- Borane evolution and its application to organic synthesis using the phase-vanishing method
-
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
-
supporting information
(2021/03/26)
-
- Regiodivergent Hydroborative Ring Opening of Epoxides via Selective C-O Bond Activation
-
A magnesium-catalyzed regiodivergent C-O bond cleavage protocol is presented. Readily available magnesium catalysts achieve the selective hydroboration of a wide range of epoxides and oxetanes yielding secondary and tertiary alcohols in excellent yields and regioselectivities. Experimental mechanistic investigations and DFT calculations provide insight into the unexpected regiodivergence and explain the different mechanisms of the C-O bond activation and product formation.
- Magre, Marc,Paffenholz, Eva,Maity, Bholanath,Cavallo, Luigi,Rueping, Magnus
-
supporting information
p. 14286 - 14294
(2020/09/15)
-
- Visible-Light-Mediated Aerobic Oxidation of Organoboron Compounds Using in Situ Generated Hydrogen Peroxide
-
A simple and general visible-light-mediated oxidation of organoboron compounds has been developed with rose bengal as the photocatalyst, substoichiometric Et3N as the electron donor, as well as air as the oxidant. This mild and metal-free protocol shows a broad substrate scope and provides a wide range of aliphatic alcohols and phenols in moderate to excellent yields. Notably, the robustness of this method is demonstrated on the stereospecific aerobic oxidation of organoboron compounds.
- Weng, Wei-Zhi,Liang, Hao,Zhang, Bo
-
supporting information
p. 4979 - 4983
(2018/08/24)
-
- Regioselective hydrosilylation of epoxides catalysed by nickel(II) hydrido complexes
-
Bench-stable nickel fluoride complexes bearing NNN pincer ligands have been employed as precursors for the regioselective hydrosilylation of epoxides at room temperature. A nickel hydride assisted epoxide opening is followed by the cleavage of the newly formed nickel oxygen bond by σ-bond metathesis with a silane.
- Wenz, Jan,Wadepohl, Hubert,Gade, Lutz H.
-
supporting information
p. 4308 - 4311
(2017/04/21)
-
- Discovery, synthesis, and structure-activity relations of 3,4-dihydro-1H-spiro(naphthalene-2,2′-piperidin)-1-ones as potassium-competitive acid blockers
-
With the aim to discover a gastric antisecretory agent more potent than the existing proton pump inhibitors, novel 3,4-dihydro-1H-spiro(naphthalene-2,2′-piperidin)-1-one derivatives, which could occupy two important lipophilic pockets (described as LP-1 and LP-2) of H+,K+-ATPase and can strongly bind to the K+-binding site, were designed based on a docking model. Among the compounds synthesized, compound 4d showed a strong H+,K+-ATPase-inhibitory activity and a high stomach concentration in rats, resulting in potent inhibitory action on histamine-stimulated gastric acid secretion in rats. Furthermore, 4d exerted significant inhibitory action on histamine-stimulated gastric-acid secretion in rats with a rapid onset and moderate duration of action after the administration. These findings may lead to a new insight into the drug design of potassium-competitive acid blockers.
