N-磺化手性β-氨基醇修饰的钛试剂催化下的酮的不对称炔基化反应研究

The easily prepared and recoverable chiral N-sulfonylated fl-amino alcohol 2 in combination with Ti（OPr-i）4 was found to be an effective chiral catalyst for the enantioselective addition of alkynylzinc to ketones, which gave the useful products, i.e. chiral tertiary propargyl alcohols, with the ee up to 92%.     

The Synthesis of trans‐Flavan‐3‐ol Gallates by Regioselective Oxidative Etherification and Their Cytotoxicity Mediated by 67 LR

We report on a chiral pool approach for the synthesis of trans‐flavan‐3‐ol gallates from epichlorohydrin. The trans‐flavan‐3‐ol gallates were prepared by the cycloetherification of the phenol at the C2 benzylic position of 2‐acylozyl‐1,3‐diarylpropane during regioselective C?H oxidation. The 1,3‐diarylpropanes were prepared starting from epichlorohydrin by epoxide opening with A and B ring precursors, followed by acylation of the resultant alcohol with galloyl chloride. The availability of both the enantiomers of epichlorohydrin allowed the preparation of the corresponding enantiomer using the same procedure. The cytotoxicity of the compounds against U266 cells was tested, in which 5‐deoxy‐7,3′‐O‐dimethyl gallocatechin gallate exhibited cytotoxicity that was more than ten times stronger than natural (?)‐EGCG. In addition, the absolute configuration of the derivatives did not critically affect the biological activity.     

Asymmetric Total Synthesis of Stagonolide G

A simple asymmetric total synthesis of stagonolide G ( 1 ) is described. Asymmetric dihydroxylation, regioselective epoxide ring opening, and vinyl Grignard reactions are involved in generating the stereogenic centers C(4) and C(8), followed by Grubbs‐II‐catalyzed ring‐closing metathesis (RCM).     

Synthesis and cationic photopolymerization of monomers based on nopol

Starting with nopol [(R)‐(−)‐2‐(2′‐hydroxyethyl)‐6,6‐dimethyl‐8‐oxatricyclo[3.1.1.1^2,3]octane, I] as a substrate, two new, interesting monomers, allyl nopol ether epoxide III and nopol 1‐propenyl ether epoxide IV, were prepared. The photoinitiated cationic polymerizations of these two monomers as well as several other model compounds were studied using real‐time infrared spectroscopy. Surprisingly, the rates of epoxide ring‐opening polymerization of both monomers were enhanced as compared to those of the model compounds. Two different mechanisms which involve the free radical induced decomposition of the diaryliodonium salt photoinitiator were proposed to explain the rate acceleration effects. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1199–1209, 1999     

Synthesis and photochemical reaction of novel p-alkylcalix[n]arene derivatives containing cationically polymerizable groups

New photoreactive p-methylcalix[6]arene (MCA) derivatives containing cationically polymerizable groups such as propargyl ether (calixarene 1), allyl ether (calixarene 2), and ethoxy vinyl ether (calixarene 3) groups were synthesized with 80, 74, and 84% yields by the substitution reaction of MCA with propargyl bromide, allyl bromide, and 2-chloroethyl vinyl ether (CEVE), respectively, in the presence of either potassium hydroxide or sodium hydride by using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC). The p-tert-butylcalix[8]arene (BCA) derivative containing ethoxy vinyl ether groups (calixarene 4) was also synthesized in 83% yield by the substitution reaction of BCA with CEVE by using sodium hydride as a base and TBAB as a PTC. The MCA derivative containing 1-propenyl ether groups (calixarene 5) was synthesized in 80% yield by the isomerization of calixarene 2, which contained allyl ether groups, by using potassium tert-buthoxide as a catalyst. The photochemical reactions of carixarene 1, 3, 4, 5, and 6 were examined with certain photoacid generators in the film state. In this reaction system, calixarene 3 containing ethoxy vinyl ether groups showed the highest photochemical reactivity when bis-[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) (DPSP) was used as the catalyst. On the other hand, calixarene 1 containing propargyl ether groups had the highest photochemical reactivity when 4-morpholino-2,5-dibuthoxybenzenediazonium hexafluorophosphate (MDBZ) was used as the catalyst. It was also found that the prepared carixarene derivatives containing cationically polymerizable groups such as propargyl, allyl, vinyl, and also 1-propenyl ethers have good thermal stability. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1805–1814, 1999     

Cyclization Reactions of Aryl Propargyl Acetates with Tethered Epoxide Induced by Ruthenium Complex

