甾族化合物不对称合成的研究XV: 光学活性3-氧杂-A-失碳甾族化合物的合成

我们在寻找新的甾体口服避孕药的研究中,设计了A-失碳-3,9(10)-二烯-18-甲基甾体(1)作为全合成研究的目的物.前文已报道从5’-甲基呋喃二噻烷阴离子2b与消旋甾体CD环合成原3b的共轭加成,合成了两个新的消旋3-氧杂-A-失碳甾体4b和5b.本文报道     

Dual-activation protocol for tandem cross-aldol condensation: An easy and highly efficient synthesis of α,α′-bis(aryl/alkylmethylidene)ketones

Commercially available lithium hydroxide monohydrate (LiOH·H₂O) was found to be a novel ‘dual activation’ catalyst for tandem cross-aldol condensation between cyclic/acyclic ketones and aromatic/heteroaromatic/styryl/alkyl aldehydes leading to an efficient and easy synthesis of α,α′-bis(aryl/alkylmethylidene)ketones at r.t. in short times. The reaction of aryl, heteroaryl, styryl and alkyl aldehydes with acyclic and five/six-membered cyclic ketones afforded excellent yields after 2 min to 1.25 h. The reaction conditions were compatible with various electron withdrawing and electron donating substituents, e.g. Cl, F, NO₂, OMe and NMe₂. The rate of the cross-aldol condensation was influenced by the nature of the ketone and electronic and steric factors associated with the aldehyde. The reaction took place at a faster rate for acyclic ketone (e.g., acetone) than that for cyclic ketone (e.g., cyclohexanone). In case of cycloalkanones, the rate of the reaction was dependent on the size of the ring of the cycloalkanone. The cross-aldol condensation of cyclopentanone was faster than that of cyclohexanone for a common aldehyde. In case of reactions involving aliphatic aldehyde having α-hydrogen atom no self-aldol condensation of the aldehyde took place.     

亲电缩聚反应合成芳香环状低聚醚酮砜及其开环聚合

"假高稀"条件下,以邻苯二酰氯为酰基化试剂,Lewis碱NMP存在下,通过亲电缩聚反应高产率地合成了2种芳香环状聚醚酮砜低聚物,利用MALDI-TOF-MS,NMR,GPC,FTIR,DSC等手段对环状结构进行了精确的表征.在负离子引发剂联苯双酚钾存在下,环状低聚物3a进行熔融开环聚合,得到了高分子量的线型聚合物,Tg为221.8℃.利用流变仪监测了环状低聚物3a开环聚合过程中的流变行为,结果表明,开环聚合初期的引发阶段,熔融体的黏度低于10Pa.s,随着时间的延长,黏度快速增长,而且低黏度的引发阶段随着引发剂浓度的增加而变短.     

Synthesis and ring‐opening polymerization of macrocyclic aryl ketone oligomers

A series of macrocyclic aryl ketone oligomers were prepared by the reaction of phthaloyl dichloride or isophthaloyl dichloride with various bridge‐linking electron‐rich aromatic hydrocarbons 3a–d under pseudo‐high dilution conditions in the presence of Lewis base via Friedel–Crafts acylation reaction. Detailed structural characterization of these oligomers confirmed the cyclic nature by a combination of MALDI‐TOF‐MS, GPC, and ¹H NMR analyses. These cyclic ketone oligomers have high solubility in organic solvents and the cyclic oligomers derived from phthaloyl dichloride are amorphous. The cyclic ketone oligomers readily undergo anionic ring‐opening polymerization in the melt by using potassium 4,4′‐biphenoxide as the initiator, producing linear, high molecular weight poly(ether ketone)s. Moreover, the isothermal chemorheology of the ring‐opening polymerization of cyclic oligomers 4a and 4b was also investigated. The results show that the shear viscosity of the molten reactive mixture is lower than 10 Pa · S at a constant shear rate of 0.05 rad/sec and increases slowly in the initial stage of ring‐opening polymerization. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of ethers and cyclic acetals in the presence of CBV-720 zeolite

СBV-720 zeolite was compared to H-Beta zeolite and KU-2 cation-exchange resin in the catalytic performance in addition of alcohols to norbornene, in condensation of aldehyde and ketone with di- and triols, and in the Prins reaction of olefins with formaldehyde. These reactions, when performed on СBV-720 zeolite, occur 1.5–2 times faster than on the other catalysts. The corresponding ethers and cyclic acetals were synthesized.     

