- The synthesis of phosphates of long-chain ω-hydroxyalkyl esters of 11-deoxyprostaglandin E1
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Di(p-methylbenzyl) phosphates of ω-hydroxyalkyl esters of 11-deoxyprostaglandin E1 were synthesized from disubstituted 1,10-decane and 1,22-docosane derivatives for studying the permeability of bilayer membranes.
- Sokolov,Turovskii,Lukevits
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- Borane evolution and its application to organic synthesis using the phase-vanishing method
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Although borane is a useful reagent, it is difficult to handle. In this study, borane was generated in situ from NaBH4 or nBu4NBH4 with several oxidants using a phase-vanishing (PV) method. The borane generated was directly reacted with alkenes, affording the desired alcohols in good yields after oxidation with H2O2 under basic conditions. The selective reduction of carboxylic acids with the evolved borane was examined. The organoboranes generated by the PV method successfully underwent Suzuki–Miyaura coupling. Using this PV system, reactions with borane can be carried out easily and safely in a common test tube.
- Soga, Nene,Yoshiki, Tomo,Sato, Aoi,Kawamoto, Takuji,Ryu, Ilhyong,Matsubara, Hiroshi
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- From intermolecular interactions to texture in polycrystalline surfaces of 1,ω-alkanediols (ω = 10–13)
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Differences on herringbone molecular arrangement in two forms of long-chain 1,?-alkanediols (CnH2n+2O2 with n = 10, 11, 12, 13) are explained from the analysis of O-H···O hydrogen-bond sequences in infinite chains and the role of a C-H···O intramolecular hydrogen-bond in stabilization of a gauche defect, as well as the inter-grooving effectiveness on molecular packing. GIXD (Glancing Incidence X-ray Diffraction) experiments were conducted on polycrystalline monophasic samples. Diffracted intensities were treated with the multi-axial March-Dollase method to correlate energetic and geometrical features of molecular interactions with the crystalline morphology and textural pattern of samples. The monoclinic (P21/c, Z = 2) crystals of the even-numbered members (n = 10, 12; DEDOL and DODOL, respectively) are diametrical prisms with combined form {104}/{-104}/{001} and present a two-fold platelet-like preferred orientation, whereas orthorhombic (P212121, Z = 4) odd-numbered members (n = 11, 13; UNDOL and TRDOL, respectively) present a dominant needle-like orientation on direction [101] (fiber texture). We show that crystalline structures of medium complexity and their microstructures can be determined from rapid GIXD experiments from standard radiation, combined with molecular replacement procedure using crystal structures of compounds with higher chain lengths as reference data.
- Luis-Raya, Gilgamesh,Ramírez-Cardona, Màrius,Luna-Bárcenas, Gabriel,Hernández-Landaverde, Martín A.,Jiménez-Nieto, Adair,García-Rivas, Jose Luis,Espa A-Sánchez, Beatriz Liliana,Sanchez, Isaac C.
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- Binding orientation and reactivity of alkyl α,ω-dibromides in water-soluble cavitands
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Host-guest complexation of long chain α,ω-dibromides was evaluated in deep water-soluble cavitands 1 and 2. The bound dibromides (C7-C12) tumble rapidly on the NMR timescale and averaged signals were observed. The complexation allows mono hydrolysis of dibromides in aqueous solution. The arrangement of the products in the host-guest complex was fixed in an unsymmetrical manner that protects the guest from further reaction. Up to 93% yields of the mono-alcohols were obtained. The α,ω-dibromides formed a capsule with cavitand 2 and remained unreactive to hydrolysis.
- Angamuthu, Venkatachalam,Petroselli, Manuel,Rahman, Faiz-Ur,Yu, Yang,Rebek, Julius
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- The head-to-head reductive coupling of homoallylic alcohols promoted by titanium(II)-olefin complexes
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Reaction of homoallylic alcohols 1a-e with i-PrMgBr in the presence of Ti(i-PrO)4 leads to the unbranched saturated diols 2a-e as the main products in moderate to good yields. The head-to-head regioselectivity in reductive coupling of 4-penten-
- Isakov, Vladimir E.,Kulinkovich, Oleg G.
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- Pheromones of insects and their analogs. LII. Sythesis of dodec-9-en-1-yl and tetradec-11-en-1-yl acetates from the products of the partial ozonolysis of cycloocta-1z,5z-diene and cyclodeca-1e,5z-diene
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A new approach to the synthesis of octane-1,8-and decane-1,10-diols based on the partial ozonolysis of cyclic oligomers has been developed.