Reactions of the ruthenium complex [Ru]Cl ([Ru]=Cp(PPh₃)₂Ru; Cp=η⁵‐C₅H₅) with several aryl propargyl acetates, each with an ortho ‐substituted chain of various length containing an epoxide on the aromatic ring and with or without methyl substitutents on the epoxide ring, bring about novel cyclizations. The cyclization reactions of HC≡CCH(OAc)(C₆H₄)CH₂(RC₂H₂O) (R=H, 6 a ; R=CH₃, 6 b , where RC₂H₂O is an epoxide ring) in MeOH give the vinylidene complexes 5 a – b , respectively, each with the Cβ integrated into a tetrahydro‐5H ‐benzo[7]annulen‐6‐ol ring. A C−C bond formation takes place between the propargyl acetate and the less substituted carbon of the epoxide ring. Further cyclizations of 5 a – b induced by HBF₄ give the corresponding vinylidene complexes 8 a – b each with a new 8‐oxabicyclo‐[3.2.1]octane ring by removal of a methanol molecule in high yield. For similar aryl propargyl acetates with a shorter epoxide chain, the cyclization gives a mixture of a vinylidene complex with a tetrahydronaphthalen‐1‐ol ring and a carbene complex with a tricyclic indeno‐furan ring. For the cyclization of 18 , with a longer epoxide chain, opening of the epoxide is required to afford the vicinal bromohydrin 22 , then tandem cyclization occurs in one pot. Products are characterized by spectroscopic methods as well as by XRD analysis.     

Cyclic poly(ε‐caprolactone) synthesized by combination of ring‐opening polymerization with ring‐closing metathesis,ring closing enyne metathesis,or “click” reaction

This article described the synthesis of cyclic poly(ε‐caprolactone) (PCL) via ring‐closing metathesis (RCM), ring closing enyne metathesis (RCEM), and “click” reaction of different difunctional linear PCL. Linear PCL precursors were prepared by ring‐opening polymerization (ROP) of ε‐caprolactone in bulk using 10‐undecen‐1‐ol or propargyl alcohol as the initiator, followed by reacting with corresponding acyl chloride containing vinyl or azido end group. The subsequent end‐to‐end intramolecular coupling reactions were performed under high dilution conditions. The successful transformation of linear PCL precursor to cyclic PCL was confirmed by Gel permeation chromatography, ¹H NMR, and Fourier transform infrared measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3022–3033, 2009     

A Direct Synthesis of Nucleoside Analogs Homologated at the 3′‐ and 5′‐Positions

A new route is presented to prepare analogs of nucleosides homologated at the 3′‐ and 5′‐positions. This route, applicable to both the D ‐ and L ‐enantiomeric forms, is suitable for the preparation of monomeric bis‐homonucleosides needed for the synthesis of oligonucleotide analogs. It begins with the known monobenzyl ether 3 of pent‐2‐yne‐1,5‐diol, which is reduced to alkenol 4 . Sharpless asymmetric epoxidation of 4 , followed by opening of the epoxide 5 with allylmagnesium bromide, gives a mixture of diols 6 and 7 . Protection of the primary alcohol as a silyl ether followed by treatment with OsO₄, NaIO₄, and mild acid in MeOH, followed by reduction, yields (2R,3R) {{[(tert‐butyl)diphenylsilyl]oxy}methyl}tetrahydro‐2‐(2‐hydroxyethyl)‐5‐methoxyfuran (=methyl 3‐{{[(tert‐butyl)diphenylsilyl]oxy}methyl}‐2,3,5‐trideoxy‐α/β‐D ‐erythro‐hexafuranoside; 10 ) (Scheme 1). Protected nucleobases are added to this skeleton with the aid of trimethylsilyl triflate (Scheme 2). The o‐toluoyl (2‐MeC₆H₄CO) and p‐anisoyl (4‐MeOC₆H₄CO) groups were used to protect the exocyclic amino group of cytosine. The bis‐homonucleoside analogs 11 and 14a are then converted to monothiol derivatives suitable for coupling (Schemes 3 and 4) to oligonucleotide analogs with bridging S‐atoms. This synthesis replaces a much longer synthesis for analogous nucleoside analogs that begins with diacetoneglucose (=1,2 : 5,6‐di‐O‐isopropylideneglucose), with the stereogenic centers in the final products derived from the Sharpless asymmetric epoxidation. The new route is useful for large‐scale synthesis of these building blocks for the synthesis of oligonucleotide analogs.     

