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91.
Ian Paterson Victoria A. Steadman neé DoughtyMalcolm D. McLeod Thomas Trieselmann 《Tetrahedron》2011,67(52):10119-10128
A highly stereocontrolled total synthesis of the 18-membered macrolide (+)-concanamycin F, a potent inhibitor of vacuolar ATPases, is described that proceeds in 5.8% yield over 26 steps. The three key fragments, C1-C13 vinyl iodide, C14-C22 vinyl stannane and C23-C28 aldehyde, were efficiently constructed using asymmetric boron-mediated aldol reactions of appropriate chiral ketone building blocks. The nature of the silyl protection of the C7/C9 hydroxyls proved to be critical for achieving macrocyclisation, with TES ethers being superior to a cyclic silylene derivative. Following a Liebeskind-Stille cross-coupling reaction between the C1-C13 vinyl iodide and C14-C22 vinyl stannane fragments to assemble the (12E,14E)-diene, a modified Yamaguchi macrolactonisation delivered the requisite 18-membered macrocyclic core. This advanced intermediate was also obtained by an alternative sequence using an esterification step to connect the C1-C13 and C14-C22 fragments followed by a Pd-catalysed intramolecular Stille reaction to install the (12E,14E)-diene. Conversion of the resulting macrocyclic intermediate into a methyl ketone then enabled a highly diastereoselective Mukaiyama aldol coupling of the derived silyl enol ether with the C13-C28 aldehyde fragment to install the fully elaborated side chain, whereby subsequent global deprotection of the resulting β-hydroxyketone under suitable conditions (TASF followed by p-TsOH) afforded (+)-concanamycin F. 相似文献
92.
The number of transversals in a Latin square 总被引:1,自引:0,他引:1
Brendan D. McKay Jeanette C. McLeod Ian M. Wanless 《Designs, Codes and Cryptography》2006,40(3):269-284
A Latin Square of order n is an n × n array of n symbols, in which each symbol occurs exactly once in each row and column. A transversal is a set of n entries, one selected from each row and each column of a Latin Square of order n such that no two entries contain the same symbol. Define T(n) to be the maximum number of transversals over all Latin squares of order n. We show that
for n ≥ 5, where b ≈ 1.719 and c ≈ 0.614. A corollary of this result is an upper bound on the number of placements of n non-attacking queens on an n × n toroidal chess board. Some divisibility properties of the number of transversals in Latin squares based on finite groups
are established. We also provide data from a computer enumeration of transversals in all Latin Squares of order at most 9,
all groups of order at most 23 and all possible turn-squares of order 14. 相似文献
93.
[Structure: see text] N,N-Bis(ethoxymethyl)alkylamines function as effective reagents in the double-Mannich annulation of cyclic ketone substrates, providing efficient access to a series of azabicyclic ketones. These ring systems are a useful scaffold for the four-step synthesis of novel constrained homocholine analogues. 相似文献
94.
95.
The detection and study of glucuronide metabolites is essential in many fields including pharmaceutical development, sports drug testing, and the detection of agricultural residues. Therefore, the development of improved methods for the synthesis of glucuronide conjugates is an important aim. The glycosynthase derived from E. coli β-glucuronidase provides an efficient, scalable, single-step synthesis of β-glucuronides under mild conditions. In this article we report on experimental and kinetic studies of the E. coli glucuronylsynthase, including the influence of acceptor substrate, pH, temperature, cosolvents, and detergents, leading to optimized conditions for glucuronide synthesis. Enzyme kinetics also reveals that both substrate and product inhibition may occur in glucuronylsynthase reactions but that these effects can be ameliorated through the judicious choice of acceptor and donor substrate concentrations. An investigation of temporary polar substituents was conducted leading to improved aqueous solubility of hydrophobic steroidal acceptors. In this way the synthesis of the steroidal metabolite dehydroepiandrosterone 3-β-D-glucuronide was achieved in three steps and 86% overall yield from dehydroepiandrosterone. 相似文献
96.
Photovoltaic research has become increasingly prominent as the search for alternatives to fossil fuels are actively sought. A novel process for the iterative synthesis of discrete donor/acceptor-flanked oligostilbenes, key constituents in dye-sensitized solar cells, is described. The aqueous Wittig process is high yielding, proceeds with high (E)-stereoselectivity and allows facile product purification. 相似文献
97.
An enantioselective formal synthesis of berkelic acid is described. The key step involves a late-stage silyl enol ether addition to a benzannulated oxonium ion with subsequent spiroketalization leading to construction of the tetracyclic core. Thermodynamically controlled equilibration under acidic conditions affords the desired spiroketal configuration as a single diastereoisomer. 相似文献
98.
Benjamin A. Kowalski Robert R. McLeod 《Journal of Polymer Science.Polymer Physics》2016,54(11):1021-1035
Diffusive photopolymers are an area of intense recent materials development, spurred by interest in holographic data storage, display holography, and custom diffractive optical elements, among other applications. This review examines a range of photopolymer formulations of academic and commercial interest, and places their design strategies in context via quantitative analysis of the recording fidelity, maximum refractive index change and the degree to which they achieve this limit. Finally, this analysis is extended to estimate the scope of achievable future performance improvements. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1021–1035. 相似文献
99.
In this paper we present studies into the scope and limitations of asymmetric PTC epoxidation of enones and the oxidation-epoxidation of allylic alcohols using aqueous NaOCl in conjunction with a dihydrocinchonidine derived quaternary ammonium salt catalyst. 相似文献
100.
The paper is concerned with the asymptotic behavior as t → ∞ of solutions u(x, t) of the equation ut—uxx—∞;(u)=O, x∈(—∞, ∞) , in the case ∞(0)=∞(1)=0, ∞′(0)<0, ∞′(1)<0. Commonly, a travelling front solution u=U(x-ct), U(-∞)=0, U(∞)=1, exists. The following types of global stability results for fronts and various combinations of them will be given.
- Let u(x, 0)=u 0(x) satisfy 0≦u 0≦1. Let \(a\_ = \mathop {\lim \sup u0}\limits_{x \to - \infty } {\text{(}}x{\text{), }}\mathop {\lim \inf u0}\limits_{x \to \infty } {\text{(}}x{\text{)}}\) . Then u approaches a translate of U uniformly in x and exponentially in time, if a? is not too far from 0, and a+ not too far from 1.
- Suppose \(\int\limits_{\text{0}}^{\text{1}} {f{\text{(}}u{\text{)}}du} > {\text{0}}\) . If a ? and a + are not too far from 0, but u0 exceeds a certain threshold level for a sufficiently large x-interval, then u approaches a pair of diverging travelling fronts.
- Under certain circumstances, u approaches a “stacked” combination of wave fronts, with differing ranges.