- Imaeda, Toshihiro,Ono, Koji,Nakai, Kazuo,Hori, Yasunobu,Matsukawa, Jun,Takagi, Terufumi,Fujioka, Yasushi,Tarui, Naoki,Kondo, Mitsuyo,Imanishi, Akio,Inatomi, Nobuhiro,Kajino, Masahiro,Itoh, Fumio,Nishida, Haruyuki
-
p. 3719 - 3735
(2017/06/13)
-
- Biocatalytic Formal Anti-Markovnikov Hydroamination and Hydration of Aryl Alkenes
-
Biocatalytic anti-Markovnikov alkene hydroamination and hydration were achieved based on two concepts involving enzyme cascades: epoxidation-isomerization-amination for hydroamination and epoxidation-isomerization-reduction for hydration. An Escherichia coli strain coexpressing styrene monooxygenase (SMO), styrene oxide isomerase (SOI), ω-transaminase (CvTA), and alanine dehydrogenase (AlaDH) catalyzed the hydroamination of 12 aryl alkenes to give the corresponding valuable terminal amines in high conversion (many ≥86%) and exclusive anti-Markovnikov selectivity (>99:1). Another E. coli strain coexpressing SMO, SOI, and phenylacetaldehyde reductase (PAR) catalyzed the hydration of 12 aryl alkenes to the corresponding useful terminal alcohols in high conversion (many ≥80%) and very high anti-Markovnikov selectivity (>99:1). Importantly, SOI was discovered for stereoselective isomerization of a chiral epoxide to a chiral aldehyde, providing some insights on enzymatic epoxide rearrangement. Harnessing this stereoselective rearrangement, highly enantioselective anti-Markovnikov hydroamination and hydration were demonstrated to convert α-methylstyrene to the corresponding (S)-amine and (S)-alcohol in 84-81% conversion with 97-92% ee, respectively. The biocatalytic anti-Markovnikov hydroamination and hydration of alkenes, utilizing cheap and nontoxic chemicals (O2, NH3, and glucose) and cells, provide an environmentally friendly, highly selective, and high-yielding synthesis of terminal amines and alcohols.
- Wu, Shuke,Liu, Ji,Li, Zhi
-
p. 5225 - 5233
(2017/08/17)
-
- Antiproliferative activity and SARs of caffeic acid esters with mono-substituted phenylethanols moiety
-
A series of CAPE derivatives with mono-substituted phenylethanols moiety were synthesized and evaluated by MTT assay on growth of 4 human cancer cell lines (Hela, DU-145, MCF-7 and ECA-109). The substituent effects on the antiproliferative activity were systematically investigated for the first time. It was found that electron-donating and hydrophobic substituents at 2′-position of phenylethanol moiety could significantly enhance CAPE's antiproliferative activity. 2′-Propoxyl derivative, as a novel caffeic acid ester, exhibited exquisite potency (IC50?=?0.4?±?0.02 & 0.6?±?0.03?μM against Hela and DU-145 respectively).
- Xie, Jin,Yang, Fengzhi,Zhang, Man,Lam, Celine,Qiao, Yixue,Xiao, Jia,Zhang, Dongdong,Ge, Yuxuan,Fu, Lei,Xie, Dongsheng
-
p. 131 - 134
(2016/12/27)
-
- Nucleophilic addition of arylmethylzinc reagents (ArCH2ZnCl) to formaldehyde: An easy access to 2-(hetro)arylethyl alcohols
-
The selective addition of arylmethylmagnesium halides with formaldehyde giving arylethyl alcohols is extremely challenging. To circumvent the difficulties, in the current communication, we have reported on the nucleophilic addition of benzyl zinc reagents derived from inexpensive and abundant benzyl chlorides to paraformaldehyde. The reaction investigated herein is hitherto unknown and was found to be selective, operationally simple, atom- and step-economical and high yielding to deliver phenethyl alcohols utilized as key perfumery ingredients in 60–83% yields. After successful establishment of the reaction condition, the reaction was also scaled up successfully to deliver a large-scale preparation of the phenethyl alcohol.
- Bhatt,Samant,Pednekar, Suhas
-
supporting information
p. 968 - 974
(2017/05/04)
-
- Hydrogenation of Esters to Alcohols Catalyzed by Defined Manganese Pincer Complexes
-
The first manganese-catalyzed hydrogenation of esters to alcohols has been developed. The combination of Mn(CO)5Br with [HN(CH2CH2P(Et)2)2] leads to a mixture of cationic and neutral Mn PNP pincer complexes, which enable the reduction of various ester substrates, including aromatic and aliphatic esters as well as diesters and lactones. Notably, related pincer complexes with isopropyl or cyclohexyl substituents showed very low activity.
