cas 18362-51-1, 1,3-BIS(4-METHOXYPHENYL)-1,3-PROPANEDIONE

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PPh3-catalyzed β-selective addition of α-fluoro β-dicarbonyl compounds to allenoates
A highly selective phosphine-catalyzed β-addition of α-fluoro β-dicarbonyl compounds to allenoates has been developed. Both α-fluoro β-diketones and α-fluoro β-keto esters prove to be competent fluorocarbon nucleophiles, giving a series of the β-addition products bearing a fluorinated quaternary carbon center in good to excellent yields and with excellent regioselectivities. A plausible reaction pathway is presented.
Liu, Yong-Liang,Wang, Xiao-Ping,Wei, Jie,Li, Ya
supporting information

(2021/12/02)

Tris-(2-pyridylmethyl)amine-ligated Cu(II) 1,3-diketonate complexes: Anaerobic retro-Claisen and dehalogenation reactivity of 2-chloro-1,3-diketonate derivatives
We report synthetic, structural and reactivity investigations of tris-(2-pyridylmethyl)amine (TPA)-ligated Cu(ii) 1,3-diketonate complexes. These complexes exhibit anaerobic retro-Claisen type C-C bond cleavage reactivity which exceeds that found in analo
Elsberg, Josiah G. D.,Anderson, Stephen N.,Tierney, David L.,Reinheimer, Eric W.,Berreau, Lisa M.
p. 1712 - 1720
(2021/02/22)

I2-Promoted [3+2] Cyclization of 1,3-Diketones with Potassium Thiocyanate: a Route to Thiazol-2(3H)-One Derivatives
An I2-promoted strategy has been developed for the synthesis of thiazol-2(3H)-one derivatives from 1,3-diketones with potassium thiocyanate. This [3+2] cyclization reaction involves C?S and C?N bond formation and exhibits good functional group tolerance. A series of thiazol-2(3H)-one derivatives are obtained in moderate to good yields. (Figure presented.).
An, Zhenyu,Liu, Yafeng,Yan, Rulong,Zhao, Pengbo
supporting information
p. 3240 - 3244
(2021/06/16)

Organocatalytic Asymmetric Cascade Michael-acyl Transfer Reaction between 2-Fluoro-1,3-diketones and Unsaturated Thiazolones: Access to Fluorinated 4-Acyloxy Thiazoles
Quinine derived bifunctional urea catalyzed cascade Michael-acyl transfer reaction of 5-alkenyl thiazolones and monofluorinated β-diketones has been developed. The fluorine containing 4-acyloxy thiazoles were synthesized in high yields and good diastereo-and excellent enantioselectivities. Synthetic transformations, including synthesis of 4-hydroxy thiazoles, have been demonstrated.
Biswas, Rayhan G.,Ray, Sumit K.,Unhale, Rajshekhar A.,Singh, Vinod K.
supporting information
p. 6504 - 6509
(2021/08/30)

Direct synthesis of 2,3,5-trisubstituted pyrroles: via copper-mediated one-pot multicomponent reaction
We have developed a copper-mediated one-pot synthesis of 2,3,5-trisubstituted pyrroles from 1,3-dicarbonyl compounds and acrylates using ammonium acetate as a nitrogen source. The reaction achieves C-C and C-N bond formation and provides an efficient approach to access highly functionalized pyrroles without further raw material preparation. This method is operationally simple, compatible with a wide range of functional groups, and provides the target products in moderate to good yields. This journal is
He, Jian-Ping,Huang, Guo-Sheng,Luo, Nan,Zhan, Zhen-Zhen,Zhang, Ming-Ming
supporting information
p. 9831 - 9835
(2021/01/05)

Enolization rates control mono-: Versus di-fluorination of 1,3-dicarbonyl derivatives
Fluorine-containing 1,3-dicarbonyl derivatives are essential building blocks for drug discovery and manufacture. To understand the factors that determine selectivity between mono- and di-fluorination of 1,3-dicarbonyl systems, we have performed kinetic studies of keto-enol tautomerism and fluorination processes. Photoketonization of 1,3-diaryl-1,3-dicarbonyl derivatives and their 2-fluoro analogues is coupled with relaxation kinetics to determine enolization rates. Reaction additives such as water accelerate enolization processes, especially of 2-fluoro-1,3-dicarbonyl systems. Kinetic studies of enol fluorination with Selectfluor and NFSI reveal the quantitative effects of 2-fluorination upon enol nucleophilicity towards reagents of markedly different electrophilicity. Our findings have important implications for the synthesis of α,α-difluoroketonic compounds, providing valuable quantitative information to aid in the design of fluorination and difluorination reactions.
Rozatian, Neshat,Beeby, Andrew,Ashworth, Ian W.,Sandford, Graham,Hodgson, David R.W.
p. 10318 - 10330
(2019/11/20)

