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1.
Shin-ichi NayaMakoto Nitta 《Tetrahedron》2003,59(21):3709-3718
Novel condensation reaction of tropone with N-substituted and N,N′-disubstitued barbituric acids in Ac2O afforded 5-(cyclohepta-2′,4′,6′-trienylidene)pyrimidine-2(1H),4(3H),6(5H)-trione derivatives (8a-f) in moderate to good yields. The 13C NMR spectral study of 8a-f revealed that the contribution of zwitterionic resonance structures is less important as compared with that of 8,8-dicyanoheptafulvene. The rotational barriers (ΔG‡) around the exocyclic double bond of mono-substituted derivatives 8a-c were obtained to be 14.51-15.03 kcal mol−1 by the variable temperature 1H NMR measurements. The electrochemical properties of 8a-f were also studied by CV measurement. Upon treatment with DDQ, 8a-c underwent oxidative cyclization to give two products, 7 and 9-substituted cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborates (11a-c·BF4− and 12a-c·BF4−) in various ratios, while that of disubstituted derivatives 8d-f afforded 7,9-disubstituted cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate (11d-f·BF4−) in good yields. Similarly, preparation of known 5-(1′-oxocycloheptatrien-2′-yl)-pyrimidine-2(1H),4(3H),6(5H)-trione derivatives (14a-d) and novel derivatives 14e,f was carried out. Treatment of 14a-c with aq. HBF4/Ac2O afforded two kinds of novel products 11a-c·BF4− and 12a,c·BF4− in various ratios, respectively, while that of 14d-f afforded 11d-f. The product ratios of 11a-c·BF4− and 12a-c·BF4− observed in two kinds of cyclization reactions were rationalized on the basis of MO calculations of model compounds 20a and 21a. The spectroscopic and electrochemical properties of 11a-f·BF4− and 12a-c·BF4− were studied, and structural characterization of 11c·BF4− based on the X-ray crystal analysis and MO calculation was also performed. 相似文献
2.
Gabriela Huelgas Sylvain Bernès Leticia Quintero Cecilia Anaya de Parrodi Patrick J. Walsh 《Tetrahedron》2007,63(51):12655-12664
The synthesis of atropisomeric 2-substituted benzamides 2a-e, 3a-e, and 4a-e, and characterization by X-ray structure analysis of 2d, 2e, 3c, 3e, 4c, and 4e are reported. Dynamic 1H NMR spectroscopic studies of benzamides 2b-d, 3b-d, and 4b-d indicate that only two of the four possible rotamers are present in solution, with population ratios ranging between 1.5:1 and 4.1:1. The measured free energy of activation to interconversion of the rotamers ranged from 12.4 to 18.9 kcal mol−1. Benzamides ArCON[(S)-phenethyl]2 (2e, 3e, and 4e), exhibited atropisomer ratios between 1.7:1 and 1:1, and free energies of interconversion of the rotamers ranged from 11.5 to 17.6 kcal mol−1. The highest rotation barriers were observed for the ortho-nitro derivatives 2a-e. Molecular calculations at the semiempirical level (PM3MM) gave free energies of activation for benzamides 2e and 3e of 23.6 and 12.4 kcal mol−1, respectively, which are comparable to the experimental values. 相似文献
3.
Shin-ichi Naya 《Tetrahedron》2005,61(21):4919-4930
Novel photo-induced oxidative cyclization was accomplished to synthesize areno[b]pyrimido[5,4-e]pyran-2,4(1,3H)-dionylium ions 13a-c+·ClO4−. Furthermore, 13a-c+·BF4− and their phenyl-substituted derivatives 19a,b+·BF4− were alternatively synthesized by the reaction of salicylaldehyde and its naphthyl derivatives with barbituric acids and subsequent treatment with aq. HBF4. Structural characteristics of 13a-c+ and 19a,b+ were clarified on inspection of the UV-vis and NMR spectral data as well as X-ray crystal analyses. The electrochemical properties were studied by the CV measurement. In a search for reactivity, reactions of 13a-c+·BF4− with some nucleophiles, hydride, benzylamine, and H2O, were also carried out. The photo-induced autorecycling oxidation reactions of 13a-c+·BF4− toward some amines under aerobic conditions were carried out to give the corresponding imines (isolated by converting to the corresponding 2,4-dinitrophenylhydrazones) in 643-3600% yield (recycling number of 13a-c+·BF4−: 6.4-36.0). 相似文献
4.