- Odinokov,Botsman,Gladysheva
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- Selective acidic cleavage of ketals in the presence of tert.-butyldimethylsilyl ethers
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Dilute methanolic HCl in anhydrous THF (3OH, ca. 10-2 molar H+) cleaves acetals and ketals, whereas t-butyldimethylsilyl ethers where recovered unchanged even at elevated temperatures.
- Zimmermann
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- ELECTROCHEMICAL REDUCTIONS IN LIQUID AMMONIA: ELECTROLYTIC BIRCH REACTIONS AND CHEMICAL BOND FISSIONS
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A procedure of electrochemical reduction in liquid ammonia using a single-compartment cell equiped with a soluble anode is described and illustrated in the case of aromatic compounds and esters.
- Chaussard, J.,Combellas, C.,Thiebault, A.
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- Multi-enzymatic cascade reactions with Escherichia coli-based modules for synthesizing various bioplastic monomers from fatty acid methyl esters?
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Multi-enzymatic cascade reaction systems were designed to generate biopolymer monomers using Escherichia coli-based cell modules, capable of carrying out one-pot reactions. Three cell-based modules, including a ω-hydroxylation module (Cell-Hm) to convert fatty acid methyl esters (FAMEs) to ω-hydroxy fatty acids (ω-HFAs), an amination module (Cell-Am) to convert terminal alcohol groups of the substrate to amine groups, and a reduction module (Cell-Rm) to convert the carboxyl groups of fatty acids to alcohol groups, were constructed. The product-oriented assembly of these cell modules involving multi-enzymatic cascade reactions generated ω-ADAs (up to 46 mM), α,ω-diols (up to 29 mM), ω-amino alcohols (up to 29 mM) and α,ω-diamines (up to 21 mM) from 100 mM corresponding FAME substrates with varying carbon chain length (C8, C10, and C12). Finally 12-ADA and 1,12-diol were purified with isolated yields of 66.5% and 52.5%, respectively. The multi-enzymatic cascade reactions reported herein present an elegant ‘greener’ alternative for the biosynthesis of various biopolymer monomers from renewable saturated fatty acids.
- Jung, Hyunsang,Kim, Byung-Gee,Kim, Ye Chan,Park, Beom Gi,Patil, Mahesh D.,Sarak, Sharad,Yoo, Hee-Wang,Yun, Hyungdon
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supporting information
p. 2222 - 2231
(2022/04/03)
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- METHOD AND CATALYST FOR PRODUCING ALCOHOL
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An alcohol production method in which an alcohol is produced from a carbonyl compound, the method including producing an alcohol by using a catalyst, the catalyst including a metal component including rhenium having an average valence of 4 or less and a carrier supporting the metal component, the carrier including zirconium oxide. A catalyst for producing an alcohol by hydrogenation of a carbonyl compound, the catalyst including a carrier including zirconium oxide and a metal component supported on the carrier, the metal component including rhenium having an average valence of 4 or less.
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Paragraph 0223-0277
(2021/05/14)
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- Chemoselective Cleavage of Si-C(sp3) Bonds in Unactivated Tetraalkylsilanes Using Iodine Tris(trifluoroacetate)
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Organosilanes are synthetically useful reagents and precursors in organic chemistry. However, the typical inertness of unactivated Si-C(sp3) bonds under conventional reaction conditions has hampered the application of simple tetraalkylsilanes in organic synthesis. Herein we report the chemoselective cleavage of Si-C(sp3) bonds of unactivated tetraalkylsilanes using iodine tris(trifluoroacetate). The reaction proceeds smoothly under mild conditions (-50 °C to room temperature) and tolerates various polar functional groups, thus enabling subsequent Tamao-Fleming oxidation to provide the corresponding alcohols. NMR experiments and density functional theory calculations on the reaction indicate that the transfer of alkyl groups from Si to the I(III) center and the formation of the Si-O bond proceed concertedly to afford an alkyl-λ3-iodane and silyl trifluoroacetate. The developed method enables the use of unactivated tetraalkylsilanes as highly stable synthetic precursors.
- Matsuoka, Keitaro,Komami, Narumi,Kojima, Masahiro,Mita, Tsuyoshi,Suzuki, Kimichi,Maeda, Satoshi,Yoshino, Tatsuhiko,Matsunaga, Shigeki
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p. 103 - 108
(2021/01/13)
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- Hydroboration Reaction and Mechanism of Carboxylic Acids using NaNH2(BH3)2, a Hydroboration Reagent with Reducing Capability between NaBH4and LiAlH4
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Hydroboration reactions of carboxylic acids using sodium aminodiboranate (NaNH2[BH3]2, NaADBH) to form primary alcohols were systematically investigated, and the reduction mechanism was elucidated experimentally and computationally. The transfer of hydride ions from B atoms to C atoms, the key step in the mechanism, was theoretically illustrated and supported by experimental results. The intermediates of NH2B2H5, PhCH= CHCOOBH2NH2BH3-, PhCH= CHCH2OBO, and the byproducts of BH4-, NH2BH2, and NH2BH3- were identified and characterized by 11B and 1H NMR. The reducing capacity of NaADBH was found between that of NaBH4 and LiAlH4. We have thus found that NaADBH is a promising reducing agent for hydroboration because of its stability and easy handling. These reactions exhibit excellent yields and good selectivity, therefore providing alternative synthetic approaches for the conversion of carboxylic acids to primary alcohols with a wide range of functional group tolerance.
