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1.
The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals. The tert-butyldimethylsilyl ketene acetal of methyl acetate adds nearly instantaneously to aromatic and olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl ether adducts. 相似文献
2.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
3.
-2,3--(3′-hydroxybenzyl)-butyrolactone (1) and 2,3--(3′-hydroxybenzyl)-butane-1,4-diol (2), recently identified in urine, have been synthesised in racemic form. 相似文献
4.
5.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
6.
This paper reviews the theory of search. The main viewpoint is statistical but considerable space is spent on connections with other fields such as logic and optimisation. Three primitive ideas dominate: consistency, entropy, and Bayes' methods. The theory of screening provides one of the central examples and there is a section on nonsequential random search deriving from the work of Renyi. The game of Bulls and Cows provides a motivating example for both sequential and nonsequential algorithms. 相似文献
7.
T.F. Wynn P. Clardy L. Vaughn J.D. Bradshaw J.N. Bower M.S. Epstein J.D. Winefordner 《Analytica chimica acta》1981,124(1):155-161
A system for measuring atomic fluorescence of atoms produced via an electrically-heated graphite filament in a flame (acetylene/air or acetylene/nitrous oxide) and excited with a 300-W Eimac xenon are lamp is described. The experimental system also included wavelength modulation for background emission/fluorescence/scatter correction and an optically-triggered electronic integrator for efficient monitoring of the analyte fluorescence signal. Copper, aluminum and molybdenum were determined in jet engine lubricating oil samples (1 μl) with no pretreatment. The determinations are evaluated with respect to the accuracy and repeatability criteria of the U.S. Joint Oil Analysis Program. 相似文献
8.
Richard C. Brewster Geňa Hahn Stacey Wynn Lamont Chester Lipka 《Discrete Mathematics》2012,312(10):1638-1645
The reconstruction number of a graph is the smallest number of vertex-deleted subgraphs needed to uniquely determine the graph up to isomorphism. Bollobás showed that almost all graphs have reconstruction number equal to three. McMullen and Radziszowski published a catalogue of all graphs on at most ten vertices with reconstruction number greater than three. We introduce constructions that generalize the examples identified in their work. In particular, we use lexicographic products of vertex transitive graphs with certain starter graphs from the work of Myrvold and from the work of Harary and Plantholt to generate new infinite families of graphs with high reconstruction numbers. In the process, we settle a question of McMullen and Radziszowski. 相似文献
9.
Dr. Amy C. Topley Valerio Isoni Dr. Thomas A. Logothetis Dr. Duncan Wynn Dr. Harry Wadsworth Dr. Alex M. R. Gibson Imtiaz Khan Dr. Neil J. Wells Prof. Cécile Perrio Prof. Richard C. D. Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1720-1725
A Resin‐linker‐vector (RLV) strategy is described for the radiosynthesis of tracer molecules containing the radionuclide 18F, which releases the labelled vector into solution upon nucleophilic substitution of a polystyrene‐bound arylsulfonate linker with [18F]‐fluoride ion. Three model linker‐vector molecules 7 a – c containing different alkyl spacer groups were assembled in solution from (4‐chlorosulfonylphenyl)alkanoate esters, exploiting a lipase‐catalysed chemoselective carboxylic ester hydrolysis in the presence of the sulfonate ester as a key step. The linker‐vector systems were attached to aminomethyl polystyrene resin through amide bond formation to give RLVs 8 a – c with acetate, butyrate and hexanoate spacers, which were characterised by using magic‐angle spinning (MAS) NMR spectroscopy. On fluoridolysis, the RLVs 8 a , b containing the longer spacers were shown to be more effective in the release of the fluorinated model vector (4‐fluorobutyl)phenylcarbamic acid tert‐butyl ester ( 9 ) in NMR kinetic studies and gave superior radiochemical yields (RCY≈60 %) of the 18F‐labelled vector. The approach was applied to the synthesis of the radiopharmaceutical O‐(2‐[18F]‐fluoroethyl)‐L ‐tyrosine ([18F]‐FET), delivering protected [18F]‐FET in >90 % RCY. Acid deprotection gave [18F]‐FET in an overall RCY of 41 % from the RLV. 相似文献
10.