Method of preparing 1,3-diketone compound by acetyenic ketone
The invention relates to a preparation method of preparing a 1,3-diketone compound by acetyenic ketone. The preparation method comprises the following steps: S1, putting alpha-alkynyl ketone compound,water, gold salt and silver salt in a reaction solvent to obtain a precursor mixture, wherein the molar ratio of the alpha-alkynyl ketone compound, water, gold salt and silver salt is 1: (1-50): (0.001-0.10): (0.002-0.15); and S2, putting the precursor mixture obtained in the S1 to react at a reaction temperature of 0-50 DEG C to obtain the 1,3-diketone compound, wherein the reaction time is 5 min to 48 h. The method is simple in reaction condition, free of acid or alkaline additives and high in yield, and can be applied to modern production on a large scale.
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Paragraph 0215-0221

(2019/06/12)

Electrochemical oxidative cyclization of olefinic carbonyls with diselenides
The tandem cyclization of olefinic carbonyls with easily accessible diselenides facilitated by electrochemical oxidation has been successfully developed, which provides an environmentally friendly method for the construction of C-Se and C-O bonds simultaneously. A series of seleno dihydrofurans and seleno oxazolines, bearing fragile heterocycles, subtle C-I bonds and supernumerary vinyl groups, were forged using this elegant chelation strategy. Neither metal catalysts nor external chemical oxidants are required to promote this transformation.
Guan, Zhipeng,Wang, Yunkun,Wang, Huamin,Huang, Yange,Wang, Siyuan,Tang, Hongding,Zhang, Heng,Lei, Aiwen
supporting information
p. 4976 - 4980
(2019/09/30)

ONE-STEP, FAST, 18F-19F ISOTOPIC EXCHANGE RADIOLABELING OF DIFLUORO-DIOXABORININS AND USE OF SUCH COMPOUNDS IN TREATMENT
A compound according to Formula (I) or a pharmaceutically acceptable salt and/or solvate thereof, wherein X1 and X2 are each independently 18F or 19F; R1 and R2 are each independently alkyl, amine, perfluoroalkyl, alkenyl, alkynyl, aryl, or aralkenyl; and R3 is H, halo, alkyl, alkyl ester, alkenyl, alkynyl, aryl, or aralkenyl; or wherein: R1 and R3 or R2 and R3 join to form a 6-membered cycloalkyl or heterocyclyl; or R1 and R3, R2 and R3, or R1, R2, and R3 join to form a substituted or unsubstituted polycyclic ring, wherein the polycyclic ring comprises fused cycloalkyl, heterocycloalkyl, aryl, or heteroaryl rings.
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Paragraph 0019; 0206-0207

(2019/12/15)

1,2-Diazacyclopentane-3,5-diyl Diradicals: Electronic Structure and Reactivity
Localized singlet diradicals are key intermediates in bond homolysis. A thorough study of the reactive species is needed to clarify the mechanisms of the homolytic bond cleavage and formation processes. In general, the singlet diradicals are quite short-lived because of the fast radical-radical coupling reactions. The short-lived characteristic has retarded the thorough study on bond homolysis. In this study, a new series of long-lived singlet diradicals, viz., 1,2-diazacyclopentane-3,5-diyl, were identified, and their electronic structures and novel reactivities were thoroughly studied using laser-flash photolysis (LFP), product analysis, and computational studies. A direct observation of the thermal equilibration (fast process) between the singlet diradicals and the corresponding ring-closing compounds was undertaken on the submicrosecond time scale. The solvent and substituent effects on the equilibration constant and rate constants for the ring-closing reaction and ring-opening reaction clarify the novel nitrogen-atom effect on the localized singlet 1,3-diyl diradicals. Two types of alkoxy-migrated compounds, 9 and 10, were isolated with high yields as the final products. Crossover, spin-trapping, and LFP experiments for the formation of alkoxy-group migration products (i.e., 9 versus 10) revealed the unique temperature effect on the product ratio of the two types of alkoxy-migration products. The temperature-insensitive intersystem crossing process (slow process, millisecond time scale) was found to be a key step in the formation of 9, which is an entropy-controlled pathway. An intramolecular migration process was identified for the formation of 10 that was accelerated by a polar solvent in an enthalpy-controlled process. This unique heteroatom effect has opened up a new series of localized singlet diradicals that are crucial intermediates in bond homolysis.
Yoshidomi, Shohei,Abe, Manabu
supporting information
p. 3920 - 3933
(2019/03/07)

Novel Bifunctionalization of Activated Methylene: Base-Promoted Trifluoromethylthiolation of β-Diketones with Trifluoromethanesulfinyl Chloride
A novel bifunctionalization of activated methylene was achieved successfully through the base-promoted trifluoromethylthiolation of β-diketones or β-ketoesters with trifluoromethanesulfinyl chloride. A series of α-trifluoromethylthiolated α-chloro-β-diketones and α-chloro-β-ketoesters were obtained in moderate to good yields under mild conditions. When β-diketones containing a phenyl group with a hydroxyl or amino substituent at the ortho position were used as substrates, intramolecular trifluoromethylthiolation/cyclization reaction took place to give the corresponding cyclic products. Furthermore, the protocol could be extended to perfluoroalkylthiolation with the sodium perfluoroalkanesulfinate/POCl3 system. On the basis of experimental results, plausible mechanisms are proposed.
Sun, Dong-Wei,Jiang, Min,Liu, Jin-Tao
supporting information
p. 10797 - 10802
(2019/07/03)

