The Total Synthesis of Inostamycin A

The first total synthesis of inostamycin A is described. With efficient and stereoselective synthetic routes to aldehyde 3 and ketone 4 developed through asymmetric aldol reactions, addition reactions and reduction, and with chiral building blocks, the two large fragments were coupled with remarkable anti stereoselectivity and efficiency by aldol condensation. The coupling reaction provided the complete carbon skeleton with all the requisite functional groups and stereogenic centers for inostamycin A. The two quaternary carbons at C20 and C16 of ketone 4 were elaborated in a highly stereocontrolled manner by addition reactions of the transmetallated 5 to ethyl ketone 6 and the transmetallated 7 to methyl ketone 8 , respectively, in which the use of LaCl₃ for transmetallation was critical for high coupling efficiency.     

Thermal Degradation Behavior of Vinyl Ketone Polymers and Copolymers with Styrene

Thermal degradation behavior of six alkyl vinyl ketone (RVK) polymers and copolymers with styrene was investigated by means of infrared spectrometry (IR), thermogravimetry (TG), derivative TG (DTG), and differential scanning calorimetry (DSC). The observed TG curves of the RVK polymers changed with both structure of their substituents and initiators used, and the temperature of the beginning of weight loss for the radical polymers increased in the order: poly(methyl isopro-penyl ketone) < poly(methyl vinyl ketone) < poly(ethyl vinyl ketone) < poly(isopropyl vinyl ketone) < poly(tert-butyl vinyl ketone). From the infrared spectral determination of thermally degraded polymers, the formation of a cyclized structure was observed. It was also found from the results of thermal degradation of the RVK copolymers with styrene at 210° C that the formation of such a cyclized unit tended to increase in the order: tert-butyl vinyl ketone < isopropyl vinyl ketone < ethyl vinyl ketone < methyl vinyl ketone.     

Stereoselective aldol coupling of α,β-acetylenic ketones promoted by MgI2

A highly stereoselective synthesis of (Z)-β-iodovinyl ketone has been achieved with the tandem formation of CC and CI bonds in a three-component reaction. This new catalysis utilizes MgI₂ as a Lewis acid as well as an iodine source for a Michael-type addition. α,β-Acetylenic ketone is initially converted to an active β-iodo allenolate intermediate and then can be attacked by a variety of aldehydes to afford Z-selective Baylis-Hillman adducts in excellent yields.     

Efficient Synthesis of Diaryl Ketones by Nickel‐Catalyzed Negishi Cross‐Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect

The first Negishi cross‐coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross‐coupling was accomplished with bench‐stable, inexpensive precatalyst [Ni(PPh₃)₂Cl₂] that shows high functional‐group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, <10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional‐group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross‐coupling under mild conditions.     

CC Coupling of Ketones with Methanol Catalyzed by a N‐Heterocyclic Carbene–Phosphine Iridium Complex

An N‐heterocyclic carbene–phosphine iridium complex system was found to be a very efficient catalyst for the methylation of ketone via a hydrogen transfer reaction. Mild conditions together with low catalyst loading (1 mol %) were used for a tandem process which involves the dehydrogenation of methanol, C?C bond formation with a ketone, and hydrogenation of the new generated double bond by iridium hydride to give the alkylated product. Using this iridium catalyst system, a number of branched ketones were synthesized with good to excellent conversions and yields.     

Synthesis of poly(aryl ether ketone)s containing diphenyl moieties by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), was prepared by Friedel–Crafts reaction of 4‐bromobenzoyl chloride and diphenyl, followed by condensation with potassium phenoxide. Novel poly(ether ketone ketone) (PEKK)/poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) copolymers were synthesized by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of diphenyl ether (DPE) and BPOBDP, in the presence of anhydrous aluminum chloride and N‐methyl‐pyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers obtained were characterized by various analytical techniques such as FT‐IR, DSC, TGA, and wide‐angle X‐ray diffraction (WAXD). The results showed that the resulting copolymers exhibited excellent thermal stability due to the existence of diphenyl moieties in the main chain. The glass transition temperatures are above 152°C, the melting temperatures are above 276°C, and the temperatures at a 5% weight loss are above 548°C in nitrogen. The copolymers with 50–70 mol% BPOBDP had tensile strengths of 101.5–102.7 MPa, Young's moduli of 3.23–3.41 GPa, and elongations at break of 12–17%. All these copolymers were semicrystalline and insoluble in organic solvents. Copyright © 2008 John Wiley & Sons, Ltd.     

