》1994,5(2):99-108
Ab initio molecular orbital calculations are used to study the modified Schlenk equilibrium: 2RMgCl (RMgCl)2 MgR2 + MgCl2 Mg(Cl2)MgR2 with R=H and CH3. In the absence of any solvents, calculations indicate that the formation of the various possible bridged dimers (RMgCl)2 is substantially exothermic. However, using dimethylether as a model solvent, we show that the formation of the dimer (Me2O)(CH3)Mg(Cl2)Mg(CH3)(OMe2) is exothermic only when entropic effects are included. 相似文献
77.
Cinabro D Henderson S Liu T Saulnier M Wilson R Yamamoto H Bergfeld T Eisenstein BI Gollin G Ong B Palmer M Selen M Thaler JJ Sadoff AJ Ammar R Ball S Baringer P Bean A Besson D Coppage D Copty N Davis R Hancock N Kelly M Kwak N Lam H Kubota Y Lattery M Nelson JK Patton S Perticone D Poling R Savinov V Schrenk S Wang R Alam MS Kim IJ Nemati B O'Neill JJ Severini H Sun CR Zoeller MM Crawford G Daubenmier CM Fulton R Fujino D Gan KK Honscheid K Kagan H Kass R Lee J Malchow R Morrow F Skovpen Y 《Physical review letters》1994,72(10):1406-1410
78.
Ammar R Ball S Baringer P Bean A Besson D Coppage D Copty N Davis R Hancock N Kelly M Kwak N Lam H Kubota Y Lattery M Nelson JK Patton S Perticone D Poling R Savinov V Schrenk S Wang R Alam MS Kim IJ Nemati B O'Neill JJ Severini H Sun CR Zoeller MM Crawford G Daubenmier CM Fulton R Fujino D Gan KK Honscheid K Kagan H Kass R Lee J Malchow R Morrow F Skovpen Y Sung M White C Butler F Fu X Kalbfleisch G Ross WR Skubic P Snow J Wang PL Wood M Brown DN Fast J McIlwain RL Miao T Miller DH Modesitt M 《Physical review D: Particles and fields》1994,49(11):5701-5704
79.
80.