Reinventing the de Mayo reaction: Synthesis of 1,5-diketones or 1,5-ketoesters via visible light [2+2] cycloaddition of β-diketones or β-ketoesters with styrenes
A visible light mediated De Mayo reaction between 1,3-diketones and styrenes following a [2+2] cycloaddition pathway via a photosensitization mechanism gives access to 1,5-diketones. The reaction has been applied to substituted styrenes and aryl- and alkyl-substituted ketones. Moreover, the method converts β-ketoesters, β-amido esters, and β-cyano ketones. Seven membered rings, a frequent structural motif of natural products, are also accessible using this methodology.
Martinez-Haya, Rebeca,Marzo, Leyre,K?nig, Burkhard
supporting information
p. 11602 - 11605
(2018/10/31)

Controlling reactivity through liquid assisted grinding: The curious case of mechanochemical fluorination
We have identified an example of a mechanochemically milled organic reaction where liquid-assisted grinding controls the selectivity, such a phenomenon has not been reported/observed before. It was found that upon milling dibenzoylmethane with Selectfluor in the absence of any solvent, a 3:1 ratio of monofluorinated:difluorinated product was observed. Whereas, addition of 0.125 mL of acetonitrile (～10% of the total volume of materials present) to the ground reaction mixture afforded 50:1 selectivity. Furthermore, this phenomenon is applicable to a small range of diketone substrates thus far explored. Additionally, we have demonstrated that difluorination can be achieved by simply switching from adding acetonitrile to addition of sodium carbonate. Most notable, in the latter case, is the reduced reaction time compared to a conventional solvent approach, 2 hours in the mill and 24 hours in the flask.
Howard, Joseph L.,Sagatov, Yerbol,Repusseau, Laura,Schotten, Christiane,Browne, Duncan L.
supporting information
p. 2798 - 2802
(2017/07/24)

Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones
A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.
He, Zhen,Qi, Xiaotian,She, Zhijie,Zhao, Yinsong,Li, Shiqing,Tang, Junbin,Gao, Ge,Lan, Yu,You, Jingsong
supporting information
p. 1403 - 1411
(2017/02/10)

Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes
An unprecedented and efficient organic base-catalysed highly chemoselective carbo- and oxytrifluoromethylation of unactivated alkenes with Togni's reagent was developed. The switchable chemoselectivity was tuned by simply changing the organic base catalyst and solvent. Mechanistic studies indicated that a radical cyclization pathway for carbotrifluoromethylation in DMSO and a carbocation pathway for oxytrifluoromethylation in DCE were probably involved.
Yang, Ning-Yuan,Li, Zhong-Liang,Ye, Liu,Tan, Bin,Liu, Xin-Yuan
supporting information
p. 9052 - 9055
(2016/07/21)

Variations in the blaise reaction: Conceptually new synthesis of 3-amino enones and 1,3-diketones
Organic compounds with 3-amino enone or 1,3-diketone functional groups are extremely important, as they can be converted into a plethora of heterocyclic or carbocyclic compounds, or can be used as ligands in metal complexes. We have achieved a new, easy, straightforward and convenient synthesis of 3-amino enones and 1,3-diketones starting from aryl/heteroaryl/alkyl nitriles and 1-aryl/alkyl 2-bromoethanones. The reaction is a variation of the classical Blaise reaction, and it works with zinc and trimethylsilyl chloride as an activator. By running the hydrolysis of the reaction intermediate with HCl (3 N aq.) at 0-30 °C or at 100 °C, it is possible to form either 3-amino enones or 1,3-diketones, respectively. The newly developed method was used for the synthesis of avobenzone, an ingredient of sun-screen lotions. Furthermore, an easy synthesis of (Z)-3-amino-1-[4-(tertbutyl) phenyl]-3-(4-methoxyphenyl)prop-2-en-1-one, with UV/Vis absorption characteristics similar to those of avobenzone, was also achieved.
Rao, H. Surya Prakash,Muthanna, Nandurka
supporting information
p. 1525 - 1532
(2015/03/04)

Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones
A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
He, Zhen,Qi, Xiaotian,Li, Shiqing,Zhao, Yinsong,Gao, Ge,Lan, Yu,Wu, Yiwei,Lan, Jingbo,You, Jingsong
p. 855 - 859
(2015/02/05)

