NaBH3CN and other systems as substitutes of tin and silicon hydrides in the light or heat-initiated reduction of halosugars: a tunable access to either 2-deoxy sugars or 1,5-anhydro-itols

UV light-promoted reduction of acetobromoglucose by NaBH₃CN in t-BuOH afforded 1,3,4,6-tetra-O-acetyl-2-deoxy-α-d-arabino-hexopyranose in high yield and purity, via a Surzur–Tanner rearrangement, while, with 10 mol % thiophenol added, acetylated 1,5-anhydro-d-glucitol was cleanly obtained. Such tin-free and mild reductions, presumed to proceed via radical pathways, were more efficient with NaBH₃CN compared to NaBH₄ or NaBD₄, and do not occur with acetochloroglucose. Similar reductions to 1,3,4,6-tetra-O-acetyl-2-deoxy-α-d-arabino-hexopyranose were achieved upon heating to 80 °C t-BuOH or CH₃CN solutions of NaBH₃CN and AIBN, but with a lower selectivity due to competing ionic reactions. With other pyranosyl bromides, reductions by NaBH₃CN could be tuned similarly (d-galacto), but some (d-manno, 5-thio-d-xylo) gave mainly or exclusively 1,5-anhydro-itols. Other conditions, or reagents promoting SET process, afforded also reduced products, but with lower rates or selectivities. Primary iodides were reduced readily with NaBH₃CN under UV light.     

Stereoselective Isomerization of Unsymmetrical Diallyl Ethers to Allyl (E)-Vinyl Ethers by a Cationic Iridium Catalyst

The stereoselective isomerization of unsymmetrical diallyl ethers to allyl (E)-vinyl ethers was carried out in the presence of a cationic iridium(I) catalyst. The catalyst prepared in situ by treating [Ir(cod)(PPh₂Me)₂]PF₆ with hydrogen was found to be an excellent catalyst to selectively isomerize the less substituted allyl group to an (E)-vinyl ether.     

Simultaneous determination of glucose, 1,5-anhydro-d-glucitol and related sugar alcohols in serum by high-performance liquid chromatography with benzoic acid derivatization

A new, simple and sensitive pre-column high-performance chromatographic method for the determination of diabetes marker d-glucose, 1,5-anhydro-d-glucitol and related compounds is reported. Sugars (d-glucose, d-galactose, d-mannose, sucrose and arabinose) were derivatized with benzoic acid (BA) at 80 degrees C for 60 min. l-Fucose, fructose, d-lactose, l-rhamnose, arabinose and ascorbic acid were not reacted. Sugar alcohols (xylitol, erythritol, mannitol, sorbitol myo-inositol) were also derivatized with BA at 80 degrees C for 60 min. The fluorescence derivatives were separated on a TSK amide 80 column (4.6 mm i.d. x 250 mm, 5 microm) with acetonitrile-50 mm acetate buffer (pH 5.6; 4:96, v/v) as the mobile phase. The detection wavelength of beizoic acid derivatives was lambda(ex) 275 nm and lambda(em) 315 nm. The detection limits of sugars were 10-80 microg/mL. The calibration graphs were linear up to 10 mg/mL. The relative standard deviations of 500 microg/mL sugars were 7.0-7.3%. The proposed method was compared with the enzymatic photometric glucose analysis method (Glucose B-Test II Wako). The correlation coefficient was 0.83 (n = 20) and y = 0.82x + 5.91, where y and x are concentrations in microg/mL obtained by the proposed pre-column HPLC and enzyme-photometric method, respectively. The detection limits of sugar alcohols were 100-1000 ng/mL. The calibration graphs were linear to 50 microg/mL and relative standard deviations of 10 microg/mL were 7.2-8.2%. The 1,5-AG data by the proposed method was also compared with the enzymatic photometric 1,5-AG analysis method (Rana AG 1,5-AG determination kit, Nihon Kayaku) and good correlation (r = 0.91, n = 20) was also obtained. The proposed method was applied to the simultaneous determination of d-glucose, 1,5-AG and related sugar alcohols in serum from healthy males.     

Synthesis and photopolymerization of 1-propenyl glycidyl ether

The ambifunctional monomer, 1-propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium-catalyzed isomerization reaction in high yield. 1-Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using ¹H- and, ¹³C-NMR spectroscopies and employing well-characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF₃OEt₂ followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether-bearing pendant 1-propenyl ether groups was subjected to a diaryliodonium salt-photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc.     