- Wang, Jin,Ju, Ming-Yue,Wang, Xinghua,Ma, Yan-Na,Wei, Donghui,Chen, Xuenian
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p. 5305 - 5316
(2021/04/12)
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- Chemoselective Oxidation of p-Methoxybenzyl Ethers by an Electronically Tuned Nitroxyl Radical Catalyst
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The oxidation of p-methoxy benzyl (PMB) ethers was achieved using nitroxyl radical catalyst 1, which contains electron-withdrawing ester groups adjacent to the nitroxyl group. The oxidative deprotection of the PMB moieties on the hydroxy groups was observed upon treatment of 1 with 1 equiv of the co-oxidant phenyl iodonium bis(trifluoroacetate) (PIFA). The corresponding carbonyl compounds were obtained by treating the PMB-protected alcohols with 1 and an excess of PIFA.
- Hamada, Shohei,Sugimoto, Koichi,Elboray, Elghareeb E.,Kawabata, Takeo,Furuta, Takumi
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supporting information
p. 5486 - 5490
(2020/07/24)
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- Selective Hydroboration–Oxidation of Terminal Alkenes under Flow Conditions
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An efficient flow process for the selective hydroboration and oxidation of different alkenes using 9-borabicyclo(3.3.1)nonane (9-BBN) allows facile conversion in high productivity (1.4 g h?1) of amorpha-4,11-diene to the corresponding alcohol, which is an advanced intermediate in the synthesis of the antimalarial drug artemisinin. The in situ reaction of borane and 1,5-cyclooctadiene using a simple flow generator proved to be a cost efficient solution for the generation of 9-BBN.
- Elsherbini, Mohamed,Huynh, Florence,Dunbabin, Alice,Allemann, Rudolf K.,Wirth, Thomas
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supporting information
p. 11423 - 11425
(2020/08/07)
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- Novel insights into oxidation of fatty acids and fatty alcohols by cytochrome P450 monooxygenase CYP4B1
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CYP4B1 is an enigmatic mammalian cytochrome P450 monooxygenase acting at the interface between xenobiotic and endobiotic metabolism. A prominent CYP4B1 substrate is the furan pro-toxin 4-ipomeanol (IPO). Our recent investigation on metabolism of IPO related compounds that maintain the furan functionality of IPO while replacing its alcohol group with alkyl chains of varying structure and length revealed that, in addition to cytotoxic reactive metabolite formation (resulting from furan activation) non-cytotoxic ω-hydroxylation at the alkyl chain can also occur. We hypothesized that substrate reorientations may happen in the active site of CYP4B1. These findings prompted us to re-investigate oxidation of unsaturated fatty acids and fatty alcohols with C9–C16 carbon chain length by CYP4B1. Strikingly, we found that besides the previously reported ω- and ω-1-hydroxylations, CYP4B1 is also capable of α-, β-, γ-, and δ-fatty acid hydroxylation. In contrast, fatty alcohols of the same chain length are exclusively hydroxylated at ω, ω-1, and ω-2 positions. Docking results for the corresponding CYP4B1-substrate complexes revealed that fatty acids can adopt U-shaped bonding conformations, such that carbon atoms in both arms may approach the heme-iron. Quantum chemical estimates of activation energies of the hydrogen radical abstraction by the reactive compound 1 as well as electron densities of the substrate orbitals led to the conclusion that fatty acid and fatty alcohol oxidations by CYP4B1 are kinetically controlled reactions.
- Thesseling, Florian A.,Hutter, Michael C.,Wiek, Constanze,Kowalski, John P.,Rettie, Allan E.,Girhard, Marco
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- Preparation method for 1,10-decanediol
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The invention relates to a preparation method for 1,10-decanediol. The method is characterized by using 9-decenoate as a raw material, and adopting an epoxidation-transfer hydrogenation two-step reaction to obtain the 1,10-decanediol, wherein an epoxidation step uses a molybdenum catalyst and an organic peroxide, and the yield of 9,10-epoxidized methyl decanoate is greater than 95%; and a transferhydrogenation reaction adopts a hydrogen donor instead of a hydrogen gas, and a reducing additive is introduced to reduce epoxy and ester groups to hydroxyl in one step at normal pressure. The methodprovided by the invention does not need to use the high-pressure hydrogen gas, so that the investment of a reaction device is reduced, the complexity of operation is reduced, the safety of the reaction is increased, the yield of a target product is improved, the problems that products are difficult to separate and a large amount of industrial waste water is difficult to treat in a traditional production technology are solved, the raw material 9-decenoate is cheap and easy to obtain, the preparation process is simple, and the method has not high requirements for equipment and is suitable for industrialized production.