The article describes the synthesis and evaluation of the dichromate anion (Cr2O72−/HCr2O7−) extraction properties of p-tert-butylcalix[4]arene diamide derivatives (5-7) containing different binding sites. Among these compounds, 6 and 7 have been synthesized via aminolysis in a toluene-methanol solvent system with 3-aminomethylpyridine and 3,6-dioxa-1,8-diamino octane, respectively. On the other hand, compound 5 has been synthesized via an acid chloride method due to its inefficiency under aminolysis. The extraction properties of these diamides toward dichromate anions are studied by liquid-liquid extraction. The results show that p-tert-butylcalix[4]arene diamide derivative 7 exhibited a much higher affinity toward dichromate anions than that of 6 due to its special structure, while 5 was an ineffective ligand for these anions. 相似文献
5.
Duangrat ThongkumThawatchai Tuntulani 《Tetrahedron》2011,67(42):8102-8109
New bispyrenyl thioureas linked by polyethylene glycol (PEG) chains, L1-L3, and methoxy benzene pyrene thiourea, L4, were synthesized. Upon binding with F− in CHCl3, L1-L3 exhibited strong excimer emission bands (IE) and weak monomer emission bands (IM), while L4 displayed the same intensity of both bands. However, little or no change was observed in fluorescence spectra of L1 upon adding OH−, AcO−, BzO−, H2PO4−, Cl−, Br−, and I−. Therefore, only F− induced the pyrene excimer formation. Job’s plots showed 1/1 or 2/2 complexation of L1 with F−. Ratios of IE/IM of L1·F− complex were dependent on the concentration of L1, implying that the dimerization of L1 proceeded via the intermolecular excimer formation. Among L1-L4, L1 possessed the highest binding constant and sensitivity toward F− implying the importance of the linking PEG chain. L1 was demonstrated to be an excellent probe for F− in CHCl3 with the detection limit as low as 46.2 μg/L. 相似文献
6.
Shin-ichi NayaMakoto Nitta 《Tetrahedron》2003,59(23):4157-4165
The synthesis and properties of a novel type of bis(heteroazulen-3-yl)methyl cations, bis(2-oxo-2H-cyclohepta[b]furan-3-yl)methyl cation salt and nitrogen analogues, (9a-c·PF6−) and (9a-c·BF4−), as well as bis(heteroazulen-3-yl)ketones (12a-d) are studied. The synthetic method was based on a TFA-catalyzed electrophilic aromatic substitution on the heteroazulenes (6a-d) with paraformaldehyde to afford the corresponding disubstituted methane derivatives 7a-d, followed by oxidative hydrogen abstraction with DDQ, and subsequent exchange of the counter-anion by using aq. HPF6 or aq. HBF4. In addition, the reaction of 7a-d with 2.2 equiv. amounts of DDQ afforded carbonyl compounds 12a-d. The delocalization of the positive charge of 9a-c was evaluated by the 1H and 13C NMR spectral data. The thermodynamic stability of cations 9a-c was evaluated to be in the order 9a<9b<9c on the basis of their reduction potentials measured by cyclic voltammetry (CV) and pKR+ values (2.6-10.3) obtained spectrophotometrically. The reduction waves of cations 9a-c were irreversible, suggesting the dimerization of the radical species generated by one-electron reduction. This was demonstrated by the reduction of 9a·BF4− with Zn powder to give dimerized product 14a. In addition, the quenching of 9a·BF4− with MeOH/NaHCO3 gives ether derivative 15a, which is proposed for the precursor for synthesizing tris(heteroazulene)-substituted methyl cations bearing two different heteroazulene-units. 相似文献
7.