- Elangovan, Saravanakumar,Garbe, Marcel,Jiao, Haijun,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
-
supporting information
p. 15364 - 15368
(2016/12/03)
-
- A General, Practical Triethylborane-Catalyzed Reduction of Carbonyl Functions to Alcohols
-
A combination of the abundant and low-cost triethylborane and sodium alkoxide generates a highly efficient catalyst for reduction of esters, as well as ketones and aldehydes, to alcohols using an inexpensive hydrosilane under mild conditions. The catalyst system exhibits excellent chemoselectivity and a high level of functional group tolerance. Mechanistic studies revealed a resting state of sodium triethylalkoxylborate that is the product of the reaction of BEt3 with sodium alkoxide. This borate species reacts with hydrosilane to form NaBEt3H, which rapidly reduces esters.
- Peng, Dongjie,Zhang, Mintao,Huang, Zheng
-
supporting information
p. 14737 - 14741
(2015/10/19)
-
- Mechanism of SmI2/amine/H2O-promoted chemoselective reductions of carboxylic acid derivatives (esters, acids, and amides) to alcohols
-
Samarium(II) iodide-water-amine reagents have emerged as some of the most powerful reagents (E° = -2.8 V) for the reduction of unactivated carboxylic acid derivatives to primary alcohols under single electron transfer conditions, a transformation that had been considered to lie outside the scope of the classic SmI2 reductant for more than 30 years. In this article, we present a detailed mechanistic investigation of the reduction of unactivated esters, carboxylic acids, and amides using SmI2-water-amine reagents, in which we compare the reactivity of three functional groups. The mechanism has been studied using the following: (i) kinetic, (ii) reactivity, (iii) radical clock, and (iv) isotopic labeling experiments. The kinetic data indicate that for the three functional groups all reaction components (SmI2, amine, water) are involved in the rate equation and that the rate of electron transfer is facilitated by base assisted deprotonation of water. Notably, the mechanistic details presented herein indicate that complexation between SmI2, water, and amines can result in a new class of structurally diverse, thermodynamically powerful reductants for efficient electron transfer to a variety of carboxylic acid derivatives. These observations will have important implications for the design and optimization of new processes involving Sm(II)-reduction of ketyl radicals. (Chemical Equation Presented).
- Szostak, Michal,Spain, Malcolm,Eberhart, Andrew J.,Procter, David J.
-
p. 11988 - 12003
(2015/01/16)
-
- Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes
-
There is currently great interest in the development of multistep catalytic processes in which one or several catalysts act sequentially to rapidly build complex molecular structures. Many enzymes - often the inspiration for new synthetic transformations - are capable of processing a single substrate through a chain of discrete, mechanistically distinct catalytic steps. Here, we describe an approach to emulate the efficiency of these natural reaction cascades within a synthetic catalyst by the temporal separation of catalytic activities. In this approach, a single catalyst exhibits multiple catalytic activities sequentially, allowing for the efficient processing of a substrate through a cascade pathway. Application of this design strategy has led to the development of a method to effect the anti-Markovnikov (linear-selective) reductive functionalization of terminal alkynes. The strategy of temporal separation may facilitate the development of other efficient synthetic reaction cascades.
- Li, Le,Herzon, Seth B.
-
-
- A highly active and air-stable ruthenium complex for the ambient temperature anti-markovnikov reductive hydration of terminal alkynes
-
The conversion of terminal alkynes to functionalized products by the direct addition of heteroatom-based nucleophiles is an important aim in catalysis. We report the design, synthesis, and mechanistic studies of the half-sandwich ruthenium complex 12, which is a highly active catalyst for the anti-Markovnikov reductive hydration of alkynes. The key design element of 12 involves a tridentate nitrogen-based ligand that contains a hemilabile 3-(dimethylamino) propyl substituent. Under neutral conditions, the dimethylamino substituent coordinates to the ruthenium center to generate an air-stable, 18-electron, κ3-complex. Mechanistic studies show that the dimethylamino substituent is partially dissociated from the ruthenium center (by protonation) in the reaction media, thereby generating a vacant coordination site for catalysis. These studies also show that this substituent increases hydrogenation activity by promoting activation of the reductant. At least three catalytic cycles, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate aldehyde, operate concurrently in reactions mediated by 12. A wide array of terminal alkynes are efficiently processed to linear alcohols using as little as 2 mol % of 12 at ambient temperature, and the complex 12 is stable for at least two weeks under air. The studies outlined herein establish 12 as the most active and practical catalyst for anti-Markovnikov reductive hydration discovered to date, define the structural parameters of 12 underlying its activity and stability, and delineate design strategies for synthesis of other multifunctional catalysts.
