- Modulation of imprinting efficiency in nanogels with catalytic activity in the Kemp elimination
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The interactions between the template and the functional monomer are a key to the formation of cavities in the imprinted nanogels with high molecular recognition properties. Nanogels with enzyme-like activity for the Kemp elimination have been synthesized
- Bonomi, Paolo,Servant, Ania,Resmini, Marina
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Read Online
- On the magnitude and specificity of medium effects in enzyme-like catalysts for proton transfer
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Medium effects are normally studied by comparing the rates of reactions in different solvents. However, medium effects at the active site of enzymes differ dramatically from bulk solvents, both in their diversity (the presence of more than one type of "so
- Hollfelder,Kirby,Tawfik
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Read Online
- Phosphination of Phenol Derivatives and Applications to Divergent Synthesis of Phosphine Ligands
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We describe a general and efficient protocol for the synthesis of organophosphine compounds from phenols and phosphines (R2PH) via a metal-free C-O bond cleavage and C-P bond formation process. This approach exhibits broad substrate scope and excellent functional group tolerance. The synthetic utilities of this protocol were demonstrated by the synthesis of chiral ligands via the various transformations of cyano groups and their applications in asymmetric catalysis.
- Li, Chenchen,Zhang, Kezhuo,Zhang, Minghao,Zhang, Wu,Zhao, Wanxiang
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supporting information
p. 8766 - 8771
(2021/11/20)
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- Catalyst-Controlled Regioselective Chlorination of Phenols and Anilines through a Lewis Basic Selenoether Catalyst
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We report a highly efficient ortho-selective electrophilic chlorination of phenols utilizing a Lewis basic selenoether catalyst. The selenoether catalyst resulted in comparable selectivities to our previously reported bis-thiourea ortho-selective catalyst, with a catalyst loading as low as 1%. The new catalytic system also allowed us to extend this chemistry to obtain excellent ortho-selectivities for unprotected anilines. The selectivities of this reaction are up to >20:1 ortho/para, while the innate selectivities for phenols and anilines are approximately 1:4 ortho/para. A series of preliminary studies revealed that the substrates require a hydrogen-bonding moiety for selectivity.
- Dinh, Andrew N.,Maddox, Sean M.,Vaidya, Sagar D.,Saputra, Mirza A.,Nalbandian, Christopher J.,Gustafson, Jeffrey L.
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p. 13895 - 13905
(2020/11/03)
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Preparation method of piperidine compound
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The invention discloses a preparation method of a piperidine compound 4-((2-(aminomethyl)-4-bromophenoxy) methyl) piperidine-1-tert-butyl formate. 5-chloro-2-hydroxybenzaldehyde is used as a starting material and subjected to oximation, elimination, ether
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Paragraph 0023; 0024
(2017/11/04)
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- The Catalyst-Controlled Regiodivergent Chlorination of Phenols
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Different catalysts are demonstrated to overcome or augment a substrate's innate regioselectivity. Nagasawa's bis-thiourea catalyst was found to overcome the innate para-selectivity of electrophilic phenol chlorination, yielding ortho-chlorinated phenols that are not readily obtainable via canonical electrophilic chlorinations. Conversely, a phosphine sulfide derived from 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) was found to enhance the innate para-preference of phenol chlorination.
- Maddox, Sean M.,Dinh, Andrew N.,Armenta, Felipe,Um, Joann,Gustafson, Jeffrey L.
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supporting information
p. 5476 - 5479
(2016/11/17)
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- Chromatography-free entry to substituted salicylonitriles: Mitsunobu-triggered domino reactions of salicylaldoximes
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A mild and efficient one-pot procedure is described to transform salicylaldoximes into salicylonitriles using Mitsunobu chemistry. The reactions proceed through the corresponding 1,2-benzisoxazoles that undergo the Kemp elimination in situ to generate the
- Whiting, Ellis,Lanning, Maryanna E.,Scheenstra, Jacob A.,Fletcher, Steven
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p. 1229 - 1234
(2015/01/30)
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- Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
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The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
- Nimnual, Phongprapan,Tummatorn, Jumreang,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
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p. 8657 - 8667
(2015/09/15)
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- HCV PROTEASE INHIBITORS
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The present invention discloses a compound of general formula (I); A is O, S, CH, NH or NR', when O links with Z3, Z1 is N or CRZ1, Z2 is CRZ2, when Z1 links with O, Z2 is CH, Z3 is C-Ar; Ra, Rb, Rc and Rd independently is H, OH, halogen or -Y1-Rm; A1 is NH or CH2; R1' is alkyl, aryl, cycloalkyl, heterocycloalkyl or heteroaryl; A2 is N, O or linking bond; R1 is hydrogen, or, R1 linking covalently with R3 forms C5-C9 saturated or unsaturated hydrocarbon chain substituted by O or N; R3 is alkyl, cycloalkyl, heterocycloalkyl, alkyl substituted by cycloalky etc; R4 is alkoxy-CO, alkyl-NHCO, (alkyl)2NCO, or formyl substituted by aryl, cycloalkyl, heterocycloalkyl.