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Paragraph 0055; 0058; 0059; 0061; 0064; 0067; 0070; 0072
(2018/08/04)
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- Method for preparing 1,10-decanediol through supercritical dimethyl sebacate hydrogenation
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The present invention discloses a method for preparing 1,10-decanediol through supercritical dimethyl sebacate hydrogenation. The method comprises that: (1) methanol is adopted as a supercritical fluid, the methanol and dimethyl sebacate are uniformly mixed, the obtained mixture is conveyed into a pre-mixer through a high-pressure injection pump, the pressure of hydrogen is increased through a hydrogen pressurization system to achieve a certain pressure, the pressurized hydrogen is conveyed to the pre-mixer and then is continuously conveyed into a fixed bed reactor loaded with a supported catalyst, and a hydrogenation reaction is performed at a reaction temature of 240-280 DEG C under a reaction pressure of 7-12 MPa according to a hydrogen to ester ratio of 30:1-150:1, wherein the reaction system is in the supercritical state of the methanol, and the used catalyst is a Cu/ZnO/Al2O3 catalyst; and (2) vapor-liquid separation is performed, the liquid phase product is collected, and the decanediol is rectified from the liquid phase product. According to the method of the present invention, the methanol is adopted as the supercritical fluid and does not have corrosion, the mass transfer resistance during the dimethyl sebacate reaction process can be eliminated, the hydrogen to ester ratio is low, and the conversion rate of the dimethyl sebacate and the selectivity of the 1,10-decanediol are high.
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Paragraph 0017-0018
(2017/03/14)
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- FeCl3-catalyzed self-cleaving deprotection of methoxyphenylmethyl-protected alcohols
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4-Methoxyphenylmethyl ethers are widely utilized as alcohol protecting groups. FeCl3 effectively catalyzes the deprotection of methoxyphenylmethyl-type ethers in a self-cleaving manner to produce oligomeric derivatives and alcohols. Remarkably, the highly pure mother alcohols can be obtained without silica gel column chromatography by using the 2,4-dimethoxyphenylmethyl group as a protective group.
- Sawama, Yoshinari,Masuda, Masahiro,Asai, Shota,Goto, Ryota,Nagata, Saori,Nishimura, Shumma,Monguchi, Yasunari,Sajiki, Hironao
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p. 434 - 437
(2015/03/03)
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- Sustainable, mild and efficient p-methoxybenzyl ether deprotections utilizing catalytic DDQ
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A procedure for the selective deprotection of p-methoxybenzyl ethers using catalytic amounts of DDQ and of sodium nitrite, with oxygen as the terminal oxidant, is reported.
- Walsh, Katie,Sneddon, Helen F.,Moody, Christopher J.
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p. 7380 - 7387
(2017/09/13)
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- Ni-catalyzed reductive homocoupling of unactivated alkyl bromides at room temperature and its synthetic application
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A room-temperature Ni-catalyzed reductive approach to homocoupling of unactivated primary, secondary, and tertiary alkyl bromides is described. The catalytic system can be easily generated from air-stable and cheap materials and demonstrates broad functional group tolerance, thus allowing facile access to useful dimeric triterpene and lignan-like molecules. Moreover, the dimerization of tertiary bromide 6 efficiently establishes sterically hindered vicinal quaternary carbons (C3a and C3a′), which is a key linkage of intriguing bispyrrolo[2,3-b]indoline alkaloids, thereby enabling us to complete the total syntheses of racemic chimonanthine (9) and folicanthine (10). In addition, this dimerization method can be expanded to the highly stereoselective synthesis of bisperhydrofuro[2,3-b]furan (5a) and the dimeric spiroketal 5b, signifying the involvement of possible radical species.
