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131.
The base induced deprotonation of H-14 of 7-triethylsilyl- (7-TES-) and 7-tert-butoxycarbonyl- (7-BOC-) protected 13-oxo-baccatins gave the corresponding enolates, which were selectively aminated with electrophilic nitrogen donors, such as azodicarboxylates and tosyl azide. In particular, tosyl azide gave the corresponding 7-BOC- and 7-TES-13-oxo-14β-azido-baccatin III. Alternatively, the last compound was prepared via NaN3 induced azidation of the 13-silyl enol ether of 7-TES-13-oxo-baccatin III under oxidative (cerium ammonium nitrate) conditions. The 13-silyl enol ether was obtained in a multistep process by DBU induced silylation of 7-TES-13-oxo-baccatin III. The 7-TES-13-oxo-14β-azido-baccatin III was used as a key intermediate for the synthesis of a new family of antitumour taxanes containing amino based functional groups at the C-14 position, such as: 14β-azido, 14β-amino, 14β-amino 1, 14-carbamate, 14β-amino 1, 14-thiocarbamate, and 14β-amino N-tert-butoxycarbonyl-1,14-carbamate.  相似文献   
132.
Claudio Paolucci  Paolo Righi 《Tetrahedron》2007,63(51):12763-12768
The electrophilic iodocyclization reaction of (Z)- and (E)-5-n-alkylsubstituted 4-alken-1-ols followed by base-induced hydrodeiodination reaction stereoselectively gave, respectively, (Z)- and (E)-alkylidentetrahydrofurans in high yield. Completely different outcomes were observed with (Z)- and (E)-6,6-dimethylhept-4-en-1-ol: their iodocyclization furnished, respectively, threo- and erythro-2-(1-iodo-2,2-dimetylpropyl)tetrahydrofuran with high stereoselectivity. The threo isomer gave clean formation of 6-tert-butyl-3,4-dihydro-2H-pyran by base-induced ring expansion, while erythro isomer underwent a base-induced ring contraction to 1-cyclopropyl-3,3-dimethylbutan-1-one. Moreover, (Z)- and (E)-5-cyclopropylpent-4-en-1-ol underwent a 6-endo-iodocyclization to threo- and erythro-2-cyclopropyl-3-iodotetrahydro-2H-pyran, respectively, that under the same basic treatment, gave two isomeric 6-cyclopropyldihydro-2H-pyrans in a stereoselective fashion.  相似文献   
133.
Nitrosation of bis arylidene acetone oximes with nitrous acid in glacial acetic acid gives 3-vinyl pyrazolone-N,N′-dioxides in 32-37% yield. Similar reactions of 2-arylidene-6-(hydroxylamino-aryl-methyl)-cyclohexanone oximes give tricyclic compounds with dioxa-2,6-diaza-spiro[4,4]nona-2,8-diene ring systems in 77-84% yield.  相似文献   
134.
A convenient stereoselective synthesis of β-lactams from thio-Michael/aldol tandem adduct is described. syn-Selective tandem reaction followed by amidation and intramolecular SN2 reaction provided β-lactams in diastereomerically pure form. The tandem reaction with aliphatic aldehydes, on the other hand, afforded a mixture of diastereomers of corresponding tandem adducts in about 3:1 ratio so that the conversion to β-lactams afforded a diastereomeric mixture. As an alternative approach to prepare the tandem adducts, the stereoselective Michael addition of aliphatic thiols to Baylis-Hillman adduct was developed. The stereoselectivity was sensitive to the protective group at the hydroxyl group and TBS protection brought the most successful syn-selective formation of the tandem adducts. The procedure could be applied to the ketone derivatives of the Baylis-Hillman adduct but no selectivity was observed for the nitrile-Baylis-Hillman adducts. A similar conversion of the adduct provided desired β-lactams stereoselectively.  相似文献   
135.
彭荣达  郝健 《有机化学》2005,25(5):485-496
含氟β-氨基酸及其衍生物具有特殊的生理活性, 其合成方法的研究近年来受到广泛关注. 以直接氟化法和间接氟化法分类, 概述了含氟β-氨基酸及其衍生物的合成方法及最新研究进展, 对一些已知化合物的生理活性及药用价值作了初步归纳.  相似文献   
136.
137.
An efficient one-pot synthesis of substituted 4H-thiopyrans has been accomplished from a three-component reaction of α,β-unsaturated ketones, Lawesson’s reagent and alkynes under microwave irradiation.  相似文献   
138.
β-内酰胺类抗生素酶促合成新进展   总被引:1,自引:0,他引:1  
吴伟波  王旭  王娜  吴起  林贤福 《有机化学》2006,26(3):292-298
β-内酰胺类抗生素的合成在制药工业中占据重要的地位, 相关的酶促合成方法研究备受关注; 酶促合成显著提高合成效率, 减少三废的排放, 是实现绿色合成的有效方法. 综述了近年来β-内酰胺类抗生素酶促合成研究的新进展, 包括一锅合成法、原位产物排出法、介质技术和酶固定化方法.  相似文献   
139.
Indirect reduction of 1-phenylethylbromide (I) and 1-(4-isobutylphenyl)ethylchloride (II) in a carbon dioxide atmosphere containing tris(2,2-bipyridyl)nickel tetrafluoroborate (BPN) is studied. In the reactions the BPN complex exhibits properties of a one-electron mediator and catalyzes radical generation from aryl halides, which mostly undergo dimerization. Electroreduction of I and II in the presence of -cyclodextrin and BPN yields biaryls with a low enanthioselectivity (1.5%), which may indicate generation of a small amount of inclusion complexes and dimerization of intermediate radicals in the hydrophobic cavity of -cyclodextrin.  相似文献   
140.
α-, β-, and γ-cyclodextrins (CDs) marketed by five different companies were characterized from the thermal and structural point of view. Three αCD samples showed two-step DSC dehydration profiles and their XRD patterns were characteristic for αCD⋅6H2O form I, whereas one brand with an apparent three-step DSC dehydration behaviour was a mixture of αCD⋅6H2O form I and anhydrous αCD. The differences in the DSC profiles after dehydration and EGA onset decomposition temperatures recorded for the five βCD brands were attributed to different manufacturing and purification processes. The five γCDs brands showed a common thermal behaviour and very similar XRD patterns. The patterns did not match the idealized pattern of γCD⋅14.1H2O, indicating the occurrence of two different hydrated crystal structures. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   
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