- Zeng, Mingshuo,Li, Le,Herzon, Seth B.
-
supporting information
p. 7058 - 7067
(2014/06/09)
-
- Highly chemoselective reduction of amides (primary, secondary, tertiary) to alcohols using SmI2/amine/H2O under mild conditions
-
Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C-N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C-O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → πC=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C-N/C-O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions.
- Szostak, Michal,Spain, Malcolm,Eberhart, Andrew J.,Procter, David J.
-
supporting information
p. 2268 - 2271
(2014/03/21)
-
- On the role of pre- and post-electron-transfer steps in the SmI 2/Amine/H2O-mediated reduction of esters: New mechanistic insights and kinetic studies
-
The mechanism of the SmI2-mediated reduction of unactivated esters has been studied using a combination of kinetic, radical clocks and reactivity experiments. The kinetic data indicate that all reaction components (SmI2, amine, H2O) are involved in the rate equation and that electron transfer is facilitated by Bronsted base assisted deprotonation of water in the transition state. The use of validated cyclopropyl-containing radical clocks demonstrates that the reaction occurs via fast, reversible first electron transfer, and that the electron transfer from simple Sm(II) complexes to aliphatic esters is rapid. Notably, the mechanistic details presented herein indicate that complexation between SmI2, H2O and amines affords a new class of structurally diverse, thermodynamically powerful reductants for efficient electron transfer to carboxylic acid derivatives as an attractive alternative to the classical hydride-mediated reductions and as a source of acyl-radical equivalents for C-C bond forming processes. Electron donors: The mechanism of the SmI 2-mediated reduction of unactivated esters has been studied by using a combination of kinetic, radical clock, and reactivity experiments. Notably, the mechanistic details presented herein indicate that complexation between SmI2, H2O, and amines gives a new class of structurally diverse, thermodynamically powerful reductants for efficient electron transfer to carboxylic acid derivatives as an attractive alternative to the classical hydride-mediated reductions and as a source of acyl-radical equivalents for C-C bond-forming processes (see scheme).
- Szostak, Michal,Spain, Malcolm,Procter, David J.
-
supporting information
p. 4222 - 4226
(2014/05/06)
-
- A Phosphine-Catalyzed Novel Asymmetric [3+2] Cycloaddition of C,N-Cyclic Azomethine Imines with δ-Substituted Allenoates
-
Catalytic asymmetric [3+2] cycloadditions of C,N-cyclic azomethine imines with δ-substituted allenoates have been developed in the presence of (S)-Me-f-KetalPhos, affording functionalized tetrahydroquinoline frameworks in good yields with high diastereo- and good enantioselectivities under mild condition. The substrate scope has been also examined. This is the first time that δ-substituted allenoates have been applied as a δ,γ-C-C bond participated C 2 synthon in asymmetric synthesis. Another round: Catalytic asymmetric [3+2] cycloaddition of C,N-cyclic azomethine imines with δ-substituted allenoates have been developed in the presence of (S)-Me-f-KetalPhos, affording functionalized tetrahydroquinoline frameworks in good yields with high diastereo- and good enantioselectivities under mild conditions. This is the first example applying δ-substituted allenoates as C 2 synthons in asymmetric δ,γ-C-C bond formation.