Photoinduced and thermally induced cationic polymerizations using S,S‐dialkyl‐S‐(3,5‐dimethylhydroxyphenyl)sulfonium salts

A study of the photoinitiated and thermally initiated cationic polymerizations of several monomer systems with S,S‐dialkyl‐S‐(3,5‐dimethylhydroxyphenyl)sulfonium salt (HPS) photoinitiators bearing different lengths of alkyl chains on the positively charged sulfur atom has been conducted. HPS photoinitiators are capable of photoinitiating the cationic polymerization of a wide variety of epoxy and vinyl ether monomers directly on irradiation with short‐wavelength UV light. Aryl ketone photosensitizers are effective in extending the spectral response of these photoinitiators into the long‐wavelength UV region. Kinetic studies with real‐time infrared spectroscopy show that HPS photoinitiators exhibit good efficiency in the polymerization of epoxide and vinyl ether monomers. Comparative studies also demonstrate that S,S‐dimethyl‐S‐(3,5‐dimethyl‐2‐hydroxyphenyl)sulfonium salts are more active photoinitiators than their isomeric S,S‐dimethyl‐S‐(3,5‐dimethyl‐4‐hydroxyphenyl)sulfonium salt counterparts. Both types of HPS photoinitiators display reversible photolysis as a result of facile termination reactions that take place between the growing chains ends with the photogenerated sulfur ylides. Preliminary studies have shown that HPS photoinitiators can also be employed as thermal initiators for the cationic ring‐opening polymerization of epoxides at moderate temperatures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2570–2587, 2003     

Synthesis of biocompatible and biodegradable block copolymers of polyvinyl alcohol‐block‐poly(ε‐caprolactone) using metal‐free living cationic polymerization

Applications of metal‐free living cationic polymerization of vinyl ethers using HCl · Et₂O are reported. Product of poly(vinyl ether)s possessing functional end groups such as hydroxyethyl groups with predicted molecular weights was used as a macroinitiator in activated monomer cationic polymerization of ε‐caprolactone (CL) with HCl · Et₂O as a ring‐opening polymerization. This combination method is a metal‐free polymerization using HCl · Et₂O. The formation of poly(isobutyl vinyl ether)‐b‐poly(ε‐caprolactone) (PIBVE‐b‐PCL) and poly(tert‐butyl vinyl ether)‐b‐poly(ε‐caprolactone) (PTBVE‐b‐PCL) from two vinyl ethers and CL was successful. Therefore, we synthesized novel amphiphilic, biocompatible, and biodegradable block copolymers comprised polyvinyl alcohol and PCL, namely PVA‐b‐PCL by transformation of acid hydrolysis of tert‐butoxy moiety of PTBVE in PTBVE‐b‐PCL. The synthesized copolymers showed well‐defined structure and narrow molecular weight distribution. The structure of resulting block copolymers was confirmed by ¹H NMR, size exclusion chromatography, and differential scanning calorimetry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5169–5179, 2009     

Photochemically Cross‐linked Poly(aryl ether ketone) Rings

Summary: Macrocyclic phenyl ether ketones were prepared via pseudo high dilution condensation. Irradiation of these rings with UV light in a solution containing isopropyl alcohol as hydrogen donor resulted in a photo‐induced reduction of benzophenone to benzopinacol and the formation linked macrocycles. These rings can be heated to undergo ring‐opening polymerization and produce a polymer network or they can be added to a polycondensation reaction to prepare poly(ether ether ketones) with variable degrees of cross‐linking.

Photochemical cross‐linking of PEK rings and ring opening polymerization (n: 2–6). (a) hν, iPrOH, DCM; (b) CsF, 260 °C (polymer 3 ); (c) 4,4′–difluorobenzophenone, hydroquinone, diphenylsulphone, K₂CO₃, 260 °C (2% polymer 4 ; 6% polymer 5 ).     

Terminal‐vinyl liquid crystal crown ether‐modified,vinyl‐functionalized hybrid silica monolith for capillary electrochromatography