Structure-based design, synthesis and evaluation in vitro of arylnaphthyridinones, arylpyridopyrimidinones and their tetrahydro derivatives as inhibitors of the tankyrases
Abstract The tankyrases are members of the PARP superfamily; they poly(ADP-ribosyl)ate their target proteins using NAD+ as a source of electrophilic ADP-ribosyl units. The three principal protein substrates of the tankyrases (TRF1, NuMA and axin) are involved in replication of cancer cells; thus inhibitors of the tankyrases may have anticancer activity. Using structure-based drug design and by analogy with known 3-arylisoquinolin-1-one and 2-arylquinazolin-4-one inhibitors, series of arylnaphthyridinones, arylpyridinopyrimidinones and their tetrahydro-derivatives were synthesised and evaluated in vitro. 7-Aryl-1,6-naphthyridin-5-ones, 3-aryl-2,6-naphthyridin-1-ones and 3-aryl-2,7-naphthyridin-1-ones were prepared by acid-catalysed cyclisation of the corresponding arylethynylpyridinenitriles or reaction of bromopyridinecarboxylic acids with β-diketones, followed by treatment with NH3. The 7-aryl-1,6-naphthyridin-5-ones were methylated at 1-N and reduced to 7-aryl-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-ones. Cu-catalysed reaction of benzamidines with bromopyridinecarboxylic acids furnished 2-arylpyrido[2,3-d]pyrimidin-4-ones. Condensation of benzamidines with methyl 1-benzyl-4-oxopiperidine-3-carboxylate and deprotection gave 2-aryl-5,6,7,8-tetrahydropyrido[4,3-d]pyrimidin-4-ones, aza analogues of the known inhibitor XAV939. Introduction of the ring-N in the arylnaphthyridinones and the arylpyridopyrimidinones caused >1000-fold loss in activity, compared with their carbocyclic isoquinolinone and quinazolinone analogues. However, the 7-aryl-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-ones showed excellent inhibition of the tankyrases, with some examples having IC50 = 2 nM. One compound (7-(4-bromophenyl)-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-one) showed 70-fold selectivity for inhibition of tankyrase-2 versus tankyrase-1. The mode of binding was explored through crystal structures of inhibitors in complex with tankyrase-2.
Kumpan, Katerina,Nathubhai, Amit,Zhang, Chenlu,Wood, Pauline J.,Lloyd, Matthew D.,Thompson, Andrew S.,Haikarainen, Teemu,Lehti?, Lari,Threadgill, Michael D.
supporting information
p. 3013 - 3032
(2015/08/03)

Antiproliferative novel isoxazoles: Modeling, virtual screening, synthesis, and bioactivity evaluation
A series of novel isoxazole derivatives were efficiently synthesized through the adaptation/modification of an in situ synthetic procedure for pyrazoles. All novel compounds were tested against four different cell lines to evaluate their antiproliferative activity. Based on the Hela cells results of this study and previous work, a classification model to predict the anti-proliferative activity of isoxazole and pyrazole derivatives was developed. Random Forest modeling was used in view of the development of an accurate and reliable model that was subsequently validated. A virtual screening study was then proposed for the design of novel active derivatives. Compounds 9 and 11 demonstrated significant cytostatic activity; the fused isoxazole derivative 18 and the virtually proposed compound 2v, were proved at least 10 times more potent as compared to compound 9, with IC50 values near and below 1 μM. In conclusion, a new series of isoxazoles was exploited with some of them exhibiting promising cytostatic activities. Further studies on the substitution pattern of the isoxazole core can potentially provide compounds with cytostatic action at the nM scale. In this direction the in silico approach described herein can also be used to screen existing databases to identify derivatives with anticipated activity.
Tzanetou, Evangelia,Liekens, Sandra,Kasiotis, Konstantinos M.,Melagraki, Georgia,Afantitis, Antreas,Fokialakis, Nikolas,Haroutounian, Serkos A.
p. 139 - 149
(2014/06/09)

Quantitative evaluation of thermodynamic parameters for thermal back-reaction after mechanically induced fluorescence change
Kinetics of the thermal back-reaction of β-diketonate boron difluoride complexes after mechanical perturbation were evaluated by fluorescence intensity changes for the first time, suggesting that the activation parameters of the reaction intermediates gov
Ito, Fuyuki,Sagawa, Takehiro
p. 19785 - 19788
(2013/11/06)

Copper-Catalyzed Synthesis of α-Thioaryl Carbonyl Compounds Through S-S and C-C Bond Cleavage
A method to access α-thioaryl ketones and α-thioaryl esters employing copper acetate (hydrate) as catalyst and readily accessible diaryl disulfides and β-diketones (or β-keto esters) has been developed. Both alkyl- and aryl-substituted carbonyl compounds can be prepared. Copyright
Zou, Liang-Hua,Priebbenow, Daniel L.,Wang, Long,Mottweiler, Jakob,Bolm, Carsten
p. 2558 - 2563
(2013/10/21)

Nucleophilic acylation of α-haloketones with aldehydes: An umpolung strategy for the synthesis of 1,3-diketones
The first example of N-heterocyclic carbene (NHC)-promoted intermolecular acylation of α-haloketones with aldehydes and α,β-unsaturated aldehydes (enals) is reported. The protocol involves carbonyl umpolung reactivity of aldehydes and enals in which the carbonyl carbon attacks nucleophilically on electrophilic terminal of α-haloketones to afford 1,3-diketones and α,β-unsaturated 1,3-diketones, respectively. Short reaction time, ambient temperature, operational simplicity, and high yields are the salient features of the present procedure.
Singh, Santosh,Singh, Pankaj,Rai, Vijai K.,Kapoor, Ritu,Yadav, Lal Dhar S.
experimental part
p. 125 - 128
(2011/02/26)