Giuseppe Romanazzi Piero Mastrorilli Ahlam Sibaouih Timo Repo Gian Paolo Suranna Cosimo Francesco Nobile 《Tetrahedron》2009,65(47):9833-355
A series of soluble quaterthiophenes (4Ta-g) bearing ester groups in the α,ω-terminal positions separated from the quaterthiophene core by ethylene (4Ta-c), vinylene (4Td-f) or ethynylene (4Tg) spacers was synthesized by means of a Pd-catalyzed homocoupling of bithiophenes proceeding via C-H bond activation. The synthetic approach gave satisfying yields of 4Ta-f but resulted in only 3% yield of 4Tg due to the competitive hydrofluorination of the triple bond. The quaterthiophenes 4Ta-g were characterized by NMR, FTIR, UV-vis, PL spectroscopies, HRMS, TGA and CV. Thin-films of 4Ta-g were deposited either by spin-coating or by thermal evaporation on Si/SiO2 for the fabrication of top-contact OTFTs. The devices prepared using 4Ta-c bearing the ester functional group separated from the quaterthiophene core by an ethylene spacer showed average hole field-effect mobility up to 2.7×10−3 cm2 V−1 s−1 and up to 6×10−3 cm2 V−1 s−1 for solution processed and for thermally evaporated OTFTs, respectively. The remarkably high solubility of 4Ta-c, along with their respectable performances in OTFTs render these molecules promising for practical applications as active layers in chemically-sensitive devices. 相似文献
8.
Zoran D?oli? Damir Kova?ek Draginja Mrvoš-Sermek Neda Slade Jan Balzarini Oliver Zerbe Leonardo Scapozza 《Journal of Molecular Structure》2003,655(2):229-241
The novel optically active derivatives of 2,2′-disubstituted-1-aminocyclopropane-1-carboxylic acid (−)-2 and (+)-3 were synthesised from the spiro-azlactone (+)-1. Oxidation of the diol moiety of (+)-3 gave by ring enlargement the racemic mixture of 2,3-dihydrofuran derivative (±)-6. This conversion is explained by stepwise rearrangement of the initially formed tetrasubstituted cyclopropanecarbaldehyde 4 through zwitterionic's reactive intermediate 5. The formation of (±)-6 is preferred energetically as established by ab initio calculations of the ground states and possible intermediates for that rearrangement. The crystal structure and absolute configuration of the compounds (+)-1, (−)-2, (+)-3 and (−)-7 were determined by single-crystal X-ray diffraction method. All four compounds possess Z-configuration of the cyclopropane ring. The dioxolane ring in the structures (+)-1 and (−)-2 adopts half-chair conformation, while the cyclopropane ring and geminally substituted groups in the structures (−)-2, (+)-3 and (−)-7 possess the anticlinal conformation. The molecules of the compound (+)-1 are connected by very weak intermolecular hydrogen bond of C-H?O type. In the compounds (−)-2, (+)-3 and (−)-7inter- and intramolecular hydrogen bonds of N-H?O type were observed. The spiro-compound (+)-1 exhibited a more pronounced inhibitory activity against the proliferation of murine leukemia and human T-lymphocytes cells than other type of tumor cell lines and normal human fibroblast cells. 相似文献
9.
Supriya Biswas 《Journal of organometallic chemistry》2007,692(14):2897-2902
Rate constants for the nucleophilic substitution reactions of imidazolide (IZ−) and benzimidazolide (BIZ−) ions with 4-Cr-Z and 5 in MeOH at 25 °C are reported and Hammett ρ values are evaluated to be 1.50 ± 0.10 and 1.51 ± 0.08 for 4-Cr-Z-IZ− and 4-Cr-Z-BIZ− reactions, respectively. The comparable reactivity and also almost identical ρ values for these reactions indicate that there is no difference in sensitivity towards electronic effects due to slightly bigger size of BIZ− over IZ− and bond formation at the transition states are equally progressed. The higher ρ values for these reactions compared to those with a wide range of nucleophiles may arise mainly due to lower polarity of the solvent MeOH which enhances the requirement for stabilization of the negative charge in the transition state by the Z-substituents. 相似文献
10.
Shin-ichi Naya 《Tetrahedron》2004,60(41):9139-9148
Ring transformation of 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]furan- 8(7H),10(9H)-dionylium tetrafluoroborate 4+·BF4− to 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]pyrrrole-8(7H),10(9H)-dionylium tetrafluoroborate 6a-d+·BF4− consists of the reaction of 4+·BF4− with amines and subsequent exchange of the counter-ion using aq. HBF4. Reactions of 4+·BF4− with aniline and 4-substituted anilines afforded the corresponding pyrrole derivatives 6a-c+·BF4− directly in good yields. On the other hand, reaction of 4+·BF4− with benzylamine gave the troponeimine intermediate 9, which was not converted to 6d+·BF4− and reverted to 4+·BF4− by adding HBF4; however, it was converted to 6d+·BF4− upon treatment with (COCl)2 or SOCl2, followed by exchange of the counter-ion. In a search for the characteristics of 9, inspection and comparison of the X-ray crystal analyses, NMR and UV-vis spectra, and CV measurement of 9 and N,N-disubstituted troponeimine derivatives 12 were carried out to suggest the remarkable structure of 12 having ionic C-O bonding between the imine-carbon atom and the oxygen atom of the barbituric acid moiety in the solid state. Thus, characteristics of 9 were ascribed to the sterically hindered and favorable conformation of N-protonated troponeimine intermediates. Furthermore, novel photo-induced oxidation reactions of a series of 4+·BF4−, 5+·BF4−, and 6a,e+·BF4− towards some amines under aerobic conditions were carried out to give the corresponding imines in 455-8362% yields [based on compounds 4+, 5+, and 6a,e+], suggesting the oxidation reaction occurs in an autorecycling process. Mechanistic aspects of the amine-oxidation reaction are also postulated. 相似文献
11.