Comparative analysis of 13C shielding constants stereospecificity in the silicon and germanium derivatives of acetylenic aldehyde and ketone oximes based on the 13C NMR spectroscopy and GIAO calculations

In the acetylenic aldehyde oximes with substituents containing silicon and germanium, the ¹³C NMR signal of the C‐2 carbon of triple bond is shifted by 3.5 ppm to lower frequency and that of the C‐3 carbon is moved by 7 ppm to higher frequency on going from E to Z isomer. A greater low‐frequency effect of 5.5 ppm on the C‐2 carbon signal and a greater high‐frequency effect of 11 ppm on the C‐3 carbon signal are observed in the analogous acetylenic ketone oximes. The carbon chemical shift of the C?N bond is larger by 4 ppm in E isomer relative to Z isomer for the aldehyde and ketone oximes. The ²⁹Si chemical shifts in the silicon containing acetylenic aldehyde and ketone oximes are almost the same for the diverse isomers. The trends in changes of the measured chemical shifts are well reproduced by the gauge‐including atomic orbital (GIAO) calculations of the ¹³C and ²⁹Si shielding constants. Copyright © 2009 John Wiley & Sons, Ltd.     

A new terpene ketone,a component of the essential oil ofElsholtzia ciliata

A new terpene ketone which has been called dehydroelsholtsia ketone has been isolated from the essential oil ofElsholtzia ciliata (Thumb.) Hyl. The structure of dehydroelsholtzia ketone as 3-methyl-2-(3-methylbut-2-enoyl)furan has been proposed on the basis of a study of its IR, PMR, mass and¹³C spectra and has been confirmed by its conversion into elsholtzia ketone.     

SBS三嵌段共聚物在丁酮溶剂中的降解

论文研究了SBS三嵌段共聚物在选择性溶剂丁酮中的降解。采用超速离心沉降速度法、毛细管粘度法、GPC和IR的研究手段,证实了SBS/丁酮溶液存放时间较长时,溶液中SBS分子发生降解,降解发生在聚丁二烯嵌段的不饱和双键。从而也表明SBS/丁酮溶液中胶束行为的不稳定归国于SBS分子的降解。     

Total syntheses of (-)-alpha-kainic acid and (+)-alpha-allokainic acid via stereoselective C-H insertion and efficient 3,4-stereocontrol

Reported herein is a novel approach to the total syntheses of (-)-alpha-kainic acid and (+)-alpha-allokainic acid, where the stereochemistries on C(2), C(3), and C(4) of the pyrrolidine core were introduced efficiently and selectively. A regio- and stereoselective C-H insertion reaction was utilized to prepare the gamma-lactam as an intermediate. A Michael-type cyclization of phenylsulfone with a conjugated acetylenic ketone was developed to prepare the tricyclic ketone as a key intermediate for (-)-alpha-kainic acid. Subsequently, a stereoselective dephenylsulfonylation was carried out successfully to secure the cis relationship at C(3) and C(4) centers. An unprecedented acetylation on the phenylsulfone, followed by a stereoselective dephenylsulfonylation, secured the trans relationship at C(3) and C(4) centers in (+)-alpha-allokainic acid.     