Synthesis and investigations on the oxidative degradation of C3/C5-Alkyl-1,2,4-triarylpyrroles as ligands for the estrogen receptor
In this study, we synthesized 1,2,4-triarylpyrroles as ligands for the estrogen receptor (ER). Two pyrrole series were prepared with either C3-alkyl or C3/C5-dialkyl residues. Compounds from both series were susceptible to oxidative degradation-dialkylated compounds (t1/2=33-66h) to a higher extent than their monoalkylated congeners (t1/2=140-211h). Nevertheless, stability was sufficient for determination of in vitro ER binding affinity. The most active agonist in hormone-dependent, ERα-positive MCF-7/2a and U2-OS/α cells was 1,2,4-tris(4-hydroxyphenyl)-3-propyl-1H-pyrrole (6d) (MCF-7/2a: EC50=70nM; U2-OS/α: EC50=1.6nM). A corresponding inactivity in U2-OS/β cells demonstrated the high ERα selectivity. This trend was confirmed in a competition experiment using estradiol (E2) and purified hERα and hERβ proteins (relative binding affinity (RBA) calculated for 6d: RBA(ERα)=1.85%; RBA(ERβ) 0.01%). Generally, C3/C5-dialkyl substitution led to reduction of activity, possibly due to lower stability. Triarylpyrroles with C3-alkyl or C3/C5-dialkyl residues were synthesized as ligands for the estrogen receptor (ER). The compounds exhibited transcription activation selectively for ERα but only marginally displaced estradiol from its binding site. The compounds were susceptible to oxidative degradation-dialkylated compounds to a higher extent than their monoalkylated congeners. The reasons for instability were elucidated; thus, by changing the substitution pattern, it will be possible to generate stable triarylpyrroles.
Schaefer, Anja,Wellner, Anja,Gust, Ronald
scheme or table
p. 794 - 803
(2012/01/06)

Photoprotective compositions comprising photosensitive 1,3,5-triazine compounds, dibenzoylmethane compounds and siliceous s-triazines substituted with two aminobenzoate or aminobenzamide groups
UV-photoprotective, topically applicable cosmetic/dermatological compositions contain: (a) at least one dibenzoylmethane compound,(b) at least one 1,3,5-triazine compound that is photosensitive in the presence of a dibenzoylmethane compound, and(c) at least one siliceous s-triazine compound substituted with two aminobenzoate or aminobenzamide groups, or a tautomeric form thereof, the 1,3,5-triazine compounds being improvedly photostable in such compositions.
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(2010/02/16)

Cosmetic/sunscreen compositions containing dibenzoylmethane compounds and dithiolane compound photostabilizers therefor
Cosmetic/sunscreen compositions contain a combination of at least one dibenzoylmethane sunscreen compound and a photostabilizing amount of at least one dithiolane compound of formula (I) below:
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(2010/04/30)

Photostable cosmetic compositions comprising dibenzoylmethane/pyrrolidinone compounds
Photostable UV-photoprotecting cosmetic sunscreen compositions contain (a) an effective UV-photoprotecting amount of at least one dibenzoylmethane compound sunscreen, (b) an effective radiation-photostablizing amount of at least one pyrrolidinone compound having the formula (I) below: and, advantageously, at least one liquid fatty phase and at least one lipophilic active sunscreen agent of low solubility, formulated into (c) a cosmetically acceptable support therefor.
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(2009/12/05)

Diastereoselective nucleophilic cyclopropanation of 1,2-diketones and α-ketoimines with bis(iodozincio)methane
A reaction of 1,2-diketones and α-ketoimines with bis(iodozincio)methane gave cyclopropan-1,2-diol and 2-aminocyclopropanol respectively via nucleophilic [2+1]cycloaddition. The reaction proceeded via a sequential nucleophilic attack of the dizinc reagent to vicinal two carbonyl group. The reaction showed high diastereoselectivity to give cis-isomer via a face-to-face coordination between the substrate and bis(iodozincio)methane.
Nomura, Kenichi,Asano, Keisuke,Kurahashi, Takuya,Matsubara, Seijiro
experimental part
p. 1381 - 1399
(2009/07/17)

Photoprotective cosmetic compositions comprising photostabilized dibenzoylmethane compounds and siloxane-containing arylalkyl benzoate amide compounds
Photostable, topically applicable cosmetic/dermatological compositions contain at least one dibenzoylmethane sunscreen compound and at least one photostabilizing siloxane-containing arylalkyl amide compound of formula (I) below:
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(2009/01/24)

Ligand effects in the rhodium-catalyzed addition of alkynes to aldehydes and diketones. Modification of the β-diketonate ligand
A catalytic amount of dicarbonylacetonato rhodium(I) and a phosphine ligand bearing bulky electron-donating alkyl groups has been shown to generate an effective catalyst for the addition of alkynes to aldehydes and activated ketones under mild, neutral conditions. While previous studies have shown that modification of the phosphine has significant effects on the activity of the catalyst, the role of the β-diketonate ligand has not been probed. Six different β-diketonate rhodium complexes were synthesized and their ability to catalyze the alkyne addition reaction was evaluated. Changing the structure of the β-diketonate ligand can have a noticeable effect on the reaction rate. Acetylacetonate derivatives with strong electron withdrawing groups have a detrimental effect on the catalytic activity, while bulky and electron rich β-diketonate derivatives provide more efficient catalysts.
Dhondi, Pawan K.,Carberry, Patrick,Chisholm, John D.
p. 8743 - 8746
(2008/03/18)