A novel terminal‐vinyl liquid crystal crown ether (2‐[4‐(3‐undeceny‐1‐yloxy)‐phenyl]‐2‐[4′‐(4′‐carboxybenzo‐15‐crown‐5)‐phenyl] propane) (LCCE) was synthesized and used to modify hybrid silica‐based monolithic column possessing vinyl ligands for CEC. The monolithic silica matrix containing vinyl functionalities was prepared by in situ co‐condensation of tetramethoxysilane and vinyl‐trimethoxysilane via sol–gel process and chemically modified with LCCE by free radical polymerization procedure using α,α'‐azobisisobutyronitrile as an initiator. Morphology of the monolithic column was examined by SEM and mercury porosimetry and the successful incorporation of terminal‐vinyl LCCE to the vinyl‐hybrid monolith was characterized by infrared spectra. Polycyclic aromatic hydrocarbons, benzenediols, carbamate pesticides and steroids, were successfully separated on the column. The separations were dominated hydrogen bonding supplied by crown ether and hydrophobic interaction offered by the liquid crystal. The effect of ACN concentration on separation performance was studied and the result indicated that RP retention mechanism played an important role. Reproducibilities of migration times for the six selected polycyclic aromatic hydrocarbons were reasonable, with relative standard deviation less than 3.50% for five consecutive within‐column runs and were 8.38–9.11% for column‐to‐column measurements of three columns.     

Combining Atom Transfer Radical Polymerization and Click Chemistry: A Versatile Method for the Preparation of End‐Functional Polymers

Summary: The bromine chain ends of well‐defined polystyrene ( = 2 700 g · mol⁻¹, = 1.11) prepared using ATRP were successfully transformed into various functional end groups (ω‐hydroxy, ω‐carboxyl and ω‐methyl‐vinyl) by a two‐step pathway: (1) substitution of the bromine terminal atom by an azide function and (2) 1,3‐dipolar cycloaddition of the terminal azide and functional alkynes (propargyl alcohol, propiolic acid and 2‐methyl‐1‐buten‐3‐yne). The “click” cycloaddition was catalyzed efficiently by the system copper bromide/4,4′‐di‐(5‐nonyl)‐2,2′‐bipyridine. In all cases, ¹H NMR spectra indicated quantitative transformation of the chain ends of polystyrene into the desired function.

Preparation of well‐defined functional polymers possessing diverse chain‐end functionalities by the combination of atom transfer radical polymerization and click chemistry.     

Synthesis and characterization of soluble polyimides derived from 2′,5′‐bis(3,4‐dicarboxyphenoxy)‐p‐terphenyl dianhydride

A novel bis(ether anhydride) monomer, 2′,5′‐bis(3,4‐dicarboxyphenoxy)‐p‐terphenyl dianhydride, was synthesized from the nitro displacement of 4‐nitrophthalonitrile by the phenoxide ion of 2′,5′‐dihydroxy‐p‐terphenyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and cyclodehydration of the resulting bis(ether diacid). A series of new poly(ether imide)s bearing laterally attached p‐terphenyl groups were prepared from the bis(ether anhydride) with various aromatic diamines via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by thermal or chemical imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were in the range of 0.62–1.26 dL/g. Most of the poly(ether imide)s obtained from both routes were soluble in polar organic solvents, such as N,N‐dimethylacetamide. All the poly(ether imide)s could afford transparent, flexible, and strong films with high tensile strengths. The glass‐transition temperatures of these poly(ether imide)s were recorded as between 214 and 276 °C by DSC. The softening temperatures of all the poly(ether imide) films stayed in the 207–265 °C range according to thermomechanical analysis. For all the polymers significant decomposition did not occur below 500 °C in nitrogen or air atmosphere. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1008–1017, 2004     

Poly(aryl ether)s containing o‐terphenyl subunits. II. Random poly(ether sulfone)s

The synthesis of a new A₂X‐type difluoride monomer, N‐2‐pyridyl‐4′,4″‐bis‐(4‐fluorobenzenesulfonyl)‐o‐terphenyl‐3,6‐dimethyl‐4,5‐dicarboxylic imide ( 3 ), is described. The monomer 3 was incorporated into a series of copoly(aryl ether sulfone)s by polymerization of 4,4′‐isopropylidenediphenol and 4,4′‐difluorophenylsulfone. The incorporation of monomer 3 had an observable effect on both the glass‐transition temperature of poly(aryl ether sulfone)s and the tendency for macrocyclic oligomers to form during polymerization. Replacement of the pyridyl imide group via a transimidization reaction with propargyl amine proceeded quantitatively and without polymer degradation. The acetylene containing copoly(aryl ether sulfone) could be crosslinked by simple thermal treatment, resulting in an increase in the glass‐transition temperature and solvent resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 9–17, 2000     

New Chiral Ligand N—Toluenesulfony1—2,2‘—dimethoxy—6,6’—di—aminobiphenyl for Catalytic Asymmetric Transfer Hydrogenation of Ketones

A new chiral ligand N‐p‐toluenesulfonyl‐2,2′‐dimethoxy‐6,6′‐diaminobiphenyl (Ts‐DMBDPPA) was prepared from 2,2′‐dimethoxy‐6,6′‐diaminobiphenyl via N‐tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee's up to 69.3%).     