Antenna-Initiated Photochemistry in Polyfunctional Steroids. Intramolecular Singlet and Triplet Energy Transfer between Aryl, Ketone, and Alkene Groups in 6beta-(Dimethylphenylsiloxy)-5beta-androstanes(1)

Steroids have been prepared that bear a dimethylphenylsiloxy (DPSO) group and additional C3 and/or C17 ketone functionalities. The DPSO group has been used to harvest 266 nm photons and then activate the ketone functionalities through intramolecular singlet-singlet energy transfer (intra-SSET). Thus, the monoketones 3,3-(ethylenedioxy)-6beta-(DPSO)-5beta-androstan-17-one (6) and 6beta-(DPSO)-5beta-androstan-3-one (8) both exhibit DPSO-initiated photochemistry at the carbonyl groups. Irradiation of the diketone, 6beta-(DPSO)-5beta-androstane-3,17-dione (5), gives two ring D-derived photoproducts, an epimer (19) and an enal (18), both coming from the C17 ketone excited singlet state. Here Phi(intra-SSET) from the aryl antenna to the carbonyl groups is ca. 88% efficients and occurs with a rate of ca. 6.5 x 10(9) s(-)(1), with the chemistry indicative of facile intra-SSET between the C3 and C17 ketones. The alkylidene group at C3 (i.e., as in 6beta-(DPSO)-3(E)-ethylidene-5beta-androstan-17-one (33) and its Z isomer (34)) has no effect on the rate or efficiency of aryl activation of the C17 ketone.     

Isolation and characterization of unsymmetrical C(60)Me(5)O(3)H, a cage-opened bisepoxide ketone: tautomerism involving a fullerene cage bond

Bisepoxide ketone C(60)Me(5)O(3)H, possessing a nine-membered hole in the cage, has been isolated from the reaction of C(60)Cl(6) with methyllithium followed by hydrolysis. It is a tautomer of the recently isolated bisepoxide fullerenol, this tautomerism being the first example involving a cage C-C bond, and may be driven by cage strain. Like the fullerenol, the ketone gives a high C(58)(+) fragmentation ion intensity during EI mass spectrometry.     

H-Cu-P络合物在有机合成中的应用

本文综述了[HCuPPh₃]₆的合成方法及氢-铜-膦化合物在有机合成中的应用。作为还原剂,[HCuPPh₃]₆可选择性地还原α,β-不饱和酸酯、酮、醛、硝基化合物、腈中的碳碳双键,炔烃中碳碳三键;作为催化剂,可促进氢气、硅氢化合物对上述化合物中碳-碳不饱和键的还原。改变膦配体的结构后的铜-氢-膦化合物可催化对上述化合物中碳碳双键或α,β-不饱和醛、酮、烷基芳基酮中羰基的选择性还原反应。采用合适的手性膦配体,已实现了对上述前手性底物中碳-碳双键、羰基的高对映选择性还原。氢-铜-膦化合物独特的反应及催化性能已用于天然产物及有重要生物活性的化合物的合成中。     

Preparation of some 2,4,6-cycloheptatriene-1-yl ketones. Strong preference for the norcaradiene isomer in the case of the 2,4,6-cycloheptatriene-1-yl t-butyl ketone

t-Butyl, i-propyl and phenyl 2,4,6-cycloheptatriene-1-yl ketone ({=1a},{=c},{=d}, respectively) have been synthesized. At ?139°C, rather unexpectedly, the t-butyl ketone {=1a} exists in a 1:1 equilibrium with its norcaradiene isomer {=2a}.     

Cationic Polymerization Behavior of Some Vinyl Ketone Cyclodimers

Cationic polymerizations of 2,3-dihydropyran derivatives, methyl isopropenyl ketone cyclodimer (MIPKD), chloromethyl vinyl ketone cyclodimer (CMVKD), and methyl isopropenyl ketone-chloromethyl vinyl ketone cyclocodimer, D(MIPK-CMVK), were investigated in the presence of various Lewis acids at 0°C. These monomers were found to undergo cationic polymerization to give low molecular weight polymer which consisted mainly of a vinylene structure. However, the ring-opening polymerization was found to occur to a minor extent in cationic polymerizations of MIPKD and D(MIPK-CMVK) cyclodimer.     

Liquid—liquid equilibria of the system water + acetic acid + methyl ethyl ketone at several temperatures

This article reports the solubilities and equilibrium data of the ternary mixture water + acetic acid + methyl ethyl ketone at 25, 35 and 45°C, and the equilibrium data of the binary system water + methyl ethyl ketone over the range 20–55°C. NRTL and UNIQUAC equations have been fitted to the experimental data for the ternary system, which are also compared with the values predicted by the UNIFAC method.     