Synthesis of 2-(Triazolyl,Oxadiazolyl, and Pyrazolyl) Substituted 1,5-Benzothiazepin-S,S-Dioxide Derivatives of Potential Medicinal Interest

Abstract

The synthetic potential of 2,3,4,5-tetrahydrobenzo[b] [1,5]thiazepine-1,1,4-trione-2-carbohydrazide (5) which resulted from ethyl-4-oxo-2,3,4,5-tetrahydrobenzo[b] [1,5]thiazepine-2-carboxylate (3), on its oxidation with H₂O₂/AcOH followed by treatment with NH₂NH₂.H₂O, was exploited to provide an access to 2-triazolo, 2-oxadiazolo, and 2-pyrazolo substituted derivatives of 1,5-benzothiazepin-4-oxo-1,1-dioxides (6–10), respectively.     

Polymers derived from fluoroketones. III. Monomer synthesis,polymerization, and wetting properties of poly(allyl ether) and poly(vinyl ether)

The synthesis and polymerization of a series of perhaloalkyl allyl and vinyl ethers derived from perhaloketones is described. Data on the critical surface tension of wetting (γ_c) for high molecular weight polymers of heptafluoroisopropyl vinyl ether and low molecular weight poly(heptafluoroisopropyl allyl ether) is also presented. Preparation of the allyl ethers is a one-step, high-yield displacement reaction between the potassium fluoride–perhaloacetone adduct and an allyl halide, such as allyl bromide. The vinyl ethersare prepared by a two-step process which involves displacement of halide from a 1,2-dihaloethane with a KF–perhaloacetone adduct and dehydrohalogenation of the 1-halo-2-perhaloalkoxyethane to a vinyl ether. Low molecular weight polymers were obtained with heptafluoroisopropyl allyl ether by using a high concentration of a free-radical initiator. The low molecular weight poly(heptafluoroisopropyl allyl ether) had a γ_c of 21 dyne/cm. No polymer was obtained with tributylborane–oxygen or with VCl₃–AIR₃, with gamma radiation, or by exposure to ultraviolet light. High molecular weight polymers were obtained from heptafluoroisopropyl vinyl either by using either lauryl peroxide or ultraviolet light but not by exposure to BF₃–etherate. The γ_c for poly(heptafluoroisopropyl vinyl ether) ranged from 14.2 to 14.6 dyne/cm., and the significance of this value is discussed in relation to the γ_c for poly(heptafluoroisopropyl acrylate).     

Regioselective Transition‐Metal‐Free Allyl–Allyl Cross‐Couplings

Readily prepared allylic zinc halides undergo S_N2‐type substitutions with allylic bromides in a 1:1 mixture of THF and DMPU providing 1,5‐dienes regioselectively. The allylic zinc species reacts at the most branched end (γ‐position) of the allylic system furnishing exclusively γ,α′‐allyl–allyl cross‐coupling products. Remarkably, the double bond stereochemistry of the allylic halide is maintained during the cross‐coupling process. Also several functional groups (ester, nitrile) are tolerated. This cross‐coupling of allylic zinc reagents can be extended to propargylic and benzylic halides. DFT calculations show the importance of lithium chloride in this substitution.     

电化学还原合成1,5-二氨基萘

研究了以1,5-二硝基萘为原料电化学还原合成1,5-二氨基萘的反应. 室温下, 运用循环伏安法研究了1,5-二硝基萘的循环伏安行为, 1,5-二硝基萘的还原是一受扩散控制的不可逆反应; 循环伏安图上两个连续的还原峰对应于两个硝基的还原; 求出了反应的传递系数α₁在0.275～0.335之间, α₂在0.360～0.437之间. 探讨了电解电位(E)、底物浓度(c₁)、电解电量(Q)、硫酸浓度(c₂)以及溶剂(DMF)与水的体积比(Y)对产物产率的影响, 在最优条件下1,5-二氨基萘的产率最高可达77%.     

Copolymerization of propylene and 1,5‐hexadiene with stereospecific metallocene/Al(i‐Bu)3/[Ph3C][B(C6F5)4]

Copolymerizations of propylene (P) with 1,5‐hexadiene (1,5‐HD) were carried out with isospecific rac‐1,2‐ethylenebis(1‐indenyl)Zr(NMe₂)₂ [rac‐(EBI)Zr(NMe₂)₂, 1] and syndiospecific isopropylidene(cyclopentadienyl)(9‐fluorenyl)ZrMe₂ [i‐Pr(Cp)(Flu)ZrMe₂, 2] compounds combined with Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] as a cocatalyst system. Microstructures of poly(propylene‐co‐1,5‐HD) were determined by ¹H NMR, ¹³C NMR, Raman spectroscopies and X‐ray powder diffraction. The isospecific 1/Al(i‐Bu)₃/[Ph₃C][B(C₆F₆)₄] catalyst showed much higher polymerization rate than 2/Al(i‐Bu)₃/[Ph₃C][B(C₆F₆)₄] system, however, the latter system showed higher incorporation of 1,5‐HD (r_P = 8.85, r_1,5‐HD = 0.274) than the former system (r_P = 16.25, r_1,5‐HD = 0.34). The high value of r_P × r_1,5‐HD far above 1 demonstrated that the copolymers obtained by both catalysts are somewhat blocky. The insertion of 1,5‐HD proceeded by enantiomorphic site control; however, the diastereoselectivity of the intramolecular cyclization reaction of 1,2‐inserted 1,5‐HD was independent of the stereospecificity of metallocene compounds, but dependent on the concentration of 1,5‐HD in the feed. The insertion of the monomers by enantiomorphic site control could also be realized by Raman spectroscopy and X‐ray powder diffraction of the polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1590–1598, 2000     

