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991.
Robert M. Archer Dr. Sylvain F. Royer William Mahy Dr. Caroline L. Winn Prof. Michael J. Danson Dr. Steven D. Bull 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2895-2902
Practical syntheses of 2‐keto‐3‐deoxy‐D ‐xylonate (D ‐KDX) and 2‐keto‐3‐deoxy‐L ‐arabinonate (L ‐KDA) that rely on reaction of the anion of ethyl 2‐[(tert‐butyldimethylsilyl)oxy]‐2‐(dimethoxy phosphoryl) acetate with enantiopure glyceraldehyde acetonide, followed by global deprotection of the resultant O‐silyl‐enol esters, have been developed. This has enabled us to confirm that a 2‐keto‐3‐deoxy‐D ‐gluconate aldolase from the archaeon Sulfolobus solfataricus demonstrates good activity for catalysis of the retro‐aldol cleavage of both these enantiomers to afford pyruvate and glycolaldehyde. The stereochemical promiscuity of this aldolase towards these enantiomeric aldol substrates confirms that this organism employs a metabolically promiscuous pathway to catabolise the C5‐sugars D ‐xylose and L ‐arabinose. 相似文献
992.
Zheng Wang Shuai Luo Dr. Shoude Zhang Wu‐Lin Yang Yang‐Zi Liu Prof. Dr. Honglin Li Prof. Dr. Xiaoyan Luo Prof. Dr. Wei‐Ping Deng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6739-6745
The first catalytic enantioselective 1,3‐dipolar cycloaddition of azomethine ylides to α‐aminoacrylate catalyzed by a AgOAc/ferrocenyl oxazolinylphosphine (FOXAP) system was developed, which exhibits excellent exo‐ and enantioselectivity (92–99 % ee). This process provides efficient access to useful 4‐aminopyrrolidine‐2,4‐dicarboxylic acid (APDC)‐like compounds containing a unique quaternary α‐amino acid unit. 相似文献
993.
Dr. Matthias Lein Dr. Linbin Jiang Dr. Wanxing Wei Prof. Dr. Jianyi Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14126-14142
The mechanism of CuI‐catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2Cu]? prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α‐ or γ‐selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α‐ and γ‐substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α‐ and γ‐substituted products are 2.75 kcal mol?1 with SPO(OiPr)2, 2.44 kcal mol?1 with SPiv, 2.33 kcal mol?1 with OPiv, and 1.98 kcal mol?1 with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2>SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2, SPiv, OPiv, and Cl groups on the Cu group. 相似文献
994.
Etienne Brachet Prof. Jean‐Daniel Brion Dr. Mouad Alami Dr. Samir Messaoudi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15276-15280
Unprotected thioglycosides were effective nucleophiles for Ni0‐catalyzed C? S bond‐forming reaction with functionalized (hetero)aryl, alkenyl, and alkynyl halides. The functional‐group tolerance on the electrophilic partner was typically high and the anomeric selectivities of the thioglycosides were high in all cases. The efficiency of this general procedure was well‐demonstrated by the synthesis of 4‐methyl‐7‐thioumbelliferyl‐β‐D ‐cellobioside (MUS‐CB). 相似文献
995.
Minami Odagi Kota Furukori Tatsuya Watanabe Prof. Dr. Kazuo Nagasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16740-16745
Highly enantioselective catalytic oxidation of 1‐tetralone‐derived β‐keto esters was achieved by using a guanidine–urea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP), a safe, commercially available oxidant. The α‐hydroxylation products were obtained in 99 % yield with up to 95 % enantiomeric excess (ee). The present oxidation was successfully applied to synthesize a key intermediate of the anti‐cancer agent daunorubicin ( 2 ). 相似文献
996.
Nissa C. Frank Dr. Darren J. Mercer Prof. Dr. Stephen J. Loeb 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14076-14080
New dibenzo[24]crown‐8 ether derivatives were prepared that contain appendages with thioether donors that can coordinate to a metal ion. These macrocycles were then combined with 1,2‐bis(pyridinium) ethane axles to create two types of [2]rotaxane ligands; those with the four thioether donors on the crown ether and those with six donor groups, four from the crown ether and two more attached to the stoppering groups of the dumbbell. The crown ethers and both types of [2]rotaxane ligands were allowed to react with AgI ions to form metal‐organic rotaxane framework (MORF) style coordination polymers. The interlocked hexadentate ligand forms the first example of a new type of lattice containing interwoven frameworks resulting from both interpenetration of frameworks due to the presence of an interlocked ligand and more classical interpenetration of independent frameworks. 相似文献
997.
Two plant proteins, soyprotein and wheat gluten, and chicken feathers used to size cotton substrates provided sizing performance similar to starch and were also easily degraded in activated sludge. Sizing is an essential process to impart protection to warp yarns and increase weaving efficiency. Cotton yarns have traditionally been sized with starch, modified starch derivatives, CMC, poly vinyl alcohol (PVA), or a combination thereof along with quite a few other fiber binding ingredients. Although starch and starch derivatives are extensively used for sizing, there can be several limitations including less-than-satisfactory sizing performance and difficulties in desizing starch based size. Plant proteins such as wheat gluten, soyproteins and poultry feathers are available in large quantities at low cost and have limited industrial applications. However, these proteins are known to have excellent film-forming properties, a primary requirement for a warp size, and have also been used as adhesives. Using proteins as warp sizing agents on cotton yarns potentially could provide acceptable sizing performance and be cost-effective, as well. In this research, soyproteins, wheat gluten, and chicken feathers were studied for exploring their feasibility for sizing, desizing, biodegradability, and ability to replace starch and PVA for sizing cotton yarns. It was found that all three proteins provided similar cohesion to fibers and abrasion resistance compared to starch. Protein sizes had significantly high BOD5/COD ratio compared to PVA, suggesting that the proteins are easily degradable in textile effluent treatment plants. 相似文献
998.
999.
1000.
Dian‐Feng Chen Feng Zhao Yue Hu Liu‐Zhu Gong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(40):10939-10943
A combination of either ruthenium(II) or rhodium(II) complexes and quinine‐derived squaramide enables 3‐diazooxindoles, indoles, and nitroalkenes to undergo highly efficient asymmetric three‐component reactions, thus affording optically active 3,3′‐bis(indole)s through a consecutive C C bond‐forming sequence, which turned out to be applicable to the facile total synthesis of (−)‐folicanthine. 相似文献