Kinetically and thermodynamically controlled synthesis of tetraoxa[14]metacyclophanes and hexaoxa[16]metacyclophanes

The nucleophilic aromatic substitution of 1,5-difluoro-2,4-dinitrobenzene with 2-propylresorcinol in Et₃N/CH₃CN produces a mixture of syn and anti conformers of the cyclic tetramer and the cyclic hexamer with a kinetically controlled product distribution. Moreover, the reaction in DMF was catalyzed by CsF to also produce a mixture of these cyclic oligomers. In this case, however, the C-O bond is cleaved by the fluoride ion and the cyclization reaction is reversible; therefore, in the presence of excess CsF, the thermodynamically favored product (syn-isomer of cyclic tetramer) is obtained as the major product. The structures of the two conformational isomers of cyclic tetramers were determined by X-ray crystallography.     

Synthesis of orthogonally protected cyclic homooligomers from sugar amino acids

Two new families of orthogonally protected cyclic homooligomers with two to four sugar units were synthesized from pyranoid sugar amino acids. Cyclic oligomers composed of amide-linked sugar amino acids (1-3) were prepared by cyclization of linear oligomers of the novel orthogonally protected pyranoid sugar amino acid 12 using a solution-phase coupling method. These orthogonally protected cyclic molecules can be selectively or fully deprotected, affording the macrocycles ready to further functionalization. The straightforward reduction of the amide bonds in the cyclic oligomers 1-3 gave the corresponding amine-linked macrocycles 4-6. This kind of amine-linked carbohydrate-based cyclic oligomer has never been reported before. These flexible molecular receptors could be studied as molecular hosts for molecular, cationic, and anionic recognition. Conformational analysis by molecular modeling (AM1) showed that all of the deprotected cyclic trimers and tetramers preferred a (4)C(1) chair conformation with oxygen atoms of the sugar ring located on the interior of the cavity and the secondary hydroxyl groups outward. In the amide-linked macrocycles, all of the amide bonds are in s-trans conformation. The estimated size of the internal cavity is about 4.5 A for the cyclic trimer and 6.9 A for the cyclic tetramer. The amine-linked macrocycles displayed similar conformational behavior with a slight decrease in internal cavity.     

3‐[4′‐(Diethylboryl)phenyl]pyridine: Exclusive Crystallization of the Cyclic Tetramer

The crystallization of 3‐[4′‐(diethylboryl)phenyl]pyridine ( 1 ), which formed a mixture of oligomers in solution with the cyclic trimer as a major component, in acetone at 0 °C afforded a cyclic tetramer that co‐crystallized with solvent molecules. Similarly, solutions of compound 1 in toluene at 10 °C and in benzene at 8 °C furnished the cyclic tetramer with the incorporation of toluene and benzene molecules, respectively, thus suggesting that the cyclic tetramer was the minor component. ¹³C CP/MAS NMR spectroscopy of precipitates of compound 1 suggested that precipitation from acetone and toluene each afforded mixtures of the cyclic trimer and the cyclic tetramer, whereas precipitation from benzene exclusively furnished the cyclic tetramer. Therefore, it appeared that crystallization readily shifted the equilibrium towards the cyclic tetramer in benzene. The thermodynamic parameters for the equilibrium between these two oligomers in [D₆]benzene, as determined from a van′t Hoff plot, were ΔH°=?8.8 kcal mol^?1 and ΔS°=?23.7 cal mol^?1 K^?1, which were coincident with previously reported calculations and observations.     

Formation of Cyclic Oligomers in Concentrated Aqueous Solutions of Formaldehyde

An MNDO calculation gave the formation enthalpies of the components of equilibrium mixtures in concentrated aqueous acid solutions of formaldehyde. The results of this study suggest that intramolecular cyclization of linear oligomers with 5 and 9 CH₂O units, respectively, is the most plausible mechanism of formation of cyclic oligomers of formaldehyde — trioxane and tetraoxane. Ring protonation by the hydroxonium ion with ring opening is the most energetically favorable route of cyclic acetal decomposition.     