Redox Reorganization: Aluminium Promoted 1,5-Hydride Shifts Allow the Controlled Synthesis of Multisubstituted Cyclohexenes

An efficient synthesis of cyclohexenes has been achieved from easily accessible tetrahydropyrans via a tandem 1,5-hydride shift–aldol condensation. We discovered that readily available aluminium reagents, e.g. Al₂O₃ or Al(O^tBu)₃ are essential for this process, promoting the 1,5-hydride shift with complete regio- and enantiospecificity (in stark contrast to results obtained under basic conditions). The mild conditions, coupled with multiple methods available to access the tetrahydropyran starting materials makes this a versatile method with exceptional functional group tolerance. A wide range of cyclohexenes (>40 examples) have been prepared, many in enantiopure form, showing our ability to selectively install a substituent at each position around the newly forged cyclohexene ring. Experimental and computational studies revealed that aluminium serves a dual role in facilitating the hydride shift, activating both the alkoxide nucleophile and the electrophilic carbonyl group.     

Side arm participation in lariat ether carboxylate-alkali metal cation complexes in solution

Lariat ether carboxylic acids of structure CECH₂OCH₂C₆H₄-2-CO₂H with crown ether (CE) ring sizes of 12-crown-4, 15-crown-5 and 18-crown-6 are prepared and converted into alkali metal-lariat ether carboxylate complexes. Absorptions for the diastereotopic benzylic protons in the ¹H NMR spectra of the complexes in CDCl₃ are utilized to probe the extent of side arm interaction with the crown ether-complexed metal ion as a function of the crown ether ring size and identity of the alkali metal cation.     

Studien zur Chemie von O,N- und S,N-haltigen Heterocyclen, 14. Mitt. Tricyclische 1,5-Benzothiazepine aus 2,3-Dihydro-1,5-benzothiazepin-4-amin

Summary Starting from 2,3-dihydro-1,5-benzothiazepin-4-amine (1) tricyclic 1,5-benzothiazepines were obtained. Reaction with ethyl bromopyruvat and ethyl aminoacetate hydrochloride led to the imidazo[2,1-d][1,5]benzothiazepines3 and6, respectively. The triazolo derivative8 was prepared by treatment of1 with triethyl orthoacetate/ammonia, followed by oxidative cyclization with sodium hypochlorite.

     

Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks

Poly(allyl glycidyl ether) and poly(allyl glycidyl ether‐co‐epichlorohydrin) were prepared by monomer‐activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i‐Bu₃Al]/[NOct₄Br] = 2?4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living‐like manner gradient‐type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate‐free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

HPLC separation of isomers of tetrahydro-1,5-benzothiazepines and tetrahydro-1,5-benzodiazepines

Summary Separation of positional and cis-trans-isomers of tetrahydro-1,5-benzothiazepines and tetrahydro-1,5-benzodiazepines was studied using reversed-phase chromatography and liquid-solid chromatography. The selection of solvent was based on the selective triangle for solvents. Systems of separation consisted of C₁₈ columns and methanol, THF or acetonitrile in water for the reversedphase method; it was suitable for the separation of positional isomers only but the liquid-solid method was suitable for separation of cis-trans-isomers as well as positional isomers using a silica column and ethyl ether, chloroform or ethyl acetate as the mobile phase respectively.     

Complexes de l'iridium avec le cyclooctadiène-1,5 VI. Le chloro η-cyclooctadiène-1,5 η-propène iridium et son produit de réaction avec l'oxyde de carbone

Treating (CODIrCl)₂, (COD = 1,5-cyclooctadiene), with allyl alcohol gives a new complex (C₁₁H₁₈ClIr), as well as the previously described addition complex with diallyl ether. It is shown to be a monomeric planar tetracoordinated complex in which a propene molecule is coordinated to iridium through its double bond.The product of reaction of this compound with CO is described, and a formula is postulated.     

