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11.
[reaction: see text] Chiral C(4)-substituted (E)- or (Z)-1-alkynyl-1-trimethylsilyloxy-2-butene systems provide anti-(Z) or syn-(Z) conjugated dienyne, with a very high level of stereocontrol, on treatment with BF(3).OEt(2) in CH(2)Cl(2) at -50 degrees C in the presence of allyltrimethylsilane. The Cieplak conformation for (E)-substrates and neighboring-group participation for (Z)-substrates are considered to be responsible for the stereochemical consequences. 相似文献
12.
The title hydride and its deuteride were successfully synthesized. The crystal structure of the deuteride was determined by time-of-flight neutron powder diffraction. BaAlD(5) crystallizes with a new orthorhombic structure in space group Pna2(1) (No. 33), cell parameters a = 9.194(1) A, b = 7.0403(9) A, and c = 5.1061(6) A, Z = 4. BaAlH(5) is the first example that contains one-dimensional zigzag chains of [AlH(6)] along the crystallographic c axis. 相似文献
13.
A convenient one-pot synthesis of α-fluoro-α,β-unsaturated esters from ethoxy- and tert-butoxycarbonylmethyltriphenylphosphonium bromide was developed. The fluorinated phosphoranes, generated in situ from alkoxycarbonylmethyltriphenylphosphonium bromides and 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor®), undergo a Wittig reaction with aldehydes to yield α-fluoro-α,β-unsaturated esters with (Z)-selectivity. 相似文献
14.
Choji Kashima Yumiko Konno Nobutoshi Yoshiwara Tadakuni Tajima 《Journal of heterocyclic chemistry》1982,19(6):1535-1536
The regioselective synthesis of 3-hydroxyisoxazoles and 5-isoxazolones is accomplished by the reaction of β-amino α,β-unsaturated esters with hydroxylamine hydrochloride in the presence of appropriate bases. The total yield of isoxazole derivatives is sensitively influenced on the β-substituent group of the esters. 相似文献
15.
Tohru Takabatake Yumiko Hasegawa Minoru Hasegawa 《Journal of heterocyclic chemistry》1993,30(6):1477-1479
The cyclocondensations of benzofuroxan 1a with carbonyl compounds were smoothly and efficiently carried out by the adsorption of the components on the surface of silica gel or a molecular sieve to form a 2,3-disubstituted quinoxaline 1,4-dioxide. When the reactions using a molecular sieve 3A (powder) were carried out at 90°, the actual reaction times were reduced to 0.5-2 hours. Although Duerckheimer has reported the isolation of only the 7-substituted quinoxaline 1,4-dioxide when 5-methoxybenzofuroxan 1e was allowed to react with ethyl acetoacetate 2j , it produced only the 6-methoxy isomer as the reaction product by our method. 5-Carboxybenzofuroxan 1f did not react with the carbonyl compound. 相似文献
16.
This paper reports the synthesis of several 11,14-dimethoxydeoxypodocarpic acid derivatives from (+)-podocarpic acid. The synthesis of the naturally occurring sesquiterpene, (+)-winterin, from Drimys winteri illustrates a synthetic application of the 11,14-dimethoxy intermediates and establishes the absolute configuration for winterin. 相似文献
17.
18.
N Saito H Kawaguchi Y Ohtsuka N Shimizu S Inayama 《Chemical & pharmaceutical bulletin》1991,39(11):3085-3087
Hansenula anomala, which catalyzes an asymmetric reduction, was immobilized in bulk or spherical crosslinked polymers. The catalytic activity of the yeast for enantio-selective reduction of 3,8-dioxo-4-methoxycarbonyl-9-methyl-delta 4(10)-octalin (lab) was severely affected by the immobilization conditions, such as the crosslink density, and by hydrophobicity of polymers and other components used for immobilization, oxygen concentration in the medium, etc. In some immobilized systems, the ratio of resulting enantiomers was inverted from that in a free yeast system. 相似文献
19.
Fumiko Ohtsuka 《Geometriae Dedicata》1991,38(2):151-157
The theory of the ideal boundary has arisen as a method of a study of noncompact manifolds. In this paper we shall investigate properties of manifolds whose ideal boundaries satisfy some conditions related to the Tits metric. In Section 2 we shall consider in what conditions the Tits topology is equivalent to the sphere topology and in Section 3 the property of points at infinity which characterize the R-factor. Furthermore, in Section 4 we shall give a sufficient condition for a projective map to be isometríc.Partially supported by Grant-in-Aid for Encouragement of Young Scientists (No. 01740011), The Ministry of Education, Science and Culture, Japan. 相似文献
20.
A tritriacontanucleotide which has the sequence of the 5half molecule of E.coli glycine tRNA2, was synthesized by the phosphotriester method involving p-anisidate protection for the 3phosphate ends. Di- and trinucleotide units were prepared from 5dimethoxytrityl-2O-tetrahydrofuranyl-3?-O-(o-chlorophenyl)phosphoryl derivatives of uridine, N-benzoylcytidine, N-benzolyadenosine and N-iso-butyrylguanosine by condensation with 35unprotected nucleosides followed by phosphorylation to give 3phosphodiester blocks. The 3terminal dimers and trimers were synthesized by using 3(o- chlorophenyl)phosphoro-p-anisidates instead of 3?,5?-unprotected nucleosides. The 3?-phosphodiesters of oligonucleotides with a chain length of larger than 5 were obtained by removal of the 3?-phosphoro-p-anisidate with isoamyl nitrite. The 5dimethoxytrityl group was removed by treatment with zinc bromide under anhydrous conditions. Fragments were designed to use common dimer blocks and to reduce the step for 5deblocking of larger fragments. Finally a 3phosphodiester block with a chain length of 20 was condensed with a 5OH component (tridecanucleotide). The fully protected 33 mer was deblocked and purified by chromatography. The structural integrity of the product was confirmed by mobility shift analysis and complete digestion with RNase T2. 相似文献