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Paragraph 0047; 0048
(2014/06/24)
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- HCV Protease Inhibitors
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A compound of general formula (I); A is O, S, CH, NH or NR′, when O links with Z3, Z1 is N or CRZ1, Z2 is CRZ2, when Z1 links with O, Z2 is CH, Z3 is C—Ar; Ra, Rb, Rc and Rd independently is H, OH, halogen or —Y1—Rm; A1 is NH or CH2; R1′ is alkyl, aryl, cycloalkyl, heterocycloalkyl or heteroaryl; A2 is N, O or linking bond; R1 is hydrogen, or, R1 linking covalently with R3 forms C5-C9 saturated or unsaturated hydrocarbon chain substituted by O or N; R3 is alkyl, cycloalkyl, heterocycloalkyl, alkyl substituted by cycloalkyl etc; R4 is alkoxy-CO, alkyl-NHCO, (alkyl)2NCO, or formyl substituted by aryl, cycloalkyl, heterocycloalkyl.
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Paragraph 0120-0124
(2014/06/24)
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- Calcium bis [ (2S) - 3- [3-[ (2S) -3- (4-chloro-2-cyanophenoxy) -2- fluoropropoxy]phenyl ]-2-isopropoxypropionate] and intermediate thereof
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The present invention relates to calcium bis[(2S)-3-[3-[(2S)-3-(4-chloro-2-cyanophenoxy)-2-fluoropropoxy]phenyl]-2-isopropoxypropionate] represented by formula (I), a hydrate thereof, a crystal of the compound of formula (I), and a crystal of the hydrate
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- CARBAMOYL-TYPE BENZOFURAN DERIVATIVES
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The present invention provides a carbamoyl-type benzofuran derivative of the formula [1]: wherein Ring Z is a group of the formula: etc.; A is a single bond, and the like; Y is a cycloalkanediyl group, etc.; R4 and R5 are the same or different and each is an optionally substituted lower alkyl group, etc.; R1 is a halogen atom, etc.; Ring B of the formula: is an optionally substituted benzene ring; and R3 is a hydrogen atom, etc., or a pharmaceutically acceptable salt thereof, which is useful as an FXa inhibitor.
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Page/Page column 67
(2008/06/13)
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- CALCIUM BIS[(2S)-3-[3-[(2S)-3-(4-CHLORO-2-CYANOPHENOXY)-2- FLUOROPROPOXY]PHENYL]-2-ISOPROPOXYPROPIONATE] AND INTERMEDIATE THEREOF
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Calcium bis[(2S)-3-[3-(2S)-3-(4-chloro-2-cyanophenoxy)- 2-fluoropropoxy]phenyl]-2-isopropoxypropionate] of the formula (I).
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Page/Page column 53-54
(2008/06/13)
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- BENZOFURAN DERIVATIVE
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The present invention provides a benzofuran derivative of the formula [1]: wherein x is a group of the formula: -N="or" -CH=; Y is an optionally substituted amino group, an optionally substituted cycloalkyl group or an optionally substituted saturated heterocyclic group; A is a single bond, a carbon chain optionally having a double bond within or at the end(s) of the chain, or an oxygen atom; R1 is a hydrogen atom or a halogen atom; Ring B is an optionally substituted benzene ring; and R3 is a hydrogen atom, or a pharmaceutically acceptable salt thereof, which is useful as a medicament, especially as an activated blood coagulation factor X inhibitor.
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- Nonspecific medium effects versus specific group positioning in the antibody and albumin catalysis of the base-promoted ring-opening reactions of benzisoxazoles
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The mechanisms by which solvents, antibodies, and albumins influence the rates of base-catalyzed reactions of benzisoxazoles have been explored theoretically. New experimental data on substituent effects and rates of reactions in several solvents, in an antibody, and in an albumin are reported. Quantum mechanical calculations were carried out for the reactions in water and acetonitrile, and docking of the transition state into a homology model of antibody 34E4 and an X-ray structure of human serum albumin was accomplished. A microenvironment made up of catalytic polar groups (glutamate in antibody 34E4 and lysine in human serum albumin) surrounded by relatively nonpolar groups is present in both catalytic proteins.