- Wang, De,Lei, Yu,Wei, Yin,Shi, Min
-
supporting information
p. 15325 - 15329
(2016/02/18)
-
- Iron-catalyzed reduction of carboxylic esters to alcohols
-
A novel catalytic system formed from Fe(stearate)2/NH 2CH2CH2NH2 and polymethylhydrosiloxane was directly developed for the hydrosilylation of carboxylic acid esters to alcohols. The catalytic method exhibits broad substrate scope, including 20 aliphatic, aromatic, and heterocyclic esters. The corresponding alcohols are obtained in moderate to very good yields. The first iron-catalyzed hydrosilylation of carboxylic acid esters to alcohols is described. A catalytic system formed by Fe(stearate)2/NH 2CH2CH2NH2 and polymethylhydrosiloxane (PMHS) is used for this transformation, which has a broad substrate scope, including 20 aliphatic, aromatic, and heterocyclic esters. The corresponding alcohols are obtained in moderate to very good yields. Copyright
- Junge, Kathrin,Wendt, Bianca,Zhou, Shaolin,Beller, Matthias
-
p. 2061 - 2065
(2013/05/09)
-
- Selective switchable iron-catalyzed hydrosilylation of carboxylic acids
-
Selective reduction of carboxylic acids either to aldehydes or alcohols is achieved using a one pot procedure based on iron-catalyzed hydrosilylations. Using phenylsilane and (COD)Fe(CO)3 catalyst under UV-irradiation at rt, alcohols were obtained specifically in good yields, whereas aldehydes were selectively obtained using TMDS and (t-PBO)Fe(CO)3 catalyst under thermal activation.
- Misal Castro, Luis C.,Li, Haoquan,Sortais, Jean-Baptiste,Darcel, Christophe
-
supporting information
p. 10514 - 10516,3
(2020/09/02)
-
- CATALYTIC ANTI-MARKOVNIKOV OXIDATION AND HYDRATION OF OLEFINS
-
The disclosure provides a dual-catalysis system for direct conversion of olefins to alcohols. The cooperative catalytic system contains one oxidizing catalyst and one transfer-hydrogenation catalyst. A wide variety of olefins, including aromatic and aliphatic olefins, can be used as the reactant. The transformation proceeds with anti-Markovnikov selectivity, and in some aspects provides primary alcohols as major products. The disclosure further provides a system for oxidation of olefins with anti-Markovnikov selectivity.
- -
-
Page/Page column 15
(2012/07/14)
-
- Primary alcohols from terminal olefins: Formal anti-Markovnikov hydration via triple relay catalysis
-
Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.
- Dong, Guangbin,Teo, Peili,Wickens, Zachary K.,Grubbs, Robert H.
-
scheme or table
p. 1609 - 1612
(2012/02/01)
-
- 3-Hydroxypyrimidine-2,4-diones as an Inhibitor Scaffold of HIV Integrase
-
Integrase (IN) represents a clinically validated target for the development of antivirals against human immunodeficiency virus (HIV). Inhibitors with a novel structure core are essential for combating resistance associated with known IN inhibitors (INIs). We have previously disclosed a novel dual inhibitor scaffold of HIV IN and reverse transcriptase (RT). Here we report the complete structure-activity relationship (SAR), molecular modeling, and resistance profile of this inhibitor type on IN inhibition. These studies support an antiviral mechanism of dual inhibition against both IN and RT and validate 3-hydroxypyrimidine-2,4-diones as an IN inhibitor scaffold.
- Tang, Jing,Maddali, Kasthuraiah,Metifiot, Mathieu,Sham, Yuk Y.,Vince, Robert,Pommier, Yves,Wang, Zhengqiang
-
scheme or table
p. 2282 - 2292
(2011/06/17)
-
- Understanding the exceptional hydrogen-atom donor characteristics of water in TiIII-mediated free-radical chemistry
-
In recent years solid evidence of HAT reactions involving water as hydrogen atom source have been presented. In this work we demonstrate that the efficiency of titanocene(III) aqua complexes as an unique class of HAT reagents is based on two key features: (a) excellent binding capabilities of water toward titanocene(III) complexes and (b) a low activation energy for the HAT step. The theory has predictive capabilities fitting well with the experimental results and may aid to find more examples of this remarkable radical reaction.