Synthesis of copolymers of poly(ether sulfone ether ketone ketone) and poly(ether ketone diphenyl ketone ether ketone ketone) by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl(BPOBDP), was synthesized via a two‐step synthetic procedure. A series of novel poly(ether sulfone ether ketone ketone)/poly(ether ketone diphenyl ketone ether ketone ketone) copolymers were prepared by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of 4,4′‐diphenoxydiphenylsulfone (DPODPS) and 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers with 10–50 mol% DPODPS are semicrystalline and have remarkably increased T_gs over commercially available PEEK and PEKK. The copolymers with 40–50 mol% DPODPS had not only high T_gs of 170–172°C, but also moderate T_ms of 326–333°C, which are extremely suitable for melt processing. These copolymers have tensile strengths of 96.5–108.1 MPa, Young's moduli of 1.98–3.05 GPa, and elongations at break of 13–26% and exhibit excellent thermal stability and good resistance to acidity, alkali, and common organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.     

Liquid—liquid equilibria for the system water + acetic acid + methyl isoamyl ketone

Liquid—liquid equilibrium data obtained over the temperature range 10–60°C for the binary system water + methyl isoamyl ketone (MIAK) are presented together with ternary data for the system water + acetic acid + MIAK at 15, 25 and 40°C. The latter system may be of particular interest for solvent extraction studies, in that MIAK has a flash point much higher than that of methyl isobutyl ketone (MIBK). The new data presented in this paper are correlated in terms of the well-known NRTL and UNIQUAC models. Using the UNIFAC model and the parameter table published recently, experimental results are compared with the predicted values.     

The Mechanism of Sugar C−H Bond Oxidation by a Flavoprotein Oxidase Occurs by a Hydride Transfer Before Proton Abstraction

Understanding the reaction mechanism underlying the functionalization of C−H bonds by an enzymatic process is one of the most challenging issues in catalysis. Here, combined approaches using density functional theory (DFT) analysis and transient kinetics were employed to investigate the reaction mechanism of C−H bond oxidation in d -glucose, catalyzed by the enzyme pyranose 2-oxidase (P2O). Unlike the mechanisms that have been conventionally proposed, our findings show that the first step of the C−H bond oxidation reaction is a hydride transfer from the C2 position of d -glucose to N5 of the flavin to generate a protonated ketone sugar intermediate. The proton is then transferred from the protonated ketone intermediate to a conserved residue, His548. The results show for the first time how specific interactions around the sugar binding site promote the hydride transfer and formation of the protonated ketone intermediate. The DFT results are also consistent with experimental results including the enthalpy of activation obtained from Eyring plots, as well as the results of kinetic isotope effect and site-directed mutagenesis studies. The mechanistic model obtained from this work may also be relevant to other reactions of various flavoenzyme oxidases that are generally used as biocatalysts in biotechnology applications.     

Synthesis of C13-C25 fragment of 24-demethylbafilomycin C(1) via diastereoselective aldol reactions of a ketone boron enolate as the key step

An efficient synthesis of the C13-C25 fragment is described for 24-demethylbafilomycin C1, a new member of the plecomacrolide family isolated from fermentation broth of Streptomyces sp. CS which is a commensal microbe of Maytenus hookeri. The targeted C13-C25 fragment possesses five oxygenated and three methyl-substituted stereogenic centers. It is obtained through formation of the C17-C18 syn aldol by using an ethyl ketone boron enolate with diastereomeric ratios of 95:5 and 83:17, respectively, for the chiral aldehydes substituted with acetoxy and methoxyacetoxy groups at C15. The results confirm the observation that the stereochemistry at C22 of the ketone is determinant to the diastereoselectivity of the aldol reaction. The synthesized C13-C25 fragment having a methoxyacetoxy group at C15 is considered as a useful precursor for construction of the 16-membered ring lactone of 24-demethylbafilomycin C1 through an aldol condensation of the methoxyacetate followed by formation of the C12-C13 double bond via a diene-ene RCM reaction.