The reactions of PhSe−, PhS− and Se2− with N-{2-(chloroethyl)}pyrrolidine result in N-{2-(phenylseleno)ethyl}pyrrolidine (L1), N-{2-(phenylthio)ethyl}pyrrolidine (L2), and bis{2-pyrrolidene-N-yl)ethyl selenide (L3), respectively, which have been explored as ligands. The complexes [PdCl2(L1/L2)] (1/7), [PtCl2(L1/L2)] (2/8), [RuCl(η6-C6H6)(L1/L2)][PF6] (3/9), [RuCl(η6-p-cymene)(L1/L2)][PF6] (4/10), [RuCl(η6-p-cymene)(NH3)2][PF6] (5) and [Ru(η6-p-cymene)(L1)(CH3CN)][PF6]2·CH3CN (6) have been synthesized. The L1-L3 and complexes were found to give characteristic NMR (Proton, Carbon-13 and Se-77). The crystal structures of complexes 1, 3-6, 9 and 10 have been solved. The Pd-Se and Ru-Se bond lengths have been found to be 2.353(2) and 2.480(11)/2.4918(9)/2.4770(5) Å, respectively. The complexes 1 and 7 have been explored for catalytic Heck and Suzuki-Miyaura coupling reactions. The value of TON has been found up to 85 000 with the advantage of catalyst’s stability under ambient conditions. The efficiency of 1 is marginally better than 7. The Ru-complexes 3 and 9 are good for catalytic oxidation of primary and secondary alcohols in CH2Cl2 in the presence of N-methylmorpholine-N-oxide (NMO). The TON value varies between 8.0 × 104 and 9.7 × 104 for this oxidation. The 3 is somewhat more efficient catalyst than 9. 相似文献
12.
Dipanwita Das 《Journal of organometallic chemistry》2010,695(7):955-2564
1-(Phenylselenomethyl)-1H-benzotriazole (L1) and 1-(4-methoxyphenyltelluromethyl)-1H-benzotriazole (L2) have been synthesized by reacting 1-(chloromethyl)-1H-benzotriazole with in situ generated nucleophiles PhSe− and ArTe−, respectively. The complexes of L1 and L2 with Pd(II) and Ru(II)(η6-p-cymene) have been synthesized. Proton, carbon-13, Se-77 and/or Te-125 NMR spectra authenticate both the ligands and their complexes. The single crystal structures of L1, L2 and [RuCl(η6-p-cymene)(L)][PF6] (L = L1: 3, L = L2: 4) have been solved. The Ru-Se and Ru-Te bond lengths have been found 2.4801(11) and 2.6183(10) Å, respectively. The palladium complexes, [PdCl2(L)] (L = L1: 1, L = L2: 2) have been explored for Heck and Suzuki-Miyaura C-C coupling reactions. The TON values are upto 95,000. The Ru-complexes have been found promising for catalytic oxidation of alcohols (TON ∼ 7.8-9.4 × 104). The complexes of telluroether ligands are as efficient catalysts as those of selenoether ones and in fact better for catalytic oxidation. 相似文献
13.