- Paradas, Miguel,Campana, Araceli G.,Jimenez, Tania,Robles, Rafael,Oltra, J. Enrique,Bunuel, Elena,Justicia, Jose,Cardenas, Diego J.,Cuerva, Juan M.
-
supporting information; experimental part
p. 12748 - 12756
(2010/10/21)
-
- An improved bouveault-blanc ester reduction with stabilized alkali metals
-
Significantly improved Bouveault-Blanc conditions for ester reduction have been developed using sodium in silica gel (Na-SG), a free-flowing powder that can be easily handled in the open atmosphere. Primary alcohols were prepared in excellent yield from a variety of aliphatic esters under mild reaction conditions. The chemistry presented here is far safer than the classic Bouveault-Blanc reduction and is competitive with more modern hydride reduction methods.
- Bodnar, Brian S.,Vogt, Paul F.
-
supporting information; experimental part
p. 2598 - 2600
(2009/08/07)
-
- The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study
-
The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots were obtained with positive slopes of +0.79 and +0.43, respectively, which indicate a buildup of negative charge in the selectivity-determining step. The kinetic isotope effects were similar for these substrates (1.73 and 1.77 for benzaldehyde and phenyl acetaldehyde, respectively), indicating that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)-H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement with the experimental values for both substrates, but only when migratory extrusion of CO was selected as the rate-determining step.
- Fristrup, Peter,Kreis, Michael,Palmelund, Anders,Norrby, Per-Ola,Madsen, Robert
-
p. 5206 - 5215
(2008/12/22)
-
- [1,2]-Wittig rearrangement from chloromethyl ethers
-
The reaction of different chloromethyl ethers 1 with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (2.5 mol %) in THF at 0 °C leads to the corresponding α-lithiomethyl ether intermediates, through a chlorine-lithium exchange, which spontaneously undergo a clean [1,2]-Wittig rearrangement affording the expected homobenzylic alcohols 2. This is the first version of this rearrangement starting from easily available chloromethyl ethers.
- Gómez, Cecilia,Maciá, Beatriz,Lillo, Victor J.,Yus, Miguel
-
p. 9832 - 9839
(2007/10/03)
-
- Regioselective hydroboration-oxidation and -amination of fluoro-substituted styrenes
-
Hydroboration of fluorinated styrenes with common hydroborating agents results in polymerization. However, regioselective hydroboration has been achieved by utilizing iodoborane-dimethyl sulfide. A series of fluorinated β-phenethyl alcohols and amines were synthesized via this methodology.
- Ramachandran, P. Veeraraghavan,Madhi, Sateesh,O'Donnell, Martin J.
-
p. 1252 - 1255
(2008/09/20)
-
- TADDOL-derived phosphites and phosphoramidites for efficient rhodium-catalyzed asymmetric hydroboration
-
Two simple TADDOL-derived monodentate ligands, the (1R,2S)-2- phenylcyclohexanol-derived phosphite and the N,N-(phenylbenzyl)-phosphoramidite, give comparably high levels of enantioselectivity (90-96% ee) in the rhodium-catalyzed hydroborations of substituted styrenes bearing either electron-donating or electron-withdrawing substituents. Rhodium(I) chloride and tetrafluoroborate catalyst precursors give comparable results. Pinacolborane is superior to catecholborane in these reactions.
- Moteki, Shin A.,Wu, Di,Chandra, Kusum L.,Sahadeva Reddy,Takacs, James M.