- Peng, Yu,Luo, Long,Yan, Chang-Song,Zhang, Jian-Jian,Wang, Ya-Wen
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p. 10960 - 10967
(2013/11/19)
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- Regioselective ω-hydroxylation of medium-chain n-alkanes and primary alcohols by CYP153 enzymes from Mycobacterium marinum and Polaromonas sp. strain JS666
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The oxofunctionalization of saturated hydrocarbons is an important goal in basic and applied chemistry. Biocatalysts like cytochrome P450 enzymes can introduce oxygen into a wide variety of molecules in a very selective manner, which can be used for the synthesis of fine and bulk chemicals. Cytochrome P450 enzymes from the CYP153A subfamily have been described as alkane hydroxylases with high terminal regioselectivity. Here we report the product yields resulting from C5-C12 alkane and alcohol oxidation catalyzed by CYP153A enzymes from Mycobacterium marinum (CYP153A16) and Polaromonas sp. (CYP153A P. sp.). For all reactions, byproduct formation is described in detail. Following cloning and expression in Escherichia coli, the activity of the purified monooxygenases was reconstituted with putidaredoxin (CamA) and putidaredoxin reductase (CamB). Although both enzyme systems yielded primary alcohols and α,ω-alkanediols, each one displayed a different oxidation pattern towards alkanes. For CYP153A P. sp. a predominant ω-hydroxylation activity was observed, while CYP153A16 possessed the ability to catalyze both ω-hydroxylation and α,ω- dihydroxylation reactions.
- Scheps, Daniel,Honda Malca, Sumire,Hoffmann, Helen,Nestl, Bettina M.,Hauer, Bernhard
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scheme or table
p. 6727 - 6733
(2011/11/30)
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- CeCl3-catalyzed reduction of methyl esters of carboxylic acids to corresponding alcohols with sodium borohydride
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A wide range of methyl esters, including esters of aromatic carboxylic acids, alkenyl carboxylic acids, aliphatic carboxylic acids, and protected amino acids, were reduced to the corresponding alcohols with NaBH4 in ethanol in the presence of a catalytic amount of CeCl3. The reaction was completed within 24h at ambient temperature and showed high functional group compatibility and chemoselectivity. With esters containing nitro, methoxyl, halogen, alkenyl, and protected amino functionalities, only the ester group was reduced. The alcohols were isolated after evaporation of the solvent and routine aqueous workup in good yields (75-95%). Copyright
- Xu, Yinan,Wei, Yunyang
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experimental part
p. 3423 - 3429
(2010/12/24)
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- Iterative tandem catalysis of secondary diols and diesters to chiral polyesters
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The well-known dynamic kinetic resolution of secondary alcohols and esters was extended to secondary diols and diesters to afford chiral polyesters. This process is an example of iterative tandem catalysis (ITC), a polymerization method where the concurrent action of two fundamentally different catalysts is required to achieve chain growth. In order to procure chiral polyesters of high enantiomeric excess value (ee) and good molecular weight, the catalysts employed need to be complementary and compatible during the polymerization reaction. We here show that Shvo's catalyst and Novozym 435 fulfil these requirements. The optimal polymerization conditions of 1,1′-(1,3-phenylene) diethanol (1,3-diol) and diisopropyl adipate required 2mol% Shvo's catalyst and 12 mg Novozym 435 per mmol alcohol group in the presence of 0.5 M 2,4-dimethyl-3- pentanol as the hydrogen donor. With these conditions, chiral polyesters were obtained with peak molecular weights up to 15kDa, an ee value up to 99% and with 1-3% ketone end groups. Also with the structural isomer, 1,4-diol, a chiral polyester was obtained, albeit with lower molecular weight (8.3 kDa) and slightly lower ee (94%). Aliphatic secondary diols also resulted in enantio-enriched polymers but at most an ee of 46% was obtained with molecular weights in the range of 3.33.7 kDa. This low ee originates from the intrinsic low enantioselectivity of Novozym 435 for this type of secondary aliphatic diols. The results presented here show that ITC can be applied to procure chiral polyesters with good molecular weight and high ee from optically inactive AA-BB type monomers.
- Van As, Bart A.C.,Van Buijtenen, Jeroen,Mes, Tristan,Palmans, Anja R.A.,Meijer
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p. 8325 - 8332
(2008/09/16)
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- Conversion of alkyl halides into alcohols via formyloxylation reaction with DMF catalyzed by silver salts
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The transformation of alkyl halides into alcohols via a two-step process based on the reaction with DMF catalyzed by Ag(I) salts followed by acid or basic hydrolysis of the intermediate formate ester has been evaluated. The results show that a large variety of primary and some secondary alkyl halides can be transformed efficiently into the corresponding alcohols, making this alkyl halide to alcohol interconversion a valuable alternative to the existing procedures, particularly in molecules with labile functional groups that are generally involved in multistep synthesis. Georg Thieme Verlag Stuttgart.
