- Scalable green approach toward fragrant acetates
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The advantageous properties of ethylene glycol diacetate (EGDA) qualify it as a useful substitute for glycerol triacetate (GTA) for various green applications. We scrutinised the lipase-mediated acetylation of structurally diverse alcohols in neat EGDA furnishing the range of naturally occurring fragrant acetates. We found that such enzymatic system exhibits high reactivity and selectivity towards activated (homo) allylic and non-activated primary/secondary alcohols. This feature was utilised in the scalable multigram synthesis of fragrant (Z)-hex-3-en-1-yl acetate in 70percent yield. In addition, the Lipozyme 435/EGDA system was also found to be applicable for the chemo-selective acetylation of (hydroxyalkyl) phenols as well as for the kinetic resolution of chiral secondary alcohols. Lastly, its discrimination power was demonstrated in competitive experiments of equimolar mixtures of two isomeric alcohols. This enabled the practical synthesis of 1-pentyl acetate isolated as a single product in 68percent yield from the equimolar mixture of 1-pentanol and 3-pentanol.
- Puchl'Ová, Eva,Szolcsányi, Peter
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- A kind of indan -5 - carboxamide ROR γ regulator and its use
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The invention relates to a structure of formula (I) compound of formula or a stereoisomer thereof, tautomers or its pharmaceutically acceptable salt or solvate or prodrug, its preparation method, a pharmaceutical composition containing these modulators and their use in the treatment ROR γ-mediated inflammatory, metabolic and autoimmune disorders.
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Paragraph 0127; 0128; 0129; 0130; 0131; 0132-0133; 0185-0191
(2019/03/15)
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- Method for preparing 5,6-diethyl-2,3-dihydro-1H-indene-2-amino hydrochloride
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The invention relates to a novel synthesis route of a method for preparing 5,6-diethyl-2,3-dihydro-1H-indene-2-amino hydrochloride. 2-indanol is adopted as a raw material, and 5,6-diethyl-2,3-dihydro-1H-indene-2-amino hydrochloride is synthesized with a high yield through seven steps of an acetylation reaction, a substitution reaction, a coupling reaction, a hydroxyl protection reaction, a substitution reaction, a reduction reaction and a salting reaction. The preparation method of the 5,6-diethyl-2,3-dihydro-1H-indene-2-amino hydrochloride, which is provided by the invention, is a preparationmethod which is high in yield, low in cost, friendly to the environment, easy to operate and applicable to industrialization.
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Paragraph 0025; 0028; 0029
(2019/10/01)
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- Retro-claisen condensation with FeIII as catalyst under solvent-free conditions
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An iron(III) salt catalyzed retro-Claisen condensation between an alcohol and a 1,3-diketone was investigated. The mechanism involves the formation of a metal-induced sixmembered cyclic transition state and cleavage of the C sp2-Csp3 bond. Regioselective esterification and one-pot couversion of silyl ethers into esters with good yields was observed. Simple reaction conditions, high yields, and broad scope of the reaction illustrate the good synthetic utility of this method.
- Rao, Chitturi Bhujanga,Rao, Dasireddi Chandra,Babu, Dokuburra Chanti,Venkateswarlu, Yenamandra
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supporting information; experimental part
p. 2855 - 2859
(2010/08/05)
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- ARYLPROPIONAMIDE, ARYLACRYLAMIDE, ARYLPROPYNAMIDE, OR ARYLMETHYLUREA ANALOGS AS FACTOR XIA INHIBITORS
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The present invention provides compounds of Formula (I): Formula (I) or a stereoisomer, tautomer, pharmaceutically acceptable salt or solvate form thereof, wherein the variables A, L1, M and R11 are as defined herein. The compounds of Formula (I) are selective inhibitors of serine protease enzymes of the coagulation cascade and/or contact activation system; for example thrombin, factor Xa, factor XIa, factor IXa, factor VIIa and/or plasma kallikrein. In particular, it relates to compounds that are selective factor XIa inhibitors. This invention also relates to pharmaceutical compositions comprising these compounds and methods of treating thromboembolic and/or inflammatory disorders using the same.
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Page/Page column 220
(2008/06/13)
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- Concise syntheses of 2-aminoindans via indan-2-ol
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2-Amino-5,6-dimethoxyindan hydrochloride was synthesized in seven steps and with an overall yield of 48%. Indan-2-ol was converted to 5,6-dibromo-indan-2- ol in three steps by acetylation, electrophilic bromination and deacetylation. Dimethoxylation of 5,6-dibromoindan-2-ol with NaOCH3 in the presence of CuI gave 5,6-dimethoxy-indan-2-ol, which was converted to 2-amino-5,6-dimethoxyindan hydrochloride by azidation, followed by Pd-C catalyzed hydrogenation. Similarly, 2-amino-5-bromoindan was synthesized in five steps and with an overall yield of 50%. Indan-2-ol was converted to 2-aminoindan by azidation followed by Pd-C catalyzed hydrogenation. The reaction of 2-aminoindan with 2.5 equiv Br2 afforded 2-amino-5,6- dibromoindan.