-
p. 3097 - 3100
(2007/10/03)
-
- Synthesis, biochemical evaluation and rationalisation of the inhibitory activity of a range of 4-substituted phenyl alkyl imidazole-based inhibitors of the enzyme complex 17α-hydroxylase/17,20-lyase (P45017α)
-
We report the preliminary results of the synthesis, biochemical evaluation and rationalisation of the inhibitory activity of a number of phenyl alkyl imidazole-based compounds as inhibitors of the two components of 17α-hydroxylase/17,20-lyase (P45017α), that is, 17α-hydroxylase (17α-OHase) and 17,20-lyase (lyase). The results show that N-3-(4-bromophenyl) propyl imidazole (12) (IC50 = 2.95 μM against 17α-OHase and IC50 = 0.33 μM against lyase) is the most potent compound within the current study, in comparison to ketoconazole (KTZ) (IC50 = 3.76 μM against 17α-OHase and IC50 = 1.66 μM against lyase). Modelling of these compounds suggests that the length of the alkyl chain enhances the interaction between the inhibitor and the area of the active site corresponding to the C(3) area of the steroid backbone, thereby increasing potency.
- Patel, Chirag H.,Dhanani, Sachin,Owen, Caroline P.,Ahmed, Sabbir
-
p. 4752 - 4756
(2007/10/03)
-
- Recyclable Polyurea-Microencapsulated Pd(0) Nanoparticles: An Efficient Catalyst for Hydrogenolysis of Epoxides
-
(Matrix presented) Pd nanoparticles (~2 nm in size) microencapsulated in polyurea is an efficient and recyclable catalyst for reductive ring-opening hydrogenolysis of epoxides, using either HCOOH/Et3N or H2 as a hydrogen donor.
- Ley, Steven V.,Mitchell, Claire,Pears, David,Ramarao, Chandrashekar,Yu, Jin-Quan,Zhou, Wuzong
-
p. 4665 - 4668
(2007/10/03)
-
- Novel compounds and their use
-
A compound of the general formula (I): wherein R1, R2, X, Y and Z are as described in the specification.
- -
-
-
- Pharmacophore-based discovery, synthesis, and biological evaluation of 4-phenyl-1-arylalkyl piperidines as dopamine transporter inhibitors
-
Pharmacophore-based discovery, synthesis, and structure-activity relationship (SAR) of a series of 4-phenyl-1-arylalkyl piperidines are disclosed. These compounds have been evaluated for their ability to inhibit reuptake of dopamine (DA) into striatal nerve endings (synaptosomes). The lead compound 5 and the most potent analogue 43 were found to have significant functional antagonism.
- Sakamuri, Sukumar,Enyedy, Istvan J,Kozikowski, Alan P,Zaman, Wahiduz A,Johnson, Kenneth M,Wang, Shaomeng
-
p. 495 - 500
(2007/10/03)
-
- The effect of vinyl esters on the enantioselectivity of the lipase-catalysed transesterification of alcohols
-
The enantioselectivity of the lipase from Pseudomonas cepacia (PCL) in the transesterification of 2-phenyl-1-propanol 1 was studied using a series of vinyl 3-arylpropanoates as acyl donors. The most enantioselective transesterification reaction of the alcohol was attained by using vinyl 3-(p-iodophenyl)- or 3-(p-trifluoromethylphenyl)propanoates, with enantiomer ratios, E, of 116 and 138, respectively. Vinyl 3-phenylpropanoate was also effective for the resolution of 1 mediated by lipases from P. fluorescens and porcine pancreas and for the PCL-catalysed transesterification of several 2-phenyl-1-alkanols. The enantiomeric resolution of 1 was practically carried out by the first enantioselective transesterification using PCL and vinyl 3-(p-iodophenyl)propanoate to afford (R)-1 and then the enantioselective hydrolysis of the resultant ester to afford (S)-1.
- Kawasaki, Masashi,Goto, Michimasa,Kawabata, Shigeki,Kometani, Tadashi
-
p. 585 - 596
(2007/10/03)
-
- A practical olefin hydroboration under liquid-liquid phase transfer catalysis conditions
-
The hydroboration of a series of representative olefins under LL-PTC conditions, followed by oxidative workup provides the corresponding alcohols in excellent yields and regio- and stereoselectivity.
