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11.
Node M Hashimoto D Katoh T Ochi S Ozeki M Watanabe T Kajimoto T 《Organic letters》2008,10(13):2653-2656
The Michael addition of a chiral amine [(-)- 6] to alpha,beta-unsaturated esters ( 4) was attained and the stereoselectivity was inverted by changing the solvent from diethyl ether to tetrahydrofuran when alpha,beta-unsaturated esters having an aromatic ring at the beta-position were employed. In addition, the chiral auxiliary in the Michael adducts ( 9A) was facilely removed with N-iodosuccinimide to afford beta-amino esters ( 10A) and 2-methoxy- d-bornylaldehyde ( 11), which can be reclaimed to the chiral amine ( 6) by reductive amination. 相似文献
12.
Kimura H Fujiwara T Katoh T Nishide K Kajimoto T Node M 《Chemical & pharmaceutical bulletin》2006,54(3):399-402
(-)-Epibatidine, an excellent candidate of non-opioidal anesthesia, was formally synthesized in short steps from di-(l)-menthyl (R)-allene-1,3-dicarboxylate that was facilely prepared as a single isomer by means of crystallization-induced asymmetric transformation from a diastereomer mixture of (R)- and (S)-allene-1,3-dicarboxylates. Taking advantage of the chiral synthesis, derivatives of (-)-epibatidine were also prepared for targeting diagnostic agents that could bind nicotinic acetylcholine receptors (nAChRs) in the mammalian central nerve system. 相似文献
13.
An efficient new route based on intramolecular Heck cyclization of the diene 11 was developed to prepare the 4a-methyltetrahydrofluorene diterpenoids and utilized for the total synthesis of (+/-)-dichroanal B with significantly improved overall yield. 相似文献
14.
Node M Kodama S Hamashima Y Katoh T Nishide K Kajimoto T 《Chemical & pharmaceutical bulletin》2006,54(12):1662-1679
(+/-)-Galanthamine (1) was synthesized in excellent yield by applying PIFA-mediated oxidative phenol coupling of N-(4-hydroxy)phenethyl-N-(3',4',5'-trialkoxy)benzyl formamide (15b) as a key step. Because of the symmetrical characteristics of the pyrogallol moiety in the substrate (15b), the phenol coupling resulted in a sole coupling product except for volatile components from the oxidizing agent. On the basis of the successful results of the above strategy, (-)-galanthamine (1) was synthesized by employing a novel remote asymmetric induction, where conformation of the seven-membered ring in the product of the phenol coupling was restricted by forming a fused-chiral imidazolidinone ring with D-phenylalanine on the benzylic C-N bond of the tri-O-alkylated gallyl amino moiety. The conformational restriction and successive debenzylation of the protected hydroxyl groups on the pyrogallol ring caused diastereoselective cyclization to yield a cyclic ether having the desired stereochemistry for the synthesis of (-)-1. 相似文献
15.
Quasiclassical trajectory calculations for the planar reaction of O(1D) + N2O --> NO + NO are performed on a newly constructed ab initio potential energy surface. In spite of the reduced dimension approximation, the agreement between the computational and experimental results is largely satisfactory, especially on the similar amount of excitation of the two kinds of NO products found by Akagi et al. [J. Chem. Phys. 111, 115 (1999)]. Analyzing the initial condition dependence of the trajectories, we find that the trajectories of this reaction can be classified into four reaction paths, which correspond to respective areas in the space of initial condition. In one of the four paths, a long-lived stable complex is formed in the course of reaction, whereas the other three paths have direct mechanism. Contradictory to conventional understanding of the chemical reaction dynamics, the direct paths show more efficient energy exchange between the NO stretching modes than that with a long-lived intermediate. This indicates that the vibrational mode coupling along the short-lived paths is considerably stronger than expected. 相似文献
16.
The reaction of excited oxygen atom, O(1D2), with propylene has been studied under helium pressure up to 150 atm. The identified oxides and their limiting fractional yields are as follows: propylene oxide 0.22, propionaldehyde 0.22, acetone 0.11, allylalcohol 0.20, acrolein 0.02 and acetaldehyde 0.06. The mechanism of primary attack of O(1D2) on olefin is inferred on the basis of these figures. 相似文献
17.
[reaction: see text] When carbonyl compounds were allowed to react with phenyl trimethylsilyl selenide and tributylstannyl hydride in the presence of a catalytic amount of AIBN as a radical initiator, the hydrosilylation of the carbonyl compounds efficiently proceeded to give the corresponding silyl ethers in moderate to good yields. 相似文献
18.
Strongly enhanced N2 first positive emission N2(B 3Πg → A 3Σ+u) has been observed on addition of N atoms into a flowing mixture of Cl and HN3. The dependence of the emission intensity on N atom concentration gave a rate constant for the reaction N + N3 → N2(B 3Πg) + N2(X 1Σ+g) of i(1.6 ± 1.1) × 10?11 cm3 molecule?1 s?1. That for the reaction Cl + HN3 → HCl + N3 is (8.9 ± 1.0) × 10?13 cm3 molecule?1 s?1 from the decay of the emission. Comparison of the emission intensity in ClHN3 with that in ClHN3N gave the rate constant of the reaction N3 + N3 → N2(B 3Πg) + 2N2(X 1Σ+g) as 1.4 × 10?12 cm3 molecule?1 s?1 on the assumption that N + N3 yields only N2(B 3Πg) + N2(X 1Σ+g). 相似文献
19.
Chi-Huey Wong Randall L. Halcomb Yoshitaka Ichikawa Tetsuya Kajimoto 《Angewandte Chemie (International ed. in English)》1995,34(5):521-546
Recognition of carbohydrates by proteins and nucleic acids is highly specific, but the dissociation constants are relatively high (generally in the mM to high μM range) because of the lack of hydrophobic groups in the carbohydrates. The high specificity of this weak binding often comes from many hydrogen bonds and the coordination of metal ions as bridge between sugars and receptors. Though weak hydrophobic interactions between sugars and proteins have also been identified, the unique shape of a complex carbohydrate under the influence of anomeric and exo anomeric effects (the glycosidic torsion angles are therefore often not flexible but are typically somewhat restricted) and the topographic orientation of the hydroxyl and charged groups contribute most significantly to the recognition process. Studies on the structure–function relationship of a complex carbohydrate therefore require deliberate manipulation of its shape and functional groups, and synthesis of oligosaccharide analogs from modified monosaccharides is often useful to address the problem. The availability of various monosaccharides and their analogs for the synthesis of complex carbohydrates together with the information resulting from structural studies (such a NMR or X-ray studies on sugar–protein complexes) will certainly provide a basic understanding of complex carbohydrate recognition. An ultimate goal is to develop simple and easy-to-make non-carbohydrate molecules that resemble the active structure involved in carbohydrate–receptor interaction or the transition-state of an enzyme-catalyzed transformation (for example, glycosidase or glycosyltransferase reactions) and have the approprite bioavailability to be used to control the carbohydrate function in a specific manner. In part one of this review we described various enzymatic approaches to the synthesis of monosaccharides, analogs, and related structures. We describe in this part enzymatic and chemoenzymatic approaches to the synthesis of oligosaccarides and analogs, including those involved in E-selectin recognition, and strategies to inhibit glycosidases and glycosyltransferases. 相似文献
20.