基质辅助激光解吸电离-飞行时间质谱表征6氟双酚A芳香环状聚醚酮(砜)

应用基质辅助激光解吸电离飞行时间质谱,在不同阳离子剂的存在下,对6氟双酚A聚芳醚酮(砜)环状低聚物的结构进行了确认,研究了环状化合物对金属离子的选择性及激光质谱表征含氟环状低聚物的适宜条件.     

New rearrangement reactions of the trichothecane framework]

Treatment of the apotrichothecane derivative 4 with H₂SO₄ in dioxan gave the acetal 6 and with H₂SO₄ in acetone the ketal 9 . Whereas the oxidation of 4 with Ag₂CO₃ yielded the hydroxy aldehyde 7 , the reaction with CrO₃ or MnO₂ led to the α,β-unsaturated ketone 8 . Upon treatment of 8 with base the cyclic keto ether 11 was obtained due to 1,4-addition. Acetylation of the latter compound gave a mixture consisting of the enolacetate 13 and the acetylketone 14 . The oxim 15 of ketone 14 was transformed to the nitrile 16 and not the Beckmann fragmentation product 18 . For the identification of the C(11) hydrogen atom in biosynthetic studies the triol 22 was oxidized to the keto aldehyde 26 which, upon treatment with methanolic K₂CO₃, gave the spirolactol 30 and the cyclic acetal 29 as second product when the reaction was carried out in dilute solution. The spirolactol 30 was oxidized to the spirolactone 31 . The corresponding 19 possessing the intact 12,13-epoxy group underwent rearrangement to the apotrichothecane derivatives 20 and 21 under the same conditions. Oxidation of the triol 22 with MnO₂ or CrO₃ gave a mixture of the acetal 23 and the keto acid 24 . – The mechanisms of the rearrangements observed are discussed.     

Reversal of chemoselectivity in Diels-Alder reaction with alpha,beta-unsaturated aldehydes and ketones catalyzed by Brønsted acid or Lewis acid

[reaction: see text] High chemoselectivity was observed in the Diels-Alder reaction of alpha,beta-unsaturated aldehyde and alpha,beta-unsaturated ketone with cyclopentadiene. Using Tf2NH as catalyst, the reaction gave Diels-Alder adduct derived from alpha,beta-unsaturated ketone as a major product. On the other hand, bulky Lewis acid, B(C6F5)3, gave mainly the cycloadduct of alpha,beta-unsaturated aldehyde and cyclopentadiene.     

氧化偶联聚合方法合成电活性聚芳醚酮

通过氧化偶联聚合方法成功地合成出电活性聚芳醚酮. 该反应条件温和, 操作简单, 室温下即可进行. 用红外光谱、核磁共振谱、高效凝胶渗透色谱、循环伏安、热失重、X射线衍射等技术对所合成的聚合物进行了表征, 并探讨了聚合物的性能.     

High-Yield Synthesis of 20-, 24-, and 28-Membered Macropentolide, -hexolide,and -heptolide,Respectively, from (R)- or (S)-3-hydroxybutanoic acid under Yamaguchi's macrolactonization conditions

The macrocyclic pentolide 1 , hexolide 2 , and heptolide 3 constitute ca. 80% of the oligomers formed in ca. 50% yield from enantiomerically pure 3-hydroxybutanoic acid under Yamaguchi's macrolactonization conditions. The FAB mass spectra of the MH⁺, M Na⁺, and MCs⁺ are reported (Figs. 2, 3, 5, and 6). No cyclic tetramer is detected. The ¹H-NMR spectra of the cyclic oligomers, of the monomer, and of the polymer (PHB) are very similar (Fig. 4). Directed synthesis of the open-chain dimer and tetramer of 3-hydroxybutanoic acid and attempted cyclization do not lead to the isolation of the cyclic tetramer.     