Shin-ichi NayaMakoto Nitta 《Tetrahedron》2003,59(37):7291-7299
Uracil-annulated heteroazulenes, 6-substituted 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]pyrrole-8(7H),10(9H)-dionylium tetrafluoroborates 7a,b·BF4−, which are the isoelectronic compounds of 5-dezazaflavin, were synthesized. X-Ray crystal analysis and MO calculations were carried out to clarify the structural characteristics of 7a,b·BF4−. The stability of cations 7a,b is expressed by the pKR+ values which were determined spectrophotometrically to be 10.9 and 11.2, respectively. The electrochemical reduction of 7a,b exhibited high reduction potentials at −0.84 and −0.87 (V vs Ag/AgNO3) upon cyclic voltammetry (CV). A good linear correlation between the pKR+ values and reduction potentials (E1red) of 7a,b·BF4− and reference compounds 4·BF4− and 5·BF4− was obtained. In a search of the reactivity, reactions of 7a,b·BF4− with some nucleophiles, hydride and diethylamine, were carried out to clarify that the introduction of nucleophiles to give regio-isomers is dependent on the nucleophile. The photo-induced oxidation reactions of 7a,b·BF4− toward some alcohols under aerobic conditions were carried out to give the corresponding carbonyl compounds in more than 100% yield [based on compounds 7a,b·BF4−], suggesting the oxidizing function of 7a,b·BF4− toward alcohols in the autorecycling process. 相似文献
14.
Two new diamagnetic, mononuclear and aminated porphyrin complexes of O,O-trans-Cd (3-trans) and O,S-cis-Cd (4-cis) have been synthesized and characterized by 1H, 13C NMR spectroscopy. The crystal structures of (acetato)(N-2-furancarboxamido-meso-tetraphenylporphyrinato)cadmium(II) [Cd(N-NHCO-2-C4H3O-tpp)(OAc); 3-trans] and (acetato)(N-2-thiophenecarboxamido-meso-tetraphenylporphyrinato)cadmium(II) [Cd(N-NHCO-2-C4H3S-tpp)(OAc); 4-cis] were determined. The coordination sphere around Cd2+ is a distorted square-based pyramid in which the apical site is occupied by a bidentate chelating OAc− group for 3-trans and 4-cis. The plane of three pyrrole nitrogen atoms [i.e., N(1), N(2), N(4) for 3-trans and N(1), N(2), N(3) for 4-cis] strongly bonded to Cd2+ is adopted as a reference plane 3N. The N(3) and N(4) pyrrole rings bearing the 2-furancarboxamido (Fr) and 2-thiophenecarboxamido groups in 3-trans and 4-cis, respectively, deviate mostly from the 3N plane, thus orienting separately with a dihedral angle of 33.4° and of 31.0°. In 3-trans, Cd2+ and N(5) are located on different sides at 1.06 and −1.49 Å from its 3N plane, while in 4-cis, Cd2+ and N(5) are also located on different sides at 1.04 and −1.53 Å from its 3N plane. An attractive electrostatic interaction between the Cd2+ and O(4)− atoms in furan stabilizes the O,O-trans conformer of 3. A repulsive electrostatic interaction between Cd2+ and S(1)+ destabilizes the O,S-trans conformer of 4. Both of these repulsive and the mutually attractive interactions between S(1)+ and O(3)− atoms favor the O,S-cis rotamer of 4 both in the vapor phase and in low polarity solvents. NOE difference spectroscopy, HMQC and HMBC were employed for the unambiguous assignment of the 1H and 13C NMR resonances of 3-trans and 4-cis in CDCl3 at 20 and −50 °C. 相似文献
15.
Nisachol NerngchamnongBenjamas Chailap Pannee LeeladeeOrawon Chailapakul Chomchai Suksai Thawatchai Tuntulani 《Tetrahedron letters》2011,52(22):2914-2917
Two derivatives of p-tert-butylcalix[4]arenes 1 and 2 containing diethyl ester and amidoferrocene units as cation and anion binding sites, respectively, have been synthesized. Both compounds were isomeric with different topology for accommodating ions. 1H NMR spectroscopy, cyclic voltammetry, and square-wave voltammetry were used to study the binding abilities of receptors 1 and 2 toward anions. Both receptors were found to bind Br− and I− selectively in the presence of Na+. The electrochemically oxidized ferrocenium form of para-isomer 2 in the free form was found to sense AcO− selectively, but demonstrated a negative sensing in the presence of Na+. In contrast, the electrochemically oxidized ferrocenium form of meta-isomer 1 was found to enhance sensing of AcO− and Cl− in the presence of Na+. 相似文献
16.