- Albanese, Domenico,Landini, Dario,Maia, Angelamaria,Penso, Michele
-
p. 997 - 998
(2007/10/03)
-
- The scope of catalytic asymmetric hydroboration/oxidation with rhodium complexes of 1,1'-(2-diarylphosphino-1-naphthyl)isoquinolines
-
Preformed cationic Rh complexes of the title ligands are effective for the asymmetric hydroboration/oxidation of vinylarenes at ambient temperature. These vinylarenes may carry E- or Z-β substituents but not a substituents. Enantiomer excesses of up to 97% can be obtained in the most favourable cases. The enantioselectivity is moderately sensitive to the structure of the ligand: the difurylphosphino ligand gave superior results for electron-poor styrenes and the diphenylphosphino ligand the best results for electron-rich reactants. Mechanistic aspects are discussed.
- Doucet, Henri,Fernandez, Elena,Layzell, Timothy P.,Brown, John M.
-
p. 1320 - 1330
(2007/10/03)
-
- METHOD FOR TREATING ANXIETY
-
The present invention provides a method for treating anxiety in humans using azacyclic or azabicyclic compounds.
- -
-
-
- Stereochemical control in microbial reduction. Part 31: Reduction of alkyl 2-oxo-4-arylbutyrates by baker's yeast under selected reaction conditions
-
Treatment of baker's yeast with phenacyl chloride in an aqueous-organic solvent has been proven to be an effective method of inhibiting the enzymes that afford (S)-enantiomers of α-hydroxy esters in the reduction of α-keto esters. The procedure is effective for the whole-cell system to produce the (R)-product with high chemical yield and high enantiomeric excess.
- Dao, Duc Hai,Okamura, Mutsuo,Akasaka, Takeshi,Kawai, Yasushi,Hida, Kouichi,Ohno, Atsuyoshi
-
p. 2725 - 2737
(2007/10/03)
-
- HETEROCYCLIC COMPOUNDS AND THEIR PREPARATION AND USE
-
The present invention relates to therapeutically active azacyclic or azabicyclic compounds, a method of preparing the same and to pharmaceutical compositions comprising the compounds. The novel compounds are useful in treating diseases in the central nervous system caused by malfunctioning of the muscarinic cholinergic system.
- -
-
-
- Selective synthesis of substituted benzylic alcohols from aromatic substrates included in β-cyclodextrin
-
The regio- and enantioselective reduction of substituted styrenic epoxides and aromatic ketones by borohydride in the presence of β-cyclodextrin is described. The regioselectivity is related to the hydrophobicity of the substrate, which governs its penetration inside the cavity of the cyclodextrin and is favorable to the β-opening of the epoxide. The stereoselectivity observed during the reduction is mainly dependent on the non-covalent interactions between the upper rim of the cyclodextrin and the substrate included in it. The chimioselectivity observed during the reduction of ketoester is assumed to be dependent on an alkoxyborohydride intermediate formed in the first step of the reaction. Elsevier.
- Doussot, Joel,Guy, Alain,Garreau, Robert,Falguieres, Annie,Cossy, Janine,Amsterdamsky, Claude
-
p. 161 - 166
(2007/10/03)
-
- FUNGAL HYDROXYLATION OF ETHYL BENZENE AND DERIVATIVES
-
The fungus Mortierella isabellina converts ethyl benzene and a number of para-substituted derivatives to the corresponding optically active 1-phenylethanols with enantiomeric excesses between 5 and 40percent.Hydrogen removal from the substrate preceeds product formation and is stereochemically independent of it.
- Holland, Herbert L.,Carter, Ian M.,Chenchaiah, P. Chinna,Khan, Shaheer H.,Munoz, Benito,et al.
-
p. 6409 - 6412
(2007/10/02)
-
- Kinetics of Hydrolysis of Some Acid Succinates in Water
-
The kinetics of hydrolysis of 1-phenylethyl hydrogen succinate and its p-alkyl (Me, Et), p-methoxy and p-halogen (F, Cl, Br) derivatives has been studied in water.The activation parameters are normal for a BAL 1 mechanism, except for the chloro and bromo derivatives.The Brown-Okomoto equation has also been applied to the present case.
- Saramma, K.,Thankamma, A.
-
p. 904 - 905
(2007/10/02)
-