Diaroyl(methanato)boron Difluoride Compounds as Medium-Sensitive Two-Photon Fluorescent Probes
This paper evaluates the use of diaroyl(methanato)boron difluoride compounds for designing efficient fluorescent probes through two-photon absorption. Three different pathways allowing for the syntheses of symmetrical and dissymmetrical molecules are reported. The stable diaroyl(methanato)-boron difluoride derivatives can be easily obtained in good yields. They exhibit a large one-photon absorption that is easily tuned in the near-UV range. Their strong fluorescence emission covers the whole visible domain. In addition to these attractive linear properties, several diaroyl(methanato)-boron difluoride derivatives possess significant cross sections for two-photon absorption. The derived structure-property relationships are promising for designing new generations of molecules relying on the diaroyl(methanato)boron difluoride backbone.
Cogne-Laage, Emmanuelle,Allemand, Jean-Francois,Ruel, Odile,Baudin, Jean-Bernard,Croquette, Vincent,Blanchard-Desce, Mireille,Jullien, Ludovic
p. 1445 - 1455
(2007/10/03)

Photostable UV-screening compositions comprising dibenzoylmethane/diarylbutadiene compounds
Topically applicable, photostable cosmetic/dermatological UV-screening compositions comprise (a) at least one photolabile UV-screening dibenzoylmethane compound and (b) a dibenzoylmethane photostabilizing amount of at least one 4,4-diarylbutadiene compound, formulated into a topically applicable, cosmetically/dermatologically acceptable support therefor; the weight ratio of the 4,4-diarylbutadiene compound(s) to the diarylbutadiene compound(s) is characteristically greater than 2.5 and the subject compositions are advantageously devoid of any cinnamate sunscreen.
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(2008/06/13)

UV-photostabilized sunscreen compositions comprising dibenzoylmethane/benzophenone compounds
Topically applicable cosmetic/dermatological sunscreen compositions well suited for the stable UV-photoprotection of human skin and/or hair are devoid of any p-methylbenzylidenecamphor, but contain (a) an effective photoprotecting amount of at least one UV-screening dibenzoylmethane compound, and (b) an effective photostabilizing amount of at least on UV-screening amino-substituted 2-hydroxybenzophenone compound having the following structural formula (I): 1formulated into (c) a topically applicable, cosmetically/dermatologically acceptable vehicle, diluent or carrier therefor.
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(2008/06/13)

Composition containing a dibenzoylmethane derivative and an alpha-alkylstyrene dimer uv stabilising method
The invention relates to a cosmetic or dermatological composition, for topical use, in particular for the photoprotection of skin and hair, characterized in that it comprises at least, in a cosmetically acceptable support: (a) from 0.1 to 20% by weight of a UV screening agent of the dibenzoylmethane-based type and (b) from 0.1 to 20% by weight of one specific alpha-alkylstyrene-based dimer. The invention relates to a novel process for improving the stability of at least one dibenzoylmethane derivative towards UV radiation, which consists in combining with the said dibenzoylmethane derivative an effective amount of at least one specific alpha-alkylstyrene-based dimer.
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(2008/06/13)

Dibenzoylmethane sunscreen compositions containing photostablizing amounts of tri-substituted butane compounds
Improvedly photostable UV-photoprotecting cosmetic/dermatological compositions for the skin and/or the hair contain (a) a UV-photoprotective amount of at least one dibenzoylmethane sunscreen, e.g., 4-(tert-butyl)-4′-methoxydibenzoylmethane or 4-isopropyldibenzoylmethane, advantageously (a′) a UV-photoprotective amount of at least one 1,3,5-triazine sunscreen, e.g., 2-[(p-(tert-butylamido]-4,6-bis[(p-(2′ethylhexyl-1′-oxycarbonyl)anilino]-1,3,5-triazine or 2,4,6-tris[p-(2′-ethylhexyl-1′-oxycarbonyl)anilino]-1,3,5-triazine, (b) an effective sunscreen photostabilizing amount of 1,1,1-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, formulated into (c) a topically applicable, cosmetically acceptable vehicle, diluent or carrier therefor.
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(2008/06/13)

Method for providing dibenzoylmethane derivatives with light stability
The invention concerns novel light-stable filtering cosmetic compositions for topically protecting the skin and/or the hair against ultraviolet radiation, in particular solar radiation, comprising in a cosmetically acceptable support, at least a dibenzoylmethane derivative and at least an oily phase, and an efficient amount of at least a thickening copolymer including at least a hydrophobic unit in sufficient amount for it to be partially or completely soluble in the oily phase and at least a hydrophilic unit in sufficient amount for thickening the oily phase as stabilizing agent for the filter. The invention also concerns the corresponding method for providing dibenzoylmethane with light stability and the use of the compositions for skin and hair protection against the effects of ultraviolet radiation.
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(2008/06/13)