Convenient route to super-expanded calixpyrroles: synthesis of Calix

meso-Alkylporphyrinogen-like cyclic oligomers containing furans and pyrroles have been synthesized by "3 + 2" and "4 + 2" approaches. Condensation of 5,5,10,10,15,15-hexaethyl-21, 22-dioxatetrapyrromethane with 2,5-bis[(alpha-hydroxy-alpha, alpha-dimethyl)furan] resulted in the formation of cyclic hexamer and cyclic dodcamer. Effects of catalysts, temperature, inorganic additives, solvent, and reaction concentration were examined.     

Calixarenes. II. The isolation and characterization of the calix[4]arene and the bishomooxacalix[4]arene from A p-t-butylphenol-formaldehyde condensation product

The base-catalyzed condensation of p-tbutylphenol and formaldehyde, which yields a cyclic octamer (I, n=8) as the major product, has been shown to also yield a cyclic tetramer (I, n=4) and a bischomooxa cyclic tetramer (II).     

Isolation and identification of the linear and cyclic oligomers of poly(ethylene terephthalate) and the mechanism of cyclic oligomer formation

Chromatographic techniques are described which can be used to isolate and identify the linear and the cyclic oligomers of poly(ethylene terephthalate). Extraction of the oligomers from high molecular weight polymer produces at least eight different cyclic species, some of which are isolated and identified. The cyclic dimer, the cyclic trimer, and the cyclic tetramer of poly(ethylene terephthalate) have also been prepared by acid chloride esterification and transesterification. Similar materials can be isolated from the ethylene glycol distillate obtained from the polymer melt. The mechanism of cyclic oligomer formation has been studied by determining the rate of formation of the cyclic oligomers during polymerization and during melt extrusion of polyesters which did not initially contain cyclic oligomers. The rate of formation depends upon the concentration of hydroxyl groups; hence, the cyclic oligomers are formed by transesterification from the chain ends or cyclodepolymerization. Therefore oligomers are inevitably produced during polymerization.     

Stereoselective synthesis ofvic-halohydrins and an unusual Knoevenagel product from an organocatalyzed aldol reaction：A non-enamine mode

Stereoselective synthesis by an aldol reaction between chloroacetone and aldehyde was studied using a synthesized chiral organocatalyst and triethylamine. The reaction gave α-chloro-β-hydroxy ketones in excellent yield with highantiselectivity and enantioselectivity. The chiral organocatalyst was also used in the Knoevenagel reaction, which gave α-cyano-β-hydroxy ketones at a low tem-perature and the usual Knoevenagel product at a high temperature. Both products were obtained in good to moderate yield with goodanti selectivity in the case of α-cyano-β-hydroxy ketone deriva-tives.     

Synthesis of new telechelic oligomers and macro-monomers by “constructive degradation”

Telechelic acrylic oligomers possessing terminal carboxylic acid, ketone, aldehyde or hydroxy groups can be synthesised in good yields by the ozonolysis of free radical copolymers of the appropriate acrylic monomer with a small amount of a 1,3-diene, such as butadiene, 2,3-dimethyl-butadiene or 2,3-diphenyl-butadiene. The oligomers so-prepared have high end-functionalities (>98%), controllable average molecular weights, relatively narrow molecular weight distributions, and can be chain extended by a variety of means to give back high molecular weight polymers. Oligomers with perfect α-phenyl ketone-ω-carboxylic acid functionality can be prepared by ozonolysing copolymers containing low concentrations of units derived from phenyl acetylene. Photolysis of copolymers of an alkyl vinyl ketone with monomers such as styrene yield, directly, oligomers with polymerisable unsaturated end-groups, i.e. macromonomers.     

MALDI-TOF质谱表征聚芳醚酮环状低聚物及其组分分布

应用介质辅助激光解吸离子化飞行时间质谱(MALDI-TOFMS),以二羟基苯甲酸为介质、N₂(337nm)为激光源,对两种聚芳醚酮环状低聚物的结构进行了确认,研究了环状低聚物不同聚合度组分的分布规律,并且与GPC质量分析法作了比较,实验结果表明,MALDI-TQF质谱是分析环状低聚物的准确、快速的工具之一.