Allyl ethers as combined plasticizing and crosslinkable side groups in polycarbonate‐based polymer electrolytes for solid‐state Li batteries

Allyl ether‐functional polycarbonates, synthesized by organocatalytic ring‐opening polymerization of the six‐membered cyclic carbonate monomer 2‐allyloxymethyl‐2‐ethyltrimethylene carbonate, were used to prepare non‐polyether polymer electrolytes. UV‐crosslinking of the allyl side groups provided mechanically stable electrolytes with improved molecular flexibility—T_g below ?20 °C—and higher ionic conductivity—up to 4.3 × 10^?7 S/cm at 25 °C and 5.2 × 10^?6 S/cm at 60 °C—due to the plasticizing properties of the allyl ether side groups. The electrolyte function was additionally demonstrated in thin‐film Li battery cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2128–2135     

Synthesis and Characterization of New 3‐(3‐Hydroxyphenyl)‐4‐ alkyl‐3,4‐dihydrobenzo[e][1,3]oxazepine‐1,5‐dione Compounds

A series of 3‐(3‐hydroxyphenyl)‐4‐alkyl‐3,4‐dihydrobenzo[e][1,3]oxazepine‐1,5‐dione compounds with general formula C_nH_2n+1CNO(CO)₂C₆H₄(C₆H₄OH) in which n are even parity numbers from 2 to 18. The structure determinations on these compounds were performed by FT‐IR spectroscopy which indicated that the terminal alkyl chain attached to the oxazepine ring was fully extended. Conformational analysis in DMSO at ambient temperature was carried out for the first time via high resolution ¹H NMR and ¹³C NMR spectroscopy.     

1,5-Diphosphabicyclo[3.3.1]nonan

1,5-Diphosphabicyclo [3.3.1]nonane 1,5-Diphosphabicyclo[3.3.1]nonane 8 has been obtained by free-radical cyclization of CH₂?CHCH₂(H)PCH₂P(H)CH₂CH?CH₂ 6 and 1-allyl-1,3-diphosphorinane 7 . For the synthesis of 6 and 7 the chlorophosphine Cl₂PCH₂PCl₂ 1 is used as a starting material, which can be converted into Me₂N(Cl)PCH₂P(Cl)NMe₂ 3 by reaction with (Me₂N)₂PCH₂P(NMe₂)₂ 2 . Treatment of 3 with two equivalents of allyl lithium and cleavage of the PN bonds in CH₂?CHCH₂(Me₂N)PCH₂P(NMe₂)CH₂CH?CH₂ 4 with diluted HCl affords CH₂?CHCH₂(H)(O)PCH₂P(O)(H)CH₂CH?CH₂ 5 . Phenylsilane is used for the first time as a reducing agent to obtain a secundary phosphine like 6 from the secundary phosphine oxide ( 5 ). Prolonged heating increases the yield of the byproduct 7 in the mixture of 6 and 7 . Reactions of the trivalent phosphorus in 8 with CS₂, CH₃I, POCl₃, NO, sulfur, and KSeCN, respectively, delivers the corresponding derivatives 9–17 . The compounds decribed are characterized by ¹H, ¹³C, ³¹P, ⁷⁷Se n.m.r., i.r., and m.s. data.     

2-取代氨基-6-甲基-5-氧代-4-正丁基-4,5-二氢-1,2,4-三氮唑并[1,5-a]嘧啶类衍生物的合成

以2-溴丙酸甲酯、α,α-二氯甲基甲醚和胍唑为原料, 经缩合以及环化反应制得2-氨基-6-甲基-5-氧代-4,5-二氢-1,2,4-三氮唑并[1,5-a]嘧啶. 为了提高其在有机溶剂中的溶解性, 该化合物再同1-溴丁烷发生亲核取代反应得到了2-氨基-6-甲基-5-氧代-4-正丁基-4,5-二氢-1,2,4-三氮唑并[1,5-a]嘧啶, 然后与芳基醛和叔丁基异氰发生Ugi多组分反应, 合成了一系列具有潜在催吐活性的2-取代氨基-6-甲基-5-氧代-4-正丁基-4,5-二氢-1,2,4-三氮唑并[1,5-a]嘧啶类衍生物, 产品结构经质谱、核磁共振谱及元素分析确认.     

Bio‐Inspired Formal Synthesis of Hirsutellones A–C Featuring an Electrophilic Cyclization Triggered by Remote Lewis Acid‐Activation

A bio‐inspired strategy was used to complete the formal synthesis of the antitubercular hirsutellone B and congeners A and C, through construction of its decahydrofluorene core from a linear polyene strand activated at both ends by a silyl enol ether and an allyl acetate. Our synthesis features a key electrophilic cyclization, starting with the remote activation (by [Yb(OTf)₃] or BF₃ ? OEt₂) of the allyl acetate and stereoselectively affording the C ring. This was followed by an intramolecular Diels–Alder reaction to get the tricyclic core of the natural product. The stereoselective reduction of the resulting ketone towards the formal intermediate was critical to the success of this strategy.