2-Methoxy- and 2-(p-methoxybenzyloxy)-1-(2-tributylstannylethylidene)cyclohexanes 22 and 23 were prepared from 2-methoxy- and 2-(p-methoxybenzyloxy)cyclohexanones 12 and 13. The allylstannane 22 was transmetallated stereoselectively with tin(IV) chloride at −78 °C to generate an allyltin trihalide, which reacted with aldehydes to give (Z)-(3-hydroxyalkylidene)-2-methoxycyclohexanes 24 with excellent 1,5-syn-stereocontrol. Similar reactions with aldehydes were observed for the 2-(p-methoxybenzyloxy) substituted allylstannane 23. The structure of the product 24f prepared from p-nitrobenzaldehyde was confirmed by an X-ray structure determination of its p-nitrobenzoate ester 27. 相似文献
17.
Shigeki Sano 《Tetrahedron letters》2005,46(16):2883-2886
α-Alkynyl-α-ethoxycarbonyl cyclopentanones 1a-c and cyclohexanones 2a-c were readily synthesized by the reaction of ethyl 2-oxocyclopentanonecarboxylate 6 and ethyl 2-oxocyclohexanonecarboxylate 7 with alkynyllead triacetates 5a-c obtained from lithium acetylides 4a-c and lead tetraacetate. Treatment of 1a-c and 2a-c with 1 N KOH in THF or with n-Bu4N+OEt− in EtOH and THF gave the corresponding conjugated allenyl esters 8a-c, 9a-c, 10a-c, and 11a-c in good to excellent yields, respectively. 相似文献
18.
A series of N-(2-pyridyl)benzamides (1)-(11) and their nickel complexes, [N-(2-pyridyl)benzamide]dinickel(II) di-μ-bromide dibromide (12)-(16) and (aryl)[N-(2-pyridyl)benzamido](triphenylphosphine)nickel(II) (17)-(24), were synthesized and characterized. The single-crystal X-ray analysis revealed that 12 and 14 are binuclear nickel complexes bridged by bromine atoms and each nickel atom adopts a distorted trigonal bipyramidal geometry. The key feature of the complexes 17, 19 and 23 is each has a six-membered nickel chelate ring including a deprotonated secondary nitrogen atom and an O-donor atom. The nickel complexes show moderate to high catalytic activity for ethylene oligomerization with methylaluminoxane (MAO) as cocatalyst. The activity of 12-16/MAO systems is up to 3.3 × 104 g mol−1 h−1 whereas for 17-24/MAO systems it is up to 4.94 × 105 g mol−1 atm−1 h−1. The influence of Al/Ni molar ratio, reaction temperature, reaction period and PPh3/Ni molar ratio on catalytic activity was investigated. 相似文献
19.
(±)-(4,5-anti)-4-Benzyloxy-5-hydroxy-(2E)-hexenoic acid 6 was subjected to δ-lactonization in the presence of 2,4,6-trichlorobenzoyl chloride and pyridine to give the α,β-unsaturated-δ-lactone congener (±)-7 (87% yield) accompanied by trans-cis isomerization. This δ-lactonization procedure was applied to the chiral synthesis of (+)-(4S,5R)-7 or (−)-(4R,5S)-7 from the chiral starting material (+)-(4S,5R)-6 or (−)-(4R,5S)-6. Deprotection of the benzyl group in (+)-(4S,5R)-7 or (−)-(4R,5S)-7 by the AlCl3/m-xylene system gave the natural osmundalactone (+)-(4S,5R)-5 or (−)-(4R,5S)-5 in good yield, respectively. Condensation of (−)-(4R,5S)-5 and tetraacetyl-β-d-glucosyltrichloroimidate 22 in the presence of BF3·Et2O afforded the condensation product (−)-8 (97% yield), which was identical to tetra-O-acetylosmundalin (−)-8 derived from natural osmundalin 9. 相似文献
20.
Epimeric 3-carboxycyclopentylglycines (+)-10/(−)-10 and (+)-11/(−)-11 were efficiently prepared by the way of a sequence of Diels-Alder and retro-Claisen reactions. The synthesis incorporates a concise and inexpensive chemoenzymatic resolution of racemic compounds 4,5a, the N,O-protected derivatives of amino acids 10,11. Systematic screening with different enzymes and microorganisms was performed to select a very efficient catalyst for the separation of the racemic mixtures. The reaction conditions allowing deprotection of both ester and amino functions and to avoiding epimerization processes were studied. Enantiomers (i.e., (+)-10/(−)-10 and (+)-11/(−)-11) were obtained in high enantiopurity. The absolute configuration of all stereocenters was unequivocally assigned. 相似文献