- Abad, Antonio,Agullo, Consuelo,Cunat, Ana C.,Navarro, Ismael
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p. 3355 - 3361
(2007/10/03)
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- METHOD OF HYDROGENATION REACTION
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Disclosed is a heterogeneous catalytic hydrogenation process comprising hydrogenating a substance to be hydrogenated under trickle flow condition using a reaction tower charged with a solid catalyst, in which hydrogen gas and a liquid phase containing the substance to be hydrogenated are made to flow co-currently downward from above, wherein dynamic liquid phase holdup amount per unit catalyst exterior surface area of the catalyst charged in the reaction tower is 0.005 × 10-3 to 0.14 × 10-3 m3/m2 and the catalyst has a catalyst strength of 1.0 Kg or more, as determined by the following formulacatalyst strength = A-2σ wherein A represents a mean value of minimum strengths of 100 catalyst samples measured according to the method described in "Test method for crushing strength" of JIS Z-8841-1993" and σ represents a mean standard deviation.
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Page/Page column 21-22
(2008/06/13)
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- DERMATOLOGICAL COMPOSITIONS AND METHODS
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Disclosed are methods and compositions for regulating the melanin content of mammalian melanocytes; regulating pigmentation in mammalian skin, hair, wool or fur; treating or preventing various skin and proliferative disorders; by administration of various compounds, including alcohols, diols and/or triols and their analogues.
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- A novel hydrogen transfer hydroalumination of alkenes with triisobutylaluminum catalyzed by Pd and other late transition metal complexes
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Hydrogen transfer hydroalumination of terminal alkenes and dienes can be achieved with 1.1 equiv. of (i-Bu)3Al and catalytic amounts of Cl2Pd(PPh3)2 and other late transition metal complexes containing Co, Rh, Ni, and Pt at ambient temperature in high yields.
- Gagneur, Sebastien,Makabe, Hidefumi,Negishi, Ei-Ichi
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p. 785 - 787
(2007/10/03)
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- Treatment of neurodegenerative diseases
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Disclosed are methods for increasing the differentiation of mammalian neuronal cells for purposes of treating neurodegenerative diseases or nerve damage by administration of various compounds including alcohols, diols and/or triols and their analogues.
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- Treatment of diseases mediated by the nitric oxide/cGMP/protein kinase G pathway
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Disclosed are methods and compositions for stimulating cellular nitric oxide (NO) synthesis, cyclic guanosine monophosphate levels (cGMP), and protein kinase G (PKG) activity for purposes of treating diseases mediated by deficiencies in the NO/cGMP/PKG signal transduction pathway, by administration of various compounds including alcohols, diols and/or triols and their analogues.
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- Trichloroacetimidate as an efficient protective group for alcohols
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The trichloroacetimidate is disclosed to be a general and efficient protective group for alcohols, which can be deprotected under mild acidic, basic, or neutral conditions, and has orthogonal stability with the acetate and tert-butyldimethylsilyl (TBS) protections.
- Yu, Biao,Yu, Hai,Hui, Yongzheng,Han, Xiuwen
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p. 753 - 755
(2007/10/03)
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- Pd/C(en)-catalyzed regioselective hydrogenolysis of terminal epoxides to secondary alcohols
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Various terminal epoxides, such as 1,2-epoxyalkanes, glycidyl ethers and glycidol, were hydrogenolyzed to give secondary alcohols with high regioselectivity using a 10% Pd/C-ethylenediamine complex as a catalyst under entirely neutral conditions.
- Sajiki, Hironao,Hattori, Kazuyuki,Hirota, Kosaku
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p. 1041 - 1042
(2007/10/03)
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- Selective deprotection of tert-butyldimethylsilyl ether with lithium bromide and 18-crown-6
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Lithium bromide, in the presence of a crown ether, has been found to selectively remove primary tert-butyldimethylsilyl ethers under controlled conditions. This selectivity has been utilized to synthesize 3'-TBDMS-2'- deoxyuridine in one step from the diprotected compound.
- Tandon, Manish,Begley, Tadhg P.
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p. 2953 - 2959
(2007/10/03)
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- Preparation of ω-hydroxy acids by reduction of α,ω-methylene diesters with NaBH4
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By reaction of the dicesium salts of long chain dicarboxylic acids (C atoms > 9) with methylene iodide the corresponding methylene diesters were prepared. These acylals, by reduction with NaBH4 in THF, give the corresponding ω-hydroxy acids.
- Benitez, Pilar,Delgado, Ana,Farrera, Joan-Anton,Ribo, Josep M.
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p. 1697 - 1702
(2007/10/03)
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- Deprotection of mono and dimethoxy phenyl methyl ethers using catalytic amounts of DDQ
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4-Methoxy and 3,4 dimethoxy benzyl ethers have been deprotected with catalytic amounts of DDQ by oxidative recycling of the byproduct DDHQ with FeCl3 for the first time.