- Hu, Yunfeng,Houk,Kikuchi, Kazuya,Hotta, Kinya,Hilvert, Donald
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p. 8197 - 8205
(2007/10/03)
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- 5-PHENYLBENZYLAMINE COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND INTERMEDIATES FOR THEIR SYNTHESIS
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The present invention relates to a 5-phenylbenzylamine compound represented by the formula [1]: wherein Ring A represents a phenyl group having a substituent(s), ???Ra, Rb1 and Rb2 each represent hydrogen atom, a halogen a
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- Chalcone derivatives and drugs containing the same
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PCT No. PCT/JP97/01652 Sec. 371 Date Nov. 17, 1998 Sec. 102(e) Date Nov. 17, 1998 PCT Filed May 16, 1997 PCT Pub. No. WO97/44306 PCT Pub. Date Nov. 27, 1997This invention relates to chalcone derivatives represented by the following formula (1): wherein A represents a phenyl group, a quinolyl group or the like, W represents a vinylene group or the like, and R1 to R5 each independently represent a carboxyl, cyano, alkyloxycarbonyl or like group, or salts of the chalcone derivatives, and also to drugs containing them as effective ingredients. These compounds have excellent cys-LT receptor antagonism, and are useful as antiallergic agents or the like.
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- Flavone derivative and medicine comprising the same
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This invention relates to a flavone derivative represented by the formula (1) or a salt thereof, and also to a medicine containing the same. wherein A represents H, halogen, phenyl, naphthyl, a group of the formula (2) in which X is H or halogen, B is -CH
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- Synthesis and structure-activity relationships of carboxylated chalcones: A novel series of CysLT1 (LTD4) receptor antagonists
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The synthesis and CysLT1 antagonistic activities of a new series of 2- , 3-, and 4-(2-quinolinylmethoxy)- and 3- and 4-[2-(2-quinolinyl)ethenyl]- substituted, 2'-, 3'-, 4'-, or 5'-carboxylated chalcones are described. Structure-activity relationship studies indicate a preference for the presence of a negatively charged (acidic) moiety, although in some cases nitrile or ester analogues also exhibit moderate activity. The quinoline moiety may be substituted at either the 3- or the 4-position. Replacement of this heterocycle by other aromatic groups results in compounds with comparable affinities [2-(7-chloroquinoline), 1-(1-methyl-2-benzimidazole), or 1-(2-benzothiazole)] or substantially lower activities [1-(1- ethoxyethyl)-2-benzimidazole, 2-naphthyl, or phenyl]. The quinoline and chalcone moieties may be connected by either an ethenyl or a methoxy spacer. The acidic moiety at the chalcone B ring may be attached to the 2'-, 3'-, 4'- , or 5'-position, for both the 3- and 4-substituted chalcones. There are no general patterns to specify which substitution positions gave the most potent compounds. The series contains several potent CysLT1 receptor antagonists, with K(D) values approaching the nanomolar range, as measured by the displacement of [3H]LTD4 from guinea pig lung membranes. Antagonism of LTD4-induced contraction of guinea pig ileum, the inhibition of antigen- induced contraction of guinea pig trachea in vitro, and the inhibition of LTD4-induced increase of vascular permeability in vivo are determined for chalcones with high CysLT1 receptor affinities (K(D) values below 0.1μM). 2'-Hydroxy-4-(2-quinolinylmethoxy)-5'-(5-tetrazolyl)chalcone (14, VUF 4819) showed good activity in both in vitro and in vivo assays and has been selected for further evaluation.
- Zwaagstra, Mari?l E.,Timmerman, Hendrik,Tamura, Masahiro,Tohma, Tsutomu,Wada, Yasushi,Onogi, Kazuhiro,Zhang, Ming-Qiang
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p. 1075 - 1089
(2007/10/03)
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- HETEROCYCLIC ACIDS
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The invention concerns novel 1,3-dioxane alkenoic acid derivatives of the formula I wherein: n is the integer 1 or 2; Y is methyleneoxy, vinylene or ethylene; A1 is (1-6C)alkylene; R1 is a group of the formula R2A2 --, in which: R2 is phenyl unsubstituted
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- TEMPLATE HOUBEN-HOESCH REACTION ON METAL PHENOLATES. SYNTHESIS OF AROMATIC KETONES, NITRILES AND AMIDES. CRYSTAL STRUCTURE OF DICHLORO-BORON
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The crystal structure of dichloro-boron (6dx) establishes for the first time the coordination mechanism of the ortho-selective reaction of metal phenolates and nitriles.Crystal data: chemical formula C9H7BCl5NO2; a = 11.743(2), b = 13.390(2), c = 8.765(3) Angstroem, β = 99.71(2) deg; space group P21/n.Variously substituted aromatic ketones, nitriles and amides have been obtained in a "one-pot" reaction.
- Bigi, Franca,Maggi, Raimondo,Sartori, Giovanni,Casnati, Giuseppe,Bocelli, Gabriele
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p. 283 - 289
(2007/10/02)
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- EXLUSIVE ORTHO CYANATION AND ALKYLTHIOCARBONYLATION OF ANILINES AND PHENOLS USING BORON TRICHLORIDE
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Use of boron trichloride with or without an aditional Lewis acid makes possible a one-step synthesis of 2-cyano and 2-alkylthiocarbonyl anilines and phenols.
- Adachi, Makoto,Sugasawa, Tsutomu
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