- Enantioselective Desymmetrization of 2-Aryl-1,3-propanediols by Direct O-Alkylation with a Rationally Designed Chiral Hemiboronic Acid Catalyst That Mitigates Substrate Conformational Poisoning
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Enantioselective desymmetrization by direct monofunctionalization of prochiral diols is a powerful strategy to prepare valuable synthetic intermediates in high optical purity. Boron acids can activate diols toward nucleophilic additions; however, the design of stable chiral catalysts remains a challenge and highlights the need to identify new chemotypes for this purpose. Herein, the discovery and optimization of a bench-stable chiral 9-hydroxy-9,10-boroxarophenanthrene catalyst is described and applied in the highly enantioselective desymmetrization of 2-aryl-1,3-diols using benzylic electrophiles under operationally simple, ambient conditions. Nucleophilic activation and discrimination of the enantiotopic hydroxy groups on the diol substrate occurs via a defined chairlike six-membered anionic complex with the hemiboronic heterocycle. The optimal binaphthyl-based catalyst 1g features a large aryloxytrityl group to effectively shield one of the two prochiral hydroxy groups on the diol complex, whereas a strategically placed "methyl blocker"on the boroxarophenanthrene unit mitigates the deleterious effect of a competing conformation of the complexed diol that compromised the overall efficiency of the desymmetrization process. This methodology affords monoalkylated products in enantiomeric ratios equal or over 95:5 for a wide range of 1,3-propanediols with various 2-aryl/heteroaryl groups.
- Estrada, Carl D.,Ang, Hwee Ting,Vetter, Kim-Marie,Ponich, Ashley A.,Hall, Dennis G.
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- MESOIONIC INSECTICIDES
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Disclosed are compounds of Formula 1, including all geometric and stereoisomers, Ν-oxides, and salts thereof (I), wherein R1, X, Q, R2, n, R3 and R4 are as defined in the disclosure, Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the disclosure.
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Page/Page column 24
(2021/07/31)
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- OXIDATIVE COUPLING OF ARYL BORON REAGENTS WITH SP3-CARBON NUCLEOPHILES, AND AMBIENT DECARBOXYLATIVE ARYLATION OF MALONATE HALF-ESTERS VIA OXIDATIVE CATALYSIS
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Described herein are methods of oxidative coupling of aryl boron reagents with sp3-carbon nucleophiles, and ambient decarboxylative arylation of malonate half-esters via oxidative catalysis.
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Paragraph 0146; 0147; 0151-0154
(2018/07/29)
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- Oxidative coupling of aryl boron reagents with sp3-carbon nucleophiles: The enolate chan–evans–lam reaction
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Reported is a versatile new oxidative method for the arylation of activated methylene species. Under mild reaction conditions (RT to 40°C), Cu(OTf)2mediates the selective coupling of functionalized aryl boron species with a variety of stabilized sp3-nucleophiles. Tertiary malonates and amido esters can be employed as substrates to generate quaternary centers. Complementing either traditional cross-coupling or SNAr protocols, the transformation is chemoselective in the presence of halogen electrophiles, including aryl bromides and iodides. Substrates bearing amide, sulfonyl, and phosphonyl groups, which are not amenable to coupling under mild Hurtley-type conditions, are suitable reaction partners.
- Moon, Patrick J.,Halperin, Heather M.,Lundgren, Rylan J.
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supporting information
p. 1894 - 1898
(2016/12/03)
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- Oxidative Coupling of Aryl Boron Reagents with sp3-Carbon Nucleophiles: the Enolate Chan-Evans-Lam Reaction
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Reported is a versatile new oxidative method for the arylation of activated methylene species. Under mild reaction conditions (RT to 40 C), Cu(OTf)2 mediates the selective coupling of functionalized aryl boron species with a variety of stabilized sp3-nucl
- Moon, Patrick J.,Halperlin, Heather M.,Lundgren, Rylan J.
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supporting information
p. 1894 - 1898
(2016/08/31)
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- SUBSTITUTED AROMATIC COMPOUNDS AND PHARMACEUTICAL COMPOSITIONS FOR TISSUE SELF-REPAIR AND REGENERATION
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Described herein are compounds of Formula I, or pharmaceutically acceptable salts thereof, or combinations thereof, as well as uses thereof. Such uses include promoting tissue self-repair or tissue regeneration of an organ, stimulating the generation of tissue growth, modulating (e.g. increasing) the level of a tissue-repair marker, treating physical injury in an organ, tissue, or cell, promoting wound healing as well as anti-aging applications. Corresponding compositions, methods and uses are also described. Formula I wherein A is C5 alkyl, C6 alkyl, C5 alkenyl, C6 alkenyl, C(0)-(CH2)n-CH3 or CH(OH)-(CH2)n-CH3 wherein n is 3 or 4; R1 is H, F of OH; R2 is H, F, OH, C5 alkyl, C6 alkyl, C5 alkenyl, C6 alkenyl, C(0)-(CH2)n-CH3 or CH(OH)-(CH2)n-CH3 wherein n is 3 or 4; R3 is H, F, OH, or CH2Ph; R4 is H, F or OH; Q is 1) (CH2),C(0)OH wherein m is 1 or 2 2) CH(CH3)C(0)OH, 3) C(CH3)2C(0)OH, 4) CH(F)-C(0)OH, 5) CF2-C(0)OH or 6) C(0)-C(0)OH.
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Paragraph 00155
(2016/06/13)
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- Substituted phenylimidazopyrazoles and their use
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The present application relates to novel 1-phenyl-1H-imidazo[1,2-b]pyrazole derivatives, to processes for their preparation, to their use for the treatment and/or prevention of diseases and to their use for preparing medicaments for the treatment and/or prevention of diseases, in particular angiogenic disorders and hyperproliferative disorders, where neovascularization plays a role, such as, for example, neoplastic disorders and tumour disorders. Such treatments can be carried out as monotherapy or else in combination with other medicaments or further therapeutic measures.
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- MIXTURES OF MESOIONIC PESTICIDES
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Disclosed are compositions comprising (a) at least one compound selected from compounds of Formula (1), N-oxides, and salt thereof, wherein R1 is phenyl optionally substituted with up to 5 substituents independently selected from R3,
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Page/Page column 33
(2011/02/24)
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- Class of cytodifferentiating agents and histone deacetylase inhibitors, and methods of use thereof
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The present invention provides the compound having the formula: wherein each of R1and R2is, substituted or unsubstituted, aryl, cycloalkyl, cycloalkylamino, naphtha, pyridineamino, piperidino, t-butyl, aryloxy, arylalkyloxy, or pyridine group; wherein A is an amido moiety, —O—, —S—, —NH—, or —CH2—; and wherein n is an integer from 3 to 8. The present invention also provides a method of selectively inducing growth arrest, terminal differentiation and/or apoptosis of neoplastic cells and thereby inhibiting proliferation of such cells. Moreover, the present invention provides a method of treating a patient having a tumor characterized by proliferation of neoplastic cells. Lastly, the present invention provides a pharmaceutical composition comprising a pharmaceutically acceptable carrier and a therapeutically acceptable amount of the compound above.
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- Heterocyclic compounds
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The present invention provides a preventive or therapeutic agent for hyperlipidemia, comprising as an active ingredient a heterocyclic compound of the formula [1], or a pharmaceutically acceptable salt thereof: R1-Het-D-E??[1] wherein: R1
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