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11.
Burke AJ Davies SG Garner AC McCarthy TD Roberts PM Smith AD Rodriguez-Solla H Vickers RJ 《Organic & biomolecular chemistry》2004,2(9):1387-1394
Conjugate addition of lithium (S)-N-benzyl-N-alpha-methylbenzylamide to a range of alpha, beta-unsaturated Weinreb amides proceeds with high levels of diastereoselectivity (>95% de). The beta-amino Weinreb amide products may be transformed into beta-amino ketones via reactions with Grignard reagents, while treatment with DIBAL-H furnishes beta-amino aldehydes. Trapping of the aldehyde via Wadsworth-Emmons reaction and subsequent manipulation offers an efficient route to homochiral delta-amino acid derivatives and 2-substituted piperidines. The application of this methodology for the synthesis of (S)-coniine is demonstrated. 相似文献
12.
Donald G. Fleming Donald J. Arseneau David M. Garner Masayoshi Senba Randall J. Mikula 《Hyperfine Interactions》1984,18(1-4):655-678
The vapor phase fractional polarizations of positive muons thermalizing as the muonium atom (P
M) and in diamagnetic environments (P
D) has been measured in H2O, CH3OH, C6H14, C6H12, CCl4, CHCl3, CH2Cl2 and TMS, in order to compare with the corresponding fractions measured in the condensed phases. There is a marked contrast in every case, with the vapor phase results being largely understandable in terms of a charge exchange/hot atom model. Unlike the situation in the corresponding liquids, there is no permanent lost fraction in the vapor phase in the limit of even moderately high pressures (1 atm); at lower pressures, depolarization is due to hyperfine mixing and is believed to be well understood. For vapor phase CH3OH, C6H14, C6H12, and TMS therelative fractions are found to be pressure dependent, suggesting the importance of termolecular hot atom (or ion) reactions in the slowing down process. For vapor phase H2O and the chloromethanes, the relative fractions are pressure independent. For CCl4,P
M=P
D0.5 in the vapor phase vs.P
D=1.0 in the liquid phase; fast thermal reactions of Mu likely contribute significantly to this difference in the liquid phase. For H2O,P
M 0.9 andP
D0.1 in the vapor phase vs.P
D 0.6 andP
M0.2 in the liquid phase. Water appears to be the one unequivocal case where the basic charge exchange/hot atom model is inappropriate in the condensed phase, suggesting, therefore, that radiation induced spur effects play a major role. 相似文献
13.
Li S Bowerman D Marthandan N Klyza S Luebke KJ Garner HR Kodadek T 《Journal of the American Chemical Society》2004,126(13):4088-4089
We describe a novel photolithographic approach to the synthesis of peptoids (oligo-N-substituted glycines). This strategy enables the construction of a spatially addressable peptoid microarray, thus providing a potentially powerful tool for the discovery of protein ligands. 相似文献
14.
The rate constants for oxygen quenching in benzene solution of the triplet states of several organic compounds with relatively high triplet energies have been measured in laser photolysis and pulse radiolysis experiments. The previously observed trend for aromatic hydrocarbons where the quenching rate constants decrease from a limiting value of about one ninth of that expected for a diffusion controlled reaction to lower values for triplet states with increasing triplet energy was not observed for the triplet states of certain aromatic ketones and amines. The higher rate constants observed, e.g. oxygen quenching of triplet N-methyl indole has kQ = 1.4 × 1010 dm3 mol?1 s?1, are interpreted as being due to the presence of low lying triplet charge-transfer states which enhance the efficiency of quenching. 相似文献
15.
Davies SG Díez D El Hammouni MM Garner AC Garrido NM Long MJ Morrison RM Smith AD Sweet MJ Withey JM 《Chemical communications (Cambridge, England)》2003,(19):2410-2411
Comparison of the kinetic and parallel kinetic resolutions of methyl (RS)-5-tert-butyl-cyclopentene-1-carboxylate allows for the efficient synthesis of both (1R,2S,5S)- and (1S,2R,5R)-enantiomers of methyl 2-amino-5-tert-butyl-cyclopentane-1-carboxylate. 相似文献
16.
The MSR (muonium spin rotation) technique was used to measure the chemical reaction rate for Mu + F2 → MuF + F in N2 moderator at ≈ 1 atm from 295 to 383 K giving the Arrhenius expression: log10k (?/mole s) = (10.83 ± 0.20) - (200 ± 50)/T, with k = (1.46 ± 0.11) × 1010 ?/mole s at 300 K. This is at least 6.8 times the room temperature rate constant for the analogous H atom reaction. The measured activation energy and enhancement over the H reaction rate are indicative of significant tunnelling in the Mu reaction, in agreement with the recent collinear quantum mechanical calculations of Connor et al. 相似文献
17.
David P. Garner 《Journal of polymer science. Part A, Polymer chemistry》1982,20(10):2979-2988
Sebacyl bisketene was generated in solution at ?78°C. Copolymerization in solution at 0°C with the secondary diamines, piperazine and N,N′dimethyl-1,6-hexamethylenediamine, yielded the polyamides poly(1,4-piperazylsebacyl) and poly[(methylimino)hexamethylene(methylimino)sebacyl], respectively. The polyamides were obtained in yields of 50–90%. The former had a glass transition temperature (Tg) at 30°C and a melting temperature at 165°C, whereas the latter had only a Tg at ?15°C. The polymers were insoluble in the usual polyamide solvents. Copolymerization with the diol bisphenol A yielded poly(oxy-1,4-phenyleneisopropylidene-1,4-phenyleneoxysebacyl). The polyester was obtained in yields up to 99%. Gel permeation chromatography (GPC) determinations showed molecular weights up to 50,000 when acetone was the reaction solvent but only 12,000 when tetrahydrofuran (THF) was the reaction solvent; the Tg for the polyester varied with the molecular weight with a maximum at 15°C. Tensile properties were obtained for the polyesters with molecular weights greater than 35,000. 相似文献
18.
The preparation of some new cationic aryldiazo complexes of platinum of formula trans-[Pt(N2Ar)(PEt3)2L]+, where N2Ar = N2C6H4F-m or -p and L = NH3, Py, Et3P or EtNC, is described. Protonation of these complexes gives the corresponding aryldiimide complexes trans-[Pt(NHNAr)(PEt3)2L]+, and reduction of the protonated complexes with molecular hydrogen in the presence of a catalyst gives the arylhydrazine complexes trans-[Pt(NH2NHAr)(PEt3)2L]+. Some of the spectroscopic properties of these new complexes are reported and discussed. 相似文献
19.
Cyril W. L. Garner 《Journal of Geometry》1979,12(2):132-138
There does not exist a general theory of conics in finite projective planes, because the many definitions of conics which are equivalent in desarguesian projective planes yield different types of conics in more general situations. Thus even the use of the word conic can lead to confusion, particularly in the finite case. This note is an attempt to clarify these various definitions and give as an example in a finite projective plane a von Staudt conic which is not an Ostrom conic. We conjecture that any finite projective plane admitting an Ostrom conic must be desarguesian. 相似文献
20.
Alternating copolymers of vinyl acetate (VAc) and maleic anhydride (MA) are produced preferentially when VAc and MA are copolymerized at moderate temperatures while random copolymers are produced at temperatures above 90°C. A charge-transfer complex (CTC) of VAc/MA exists at moderate temperatures but does not exist at temperatures above 90°C. 相似文献