- Chandrasekhar,Sumithra,Yadav
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p. 1645 - 1646
(2007/10/03)
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- Reaction of diisopropoxytitanium (III) tetrahydroborate with selected organic compounds containing representative functional groups
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Diisopropoxytitanium(III) tetrahydroborate, (1PrO)2TiBH4), generated in situ in dichloromethane from diisopropoxytitanium dichloride and benzyltriethylammonium borohydride in a 1:2 ratio selectively reduces aldehydes, ketones, acid chlorides, carboxylic acids, and N-Boc-protected amino acids to the corresponding alcohols in excellent yield under very mild reaction conditions (-78 to 25°C).
- Ravikumar,Chandrasekaran, Srinivasan
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p. 826 - 830
(2007/10/03)
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- Hydrogenation of carboxylic acids using bimetallic catalysts consisting of Group 8 to 10, and Group 6 or 7 metals
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Hydrogenation of carboxylic acids to alcohols was effectively catalyzed by bimetallic systems consisting of Group 8 to 10 late transition-metals, and Group 6 or 7 early transition-metal carbonyls. These catalysts easily converted α,ω-dicarboxylic acid monoesters into ω-hydroxyalkanoic esters in good yields.
- He, De-Hua,Wakasa, Noriko,Fuchikami, Takamasa
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p. 1059 - 1062
(2007/10/02)
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- Synthesis of diols, for use as intermediates for polymeric materials, by starting from terminal diolefins
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Disclosed is the synthesis of terminal diols, which are organic intermediates used in order to produce polymeric materials, by starting from terminal diolefins, which synthesis is based on the oxidation of diolefins to yield diepoxides, in a double-phase aqueous-organic system with hydrogen peroxide and in the presence of catalysts soluble in the organic phase, followed by a reaction of reduction of the resulting diepoxides.
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- Method for blood coagulation on hard tissues
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A method of using resorbable waxes for coagulation of blood on endogenous hard tissue, especially bone, which waxes consist of waxy polyester-oligomers of hydroxybarboxylic acids which are viscous to solid at body temperature. On the basis of their structure, these waxes are degradable by endogenous metabolic mechanism, wherein the rate of degradation can be adjusted.
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- Cosmetic composition
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A water-pin-silicone oil emulsion, suitable for topical application to mammalian skin or hair, comprises, in addition to water, a volatile polydimethylsiloxane, a silicone surfactant ingredient comprising a polymer of dimethylpolysiloxane with polyoxyethylene and/or polyoxypropylene side chains having a molecular weight of from 10,000 to 50,000, a 2-hydroxyalkanoic acid or derivative thereof, ultrafine titanium dioxide, and an inorganic electrolyte.
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- Facile Electroreduction of Methyl Esters and N,N-Dimethylamides of Aliphatic Carboxylic Acids to Primary Alcohols
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In the presence of t-BuOH, methyl esters and N,N-dimethylamides of aliphatic carboxylic acids are electroreduced at a Mg cathode to the corresponding primary alcohols.In the presence of t-BuOD instead of t-BuOH, the electroreduction of the esters gives the corresponding 1,1-dideuterated alcohol.In all cases, the yields are excellent.
- Shono, Tatsuya,Masuda, Haruhisa,Murase, Hiroaki,Shimomura, Masatoshi,Kashimura, Shigenori
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p. 1061 - 1063
(2007/10/02)
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- Reduction of carboxylic acids into alcohols using NaBH4 in the presence of catechol and/or CF3COOH
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Reaction of aliphatic carboxylic acids (1 eq) using NaBH4 (2 eq) and catechol (2 eq) in THF at 25°C gives the corresponding alcohols in 47-49% yield besides the unreacted carboxylic acids. Reduction of aliphatic carboxylic acids (1 eq) using NaBH4 (2 eq), catechol (2 eq) and CF3COOH (1 eq) gives the aliphatic alcohols in 87-94% yields. Reductions using aliphatic acids (1 eq), NaBH4 (1 eq) and CF3COOH (1 eq) also give aliphatic alcohols in 93-95% yields. Under these conditions, the aromatic acids give poor yields. However, capric acid (1 eq) is selectively reduced to 1-decanol in 72% yield in the presence of benzoic acid (1 eq).
- Suseela, Yantrapragada,Periasamy, Mariappan
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p. 371 - 376
(2007/10/02)
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- Cosmetic composition
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A water-in-silicone oil emulsion, suitable for topical application to mammalian skin or hair, comprises, in addition to water, a volatile polydimethylsiloxane, a silicone surfactant ingredient comprising a polymer of dimethylpolysiloxane with polyoxyethylene and/or polyoxypropylene side chains having a molecular weight of from 10,000 to 50,000, an inorganic electrolyte and preferably a 2-hydroxyalkanoic acid or derivative thereof, and an alkane diol.