Total Synthesis of Siomycin A: Construction of Synthetic Segments

The five practical segments for the total synthesis of siomycin A, that is, the dehydropiperidine segment A ( 5 ), the pentapeptide segment B ( 3 ), the dihydroquinoline segment C ( 6 ), and the β‐phenylselenoalanine dipeptide segments D ( 7 ) and E ( 4 ), were synthesized. Segment A ( 5 ) was constructed by the coupling of the azomethine ylide and the chiral sulfinimine, followed by the stereoselective reduction of the six‐membered imine function. Segment B ( 3 ) was synthesized by the phenylselenylation of the β‐lactone, stereoselective vinylzinc addition to the chiral sulfinimine, and oxazoline–thioamide conversion. Segment C ( 6 ) was prepared by the one‐pot olefination of the tetrahydroquinoline N‐oxide using triflic anhydride and triethylamine, stereoselective reduction of the methyl ketone function, and regioselective Yb(OTf)₃‐catalyzed epoxide opening by the amino group. Segments D ( 7 ) and E ( 4 ) were synthesized by coupling of the properly protected β‐phenylselenoalanines.     

Synthesis and asymmetric polymerization of (S)‐N‐maleoyl‐L‐leucine propargyl ester

A kind of N‐substituted maleimide (RMI), chiral (S)‐N‐maleoyl‐L ‐leucine propargyl ester ((S)‐PLMI) with a specific rotation of [α]₄₃₅ = ?27.5° was successfully synthesized from maleic anhydride, L ‐leucine, and propargyl alcohol. (S)‐PLMI was polymerized by three polymerization methods to obtain the corresponding optically active polymers. Asymmetric anionic, radical, and transition‐metal‐catalyzed polymerizations were carried out using organometal/chiral ligands, 2,2′‐azobisisobutyronitrile (AIBN) and (bicyclo [2,2,1]hepta‐2,5‐diene) chloro rhodium (I) dimer ([Rh(nbd) Cl]₂), respectively. Poly((S)‐PLMI) obtained by [Rh(nbd)Cl]₂ in DMF showed the highest specific rotation of ?280.6°. Chiroptical properties and structures of the polymers obtained were investigated by GPC, CD, IR, and NMR measurements. Two types of poly((S)‐PLMI)‐bonded‐silica gels as the chiral stationary phase (CSP) were prepared for high‐performance liquid chromatography (HPLC). Their optical resolution abilities were also elucidated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3722–3738, 2007     

Synthesis of Both Enantiomers of Flavanone and 2‐Methylchromanone

An efficient enantiospecific synthesis of the (R)‐ and (S)‐enantiomers of flavanone and 2‐methylchromanone is described. The key steps are a C,C‐bond formation by ring opening of a chiral epoxide with a dithiane anion, followed by a Mitsunobu cyclization. The products obtained have high enantiomeric purity.     

Efficient asymmetric addition of diethylzinc to aldehydes using C2‐novel chiral pyridine β‐amino alcohols as chiral ligands

A series of novel C₂‐symmetric chiral pyridine β‐amino alcohol ligands have been synthesized from 2,6‐pyridine dicarboxaldehyde, m‐phthalaldehyde and chiral β‐amino alcohols through a two‐step reaction. All their structures were characterized by ¹H NMR, ¹³C NMR and IR. Their enantioselective induction behaviors were examined under different conditions such as the structure of the ligands, reaction temperature, solvent, reaction time and catalytic amount. The results show that the corresponding chiral secondary alcohols can be obtained with high yields and moderate to good enantiomeric excess. The best result, up to 89% ee, was obtained when the ligand 3c (2S,2′R)‐2,2′‐((pyridine‐2,6‐diylbis(methylene))bisazanediyl))bis(4‐methyl‐1,1‐diphenylpentan‐1‐ol) was used in toluene at room temperature. The ligand 3g (2S,2′R)‐2,2′‐((1,3‐phenylenebis(methylene))bis(azanediyl))bis(4‐methyl‐1,1‐diphenylpentan‐1‐ol) was prepared in which the pyridine ring was replaced by the benzene ring compared to 3c in order to illustrate the unique role of the N atom in the pyridine ring in the inductive reaction. The results indicate that the coordination of the N atom of the pyridine ring is essential in the asymmetric induction reaction. Copyright © 2014 John Wiley & Sons, Ltd.