- G?ksu, Süleyman,Se?en, Hasan
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p. 6801 - 6807
(2007/10/03)
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- Transesterification/Acylation of Secondary Alcohols Mediated by N-Heterocyclic Carbene Catalysts
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N-Heterocyclic carbenes (NHC) are efficient catalysts for transesterification/acylation reactions involving secondary alcohols. The catalytic transformations are carried out employing low catalyst loadings in convenient reaction times at room temperature.
- Singh, Rohit,Kissling, Rebecca M.,Letellier, Marie-Anne,Nolan, Steven P.
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p. 209 - 212
(2007/10/03)
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- Carboxamides useful as inhinitors of microsomal triglyceride transfer protein and of apolipoprotein b secretion
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Compounds of formula (1) wherein R2—C, R3—C, R4—C or R5—C may be replaced by N; and wherein n is 1, 2 or 3; R1 is aryl, heteroaryl or (aryl or heteroaryl)-lower alkoxy; R2, R3, R4 and R5 are independently hydrogen, lower alkyl, lower alkoxy, halo, trifluoromethyl or cyano; R6 is (i) or (ii) m is 1, 2 or 3; R7 is hydrogen, lower alkyl (aryl or heteroaryl)-lower alkyl, lower alkoxy, (aryl or heteroaryl)-lower alkoxy, hydroxy, oxo, lower alkylenedioxy or lower alkanoyloxy; W is O, S or NR8; R8 is —CORa, (iii), —COORd, —SO2Re, hydrogen, optionally substituted lower alkyl, aryl, heteroaryl or (aryl or heteroaryl)-lower alkyl; Ra, Rd and Re, are independently optionally substituted lower alkyl, cycloalkyl, adamantyl, aryl, heteroaryl or (aryl or heteroaryl)-lower alkyl; Rb and Rc are independently hydrogen, cycloalkyl, optionally substituted lower alkyl, aryl, heteroaryl or (aryl or heteroaryl) lower alkyl; or Rb and Rc together represent lower alkylene; and pharmaceutically acceptable salts thereof; and enantiomers thereof; which are useful as inhibitors of microsomal triglyceride transfer protein (MTP) and of apolipoprotein B (apoB) secretion.
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- Stereoselective benzylic hydroxylation of 2-substituted indanes using toluene dioxygenase as biocatalyst
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Indane, 1A, and a series of 2-substituted indane substrates, 1B-1D, 1G, 1I-1L, were found to undergo benzylic monohydroxylation catalysed by toluene dioxygenase, present in the intact cells of Pseudomonas putida UV 4, to yield enantiopure cis-indan-1-ols, 2A-2D, 2G, 2I-2L of the same absolute configuration at C-1 as major bioproducts. Enantiopure trans-indan-1-ols 6B, 6C, and 6G were also obtained as minor metabolites. Evidence of further sequential benzylic hydroxylation (bis-hydroxylation) was found only with substrates 2A, 1C, 1D and 1L to yield the corresponding enantiopure trans-1,3-diols, 3A, 3C, 3D and 3L. Minor enzyme-catalysed processes also observed include benzylic alcohol oxidation to ketones (4A, 5A, 4B, 4L, 5L), ketone reduction to benzylic alcohol 6A, ester hydrolysis to indan-2-ol 1B, and cis-dihydroxylation of indan-1-ol 6A to triol 7. The enantiopurities and absolute configurations of bioproducts have been determined using MTPA ester formation, circular dichroism spectroscopy and stereochemical correlation methods. The contribution of asymmetric oxidation and kinetic resolution to the production of bioproducts of high ee (>98%), and the metabolic sequence involved in their biotransformation by P. putida UV4 is discussed. Enantiocomplementarity was found during the benzylic hydroxylation of indan-2-ol 1B, using toluene dioxygenase and naphthalene dioxygenase, when both single enantiomers of the metabolites 2B, 4B and 6B of opposite configurations were obtained.
- Bowers, Nigel I.,Boyd, Derek R.,Sharma, Narain D.,Goodrich, Peter A.,Groocock, Melanie R.,Blacker, A. John,Goode, Paul,Dalton, Howard
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p. 1453 - 1461
(2007/10/03)
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- Reaction of 1-Substituted Indenes with Diborane or N-Bromoacetamide in Protic Solvents. The Effect of the Substituent on the Stereochemistry of Addition
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The reaction of 1-substituted indenes with diborane or N-bromoacetamide (NBA) in protic solvents has been investigated to determine the effect of an increase of steric bulk of the substituent on the stereochemical course of addition.In the hydroboration reaction the proportion of the products via attack by diborane from the less hindered side increases, as the steric bulk of the substituent at C-1 increases.The reaction with NBA in aqueous dioxan, followed by acetylation, gave a mixture of 3-substituted-1-acetoxy-2-bromoindans with trans, trans and trans,cis-configuration: 1-phenylindene gave mainly trans, trans-1-acetoxy-2-bromo-3-phenylindan, while trans,cis-1-acetoxy-2-bromo-3-methylindan was the maior product in the case of 1-methylindene.
- Miura, Masahiro,Yoshida, Masaya,Nojima, Masatomo,Kusabayashi, Shigekazu
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