Synthesis and study of the anodic behavior of 1,3,4,6-tetraaryl-2λ4δ2-thieno[3,4-c] thiophenes
Two heterocyclic compounds based on the thieno[3,4-c]thiophene structure with four aryl substituents were prepared and their behavior in electrooxidation studied. These tetraarylthieno[3,4-c]thiophenes were synthesized in three steps starting from 1,3-dibenzoylmethane in the case of 1,3,4,6-tetraphenyl-2λ4δ2-thieno[3,4-c] thiophene 1a and from 1,3-bis(4′-methoxyphenyl)propane-1,3-dione in the case of 1,3,4,6-tetrakis(4′-methoxyphenyl)-2λ4δ 2-thieno[3,4-c]thiophene 1b, a new compound. Both cyclic and hydrodynamic voltamperometric analyses indicate two reversible one-electron oxidation stages for compound 1b, while for compound 1a only the first stage is reversible. The preparative electrooxidation of the two compounds results in the opening of one thiophene ring giving rise to γ-keto-thioketones.
Douadi, Tahar,Cariou, Michel
p. 509 - 520
(2007/10/03)

Enantioselective borohydride reduction catalyzed by optically active cobalt complexes
The highly enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing the appropriate alcohol as modifiers and a suitable β-ketoiminato ligand of the catalyst. The enantioselective borohydride reduction has been successfully applied to the preparation of optically active 1,3-diols, the stereoselective reduction of diacylferrocenes, and dynamic and/or kinetic resolution of 1,3-dicarbonyl compounds.
Yamada, Tohru,Nagata, Takushi,Sugi, Kiyoaki D.,Yorozu, Kiyotaka,Ikeno, Taketo,Ohtsuka, Yuhki,Miyazaki, Daichi,Mukaiyama, Teruaki
p. 4485 - 4509
(2007/10/03)

Estrogen receptor modulators
Estrogen receptor-modulating pyrazole compounds are described in addition to methods and compositions for treating or preventing estrogen receptor-mediated disorders. The compounds described have been found to have unexpected and surprising activity in modulating estrogen receptor activity. Thus, the compounds of the present invention have utility in preventing or treating estrogen receptor-mediated disorders such as osteoporosis, breast and endometrial cancers, atherosclerosis, and Alzheimer's disease.
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(2008/06/13)

Halogen-substituted triarylpyrazoles: potential estrogen receptor-alpha selective radiopharmaceuticals
Halogen-substituted analogs of a pyrazole ligand for the estrogen receptor have been synthesized. These analogs retain much of the affinity preference of the parent ligand for the estrogen receptor alpha sybtype (ERα) vs beta subtype (ERβ).
Vijaykumar, Dange,Katzenellenbogen, John A.
p. S342 - S344
(2007/10/03)

Composition comprising a dibenzoylmethane derivative and a polyamino polymer
Cosmetic and/or dermatalogoical compositions comprising, in a cosmetically and/or dermatologically acceptable vehicle, i) a dibenzoylmethane derivative, in particular 4-tert-butyl-4′-methoxydibenzoylmethane, and ii) at least one polyamino polymer. These compositions are particularly photostable.
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(2008/06/13)

Photostable sunscreen compositions comprising dibenzoylmethane compounds and 2-hydroxybenzophenone-substituted silanes/organosiloxanes
Improvedly photostable, topically applicable cosmetic/dermatological sunscreen compositions well suited for the photoprotection of human skin and/or hair against the damaging effects of UV-irradiation, particularly solar radiation, comprise (1) a UV-photoprotecting effective amount of at least one dibenzoylmethane sunscreen compound and (2) a photostabilizing effective amount of at least one silane or organosiloxane bearing a 2-hydroxybenzophenone substituent.
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(2008/06/13)

UV-photoprotective dibenzoylmethane compositions comprising photostabilizing amounts of benzalmalonate silanes
Topically applicable, stable, UV-photoprotective cosmetic/dermatological compositions well suited for the photoprotection of human skin and/or hair against the damaging effects of UV-A and UV-B irradiation, comprise (a) an effective UV-photoprotecting amount of at least one dibenzoylmethane UV-sunscreen compound and (b) an effective dibenzoylmethane compound (a) photostabilizing amount of at least one benzalmalonate silane having the structural formula (I): STR1
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(2008/06/13)

A facile route to convert acetylacetone into other β-diketones with acyl chlorides promoted by samarium triiodide
Reaction of acetylacetone with acyl chlorides in the presence of SmI3 gave β-diketones RCOCH2COCH3 (I) or RCOCH2COR (II) in good yields under mild and neutral conditions.
Hao, Wenying,Zhang, Yongmin,Ying, Taokai,Lu, Pin
p. 2421 - 2427
(2007/10/03)

New Dithio-bis-(diaroylmethanes) and Acetyl Diaroylchloromethyl Bisulfides: Attractive Synthons and Precursors for the Liberation of Highly Reactive Dithiiranes or Thiosulfines
In a new, feasible procedure five symmetrical para-substituted diaroylmethanes ((4-X-C6H4-CO)2-CH2; X = F, Cl, Br, CH3, and CH3O) are prepared, in most cases in very good yields. For purification and activation, they are converted into the copper(II) complexes of their enolates. Subsequently, three reaction steps with disulfur dichloride (S2Cl2), chlorine, and ethanethioic acid yield new CH-acidic dithio-bis-(diaroylmethanes), α-chlorosulfenic acid chlorides, and acetyl diaroylchloromethyl disulfides. The latter compounds are of interest for the liberation of highly reactive dithiirane/thiosulfine species. With thiomorpholine, α-chlorosulfenic acid chlorides give α-chlorosulfenic acid amides.
Franek
p. 895 - 907
(2007/10/03)