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- Cosmetic emulsion
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A cosmetic emulsion suitable for topical application to human skin or hair comprises in addition to water: i. from 2 to 95% by weight of a polyol fatty acid polyester, the polyol having at least 4 free hydroxyl groups, at least 60% of which are then esterified with one or more fatty acids having from 8 to 22 carbon atoms; ii. from 1 to 20% by weight of an emulsifier; the emulsion having an aqueous phase which forms from 4 to 97% by volume, and a non-aqueous phase which forms from 3 to 96% by volume;, provided that when the emulsion is an oil-in-water emulsion, the emulsion is substantially free from an emulsifier having an HLB value of 6.
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- Use of Zinc Borohydride for Efficient Reduction of Carboxylic Ester to Alcohol. Selective Reduction of Aliphatic Ester in Presence of Aromatic Ester Under Sonication
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An efficient methodology using zinc borohydride under sonication for the reduction of carboxylic esters to alcohols in presence of N,N-dimethylaniline and selective reduction of an aliphatic ester over an aromatic one without N,N-dimethylaniline is described.
- Ranu, Brindaban C.,Basu, Manas K.
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p. 3243 - 3246
(2007/10/02)
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- Lactones. 2. Enthalpies of hydrolysis, reduction, and formation of the C4-C13 monocyclic lactones. Strain energies and conformations
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The enthalpies of hydrolysis of the monocyclic lactones from γ-butyrolactone to tridecanolactone were determined calorimetrically, and the acyclic ethyl having the number of atoms were studied in the fashion. The enthalpies of reduction of the lactones to the corresponding α,ω-alkanediols with lithium triethylborohydride also were determined. The enthalpies of formation of the lactones and the ethyl esters were derived from these data. They were converted to values for the gas phase by measuring the enthalpies of vaporization of ethyl esters and of lactones. In the of γ-butyrolactone and δ-valerolactone, the enthalpies of formation were in good accord with the previously reported values determined via combustion calorimetry. The strain energies of the lactones were obtained via isodesmic reactions. Valerolactone had a strain energy of 11 kcal/mol, and the largest strain energy was found with octanolactone (13 kcal/mol). The conformations of γ-butyrolactone and δ-valerolactone were studied via MP2/6-31G* geometry optimizations, and the conformations of the other lactones were studied with use of the molecular mechanics program MM3. The energies of the lactones estimated via molecular mechanics were compared with the experimental results.
- Wiberg, Kenneth B.,Waldron, Roy F.
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p. 7697 - 7705
(2007/10/02)
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- MASS-SPECTROMETRIC STUDY OF THE PHEROMONE OF THE COTTON BOLLWORM AND ITS PRECURSORS
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The structures of the products of intermediate stages of the synthesis of the sex pheromone hexadec-11Z-enal that are labile to electron impact have been studied with the aid of low-resolution mass spectrometry and metastable ions.
- Igrasheva, G. A.,Razakov, R. R.
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p. 208 - 212
(2007/10/02)
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- THIOL ESTER IN ORGANIC SYNTHESIS XV. REDUCTION WITH TETRABUTYLAMMONIUM BOROHYDRIDE
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Treatment of thiol ester with tetrabutylammmonium borohydride in refluxing chloroform gave rise to the corresponding alcohols.
- Liu, Hsing-Jang,Luo, Weide
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p. 387 - 392
(2007/10/02)
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- Ozonolysis of Tetrasubstituted Ethylenes, Cycloolefins, and Conjugated Dienes on Polyethylene
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Ozonolyses of four tetrasubstituted ethylenes (7a-d), of two medium-sized cycloolefins (10a,b), and of norbornene (14) on polyethylene gave the corresponding ozonides, which could not be obtained by ozonolyses in solution.Ozonolyses of three conjugated dienes (25a,b,28) on polyethylene gave the corresponding diozonides, as the first examples of this class of ozonides.The thermal decomposition of some of the ozonides has been studied.
- Griesbaum, Karl,Volpp, Willi,Greinert, Reinhard,Greunig, Hans-Joachim,Schmid, Jurgen,Henke, Henning
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p. 383 - 389
(2007/10/02)
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- Ring Enlargement of Boracyclanes via Sequential One-Carbon Homologation. The First Synthesis of Boracyclanes in the Strained Medium Ring Range.
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We explored the Matteson homologation procedure as a means of enlarging the size of the ring in B-methoxyboracyclanes.
- Brown, Herbert C.,Phadke, Avinash S.,Rangaishenvi, Milind V.
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p. 6263 - 6264
(2007/10/02)
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