Synthesis of dibenzoylmethane derivatives and inhibition of mutagenicity in Salmonella typhimurium
Twenty dibenzoylmethanes with methyl, methoxy, bromo, chloro, or fluoro substitution on either one or both benzene rings were synthesized and assayed for inhibition of the mutagenicity of 2-nitrofluorene in S. typhimurium TA98. 2,2-Dimethoxy, 3,3-dimethoxy and 3,3,4,4-tetramethoxydibenzoylmethane was as active as dibenzoylmethane. None of the halogen-substituted dibenzoylmethanes were active. These results demonstrate that dibenzoylmethanes can inhibit the mutagenicity of 2-nitrofluorene, and that modifications made on the benzene rings of dibenzoylmethane cannot enhance the antimutagenicity of this parent compound.
Choshi,horimoto,Wang,Nagase,Ichikawa,Sugino,Hibino
p. 1047 - 1049
(2007/10/02)

Direct Epoxidation of Olefins Catalyzed by Nickel(II) Complexes with Molecular Oxygen and Aldehydes
The presence of a bis(1,3-diketonato)nickel(II) complex, various olefins are directly monooxygenated into the corresponding epoxides on treatment with atmospheric pressure of oxygen or air and aldehydes.Especially, it is noted that bisnickel(II) behaves as an excellent catalyst in the present epoxidation.
Yamada, Tohru,Takai, Toshihiro,Rhode, Oliver,Mukaiyama, Teruaki
p. 2109 - 2117
(2007/10/02)

Aerobic Epoxidation of Olefinic Compounds Catalyzed by Tris(1,3-diketonato)iron(III)
Trisiron(III) (Fe(dmp)3) was found to be an excellent catalyst for oxygenation of a number of olefinic compounds including styrene analogues and olefinic alcohols into the corresponding epoxides in good to quantitative yields with combined use of molecular oxygen and an aldehyde at room temperature.
Takai, Toshihiro,Hata, Eiichiro,Yamada, Tohru,Mukaiyama, Teruaki
p. 2513 - 2518
(2007/10/02)

Nickel(II) Complex Catalyzed Epoxidation of Olefins with Molecular Oxygen and Primary Alcohol
In the presence of a catalytic amount of bisnickel(II) (=Ni(dmp)2), various olefins are smoothly monooxygenated into the corresponding epoxides in good yields with combined use of molecular oxygen and primary alcohol.
Mukaiyama, Teruaki,Takai, Toshihiro,Yamada, Tohru,Rhode, Oliver
p. 1661 - 1664
(2007/10/02)

First Examples Exhibiting both Double Melting Behavior and Mesomorphism in a Series of Long Chain Substituted Compounds: 1,3-Di(p-n-alkoxyphenyl)propane-1,3-dione
A new series of β-diketones substituted by the same kind of chains, (alkoxy groups) having different lengths (CnO-Diketone, n = 1-12), has been synthesized.It was found that CnO-Diketone shows triple melting behavior for n = 1, double melting behavior for n = 2-7, and smectic mesomorphism for n = 8-12.It is the first example exhibiting both double (triple) melting behavior and mesomorphism in a series of long chain substituted compounds, so far as we know.Furthermore, it is noteworthy that the critical change from double melting behavior to mesomorphism occurs between n = 7 and n = 8, which is also the first example in the long chain substituted compounds, so far as we know.Keywords: double melting behavior, smectic mesomorphism, long chain substituted compounds, β-diketone
Ohta, Kazuchika,Muroki, Hiromitsu,Hatada, Koh-Ichi,Takagi, Akira,Ema, Hiroshi,et al.
p. 163 - 178
(2007/10/02)

Discotic Liquid Crystals of Transition Metal Complexes, 3: the First-Established Discotic Lamellar Phase in Biscopper(II)
A new series of disk-like complexes, biscopper(II) (abbreviated as CnO-Cu, n = 1-12), has been synthesized.It was found that each of the complexes from C3O-Cu to C12O-Cu is a discogen, and that each of them has only one discotic mesophase.C3O-Cu is the first compound substituted by the shortest side chains in the discogen, so far as we know.The mesomorphic textures could be observed as mosaic textures for C3O-Cu ca.C5O-Cu and a big broken fan-like textures for C6O-Cu ca.C12O-Cu.The eutectic point calculated from Le Chatelier-Schroeder relations agrees well with the found eutectic point in the binary phase diagram between C8O-Cu and C8-Cu.This is the first example of such agreement in the discogens of the organic transition metal complexes.It has been established for the first time from X-ray diffraction measurements that each of the discotic mesophases in the complexes from C6O-Cu to C12O-Cu is a discotic lamellar phase.It becomes clear that this discotic mesophase is truly a new discotic lamellar phase (DL) different from the mesophase in C10-Cu, and that the DL phase has a structure in which the molecules tilt to the layers.Keywords: discotic liquid crystal, transition metal complex, bis(β-diketonato)copper(II), discotic lamellar phase
Ohta, Kazuchika,Muroki, Hiromitsu,Takagi, Akira,Hatada, Koh-Ichi,Ema, Hiroshi,et al.
p. 131 - 152
(2007/10/02)