- Highly enantioselective construction of CF3-bearing all-carbon quaternary stereocenters: Hiral spiro-fused bisoxazoline ligands with 1,1′-binaphthyl sidearm for asymmetric Michael-type Friedel-Crafts reaction
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A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared. The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Crafts reaction, affording the products bearing a trifluoromethylated all-carbon quaternary stereocenter with moderate to excellent yields (up to 99%) and good to excellent enantioselectivies (up to > 99.9% ee). Moreover, a proposed model of chiral pocket revealed that the attack of indole from the Re-face of β-CF3-β-disubstituted nitroalkene was favorable.
- Bao, Robert Li-Yuan,Fu, Kang,Shi, Lei
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- Asymmetric Hydrogenation of Aryl Perfluoroalkyl Ketones Catalyzed by Rhodium(III) Monohydride Complexes Bearing Josiphos Ligands
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The asymmetric hydrogenation of 2,2,2-trifluoroacetophenones and aryl perfluoroalkyl ketones was developed using a unique, well-defined chloride-bridged dinuclear rhodium(III) complex bearing Josiphos-type diphosphine ligands. These complexes were prepared from [RhCl(cod)]2, Josiphos ligands, and hydrochloric acid. As catalyst precursors, they allow for the efficient and enantioselective synthesis (up to 99 % ee) of chiral secondary alcohols with perfluoroalkyl groups. This system does not require an activating base for the hydrogenation of 2,2,2-trifluoroacetophenones. Additionally, the enantioselective C=O hydrogenations of 2-phenyl-3-(haloacetyl)-indoles, a class of privileged structures in medicinal chemistry, is reported for the first time.
- Brüning, Fabian,Nagae, Haruki,K?ch, Daniel,Mashima, Kazushi,Togni, Antonio
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supporting information
p. 10818 - 10822
(2019/07/31)
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- Visible light-promoted umpolung coupling of aryl tri-/difluoroethanones with 2-alkenylpyridines
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Tertiary alcohols bearing a trifluoromethyl group are of considerable medicinal interest. Using an umpolung strategy, we herein report the first intermolecular reductive cross-coupling of aryl tri-/difluoroethanones with 2-alkenylpyridines with the aid of a Br?nsted acid catalyst upon visible-light irradiation. This metal-free reaction is operationally simple and performed at ambient temperature, allowing access to desired tertiary alcohols with tri-/difluoromethyl groups in moderate to excellent yields. The commercially available and easily handled Hantzsch ester effectively serves as an electron donor, as well as a hydrogen atom source.
- Xu, Xiao,Min, Qing-Qiang,Li, Na,Liu, Feng
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supporting information
p. 11017 - 11020
(2018/10/08)
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- Pesticidal compositions and processes related thereto
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This document discloses molecules having the following formula (“Formula One”): and processes associated therewith.
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Page/Page column 46; 127
(2016/01/09)
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- PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
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This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca, processes to produce such molecules and intermediates used in such processes, compositions containing such molecules, and processes of using such molecules against such pests. These molecules may be used, for example, as nematicides, acaricides, insecticides, miticides, and/or molluscicides. This document discloses molecules having the following formula (“Formula One”).
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Paragraph 0141; 0165; 0166
(2015/12/30)
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- PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
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This document discloses molecules having the following formula ("Formula One"): and processes associated therewith.
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Page/Page column 47; 126
(2014/07/08)
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- PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
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This document discloses molecules having the following formula (“Formula One”): and processes associated therewith.
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Paragraph 0620-0621
(2014/06/25)
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- PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
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This document discloses molecules having the following formula ("Formula One") and processes associated therewith.
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Page/Page column 126; 127
(2014/07/08)
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- Highly efficient synthesis of aryl and heteroaryl trifluoromethyl ketones via o-iodobenzoic acid (IBX)
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A two-step process for the synthesis of aryl and heteroaryl trifluoromethyl ketones from the corresponding aldehydes is described. Trifluoromethyl alcohols were prepared from aryl and heteroaryl aldehydes in excellent yields using catalytic amount of K2CO3. The trifluoromethyl alcohols were then oxidized conveniently and efficiently by o-iodoxybenzoic acid (IBX) under mild conditions to get the desired functionalized aryl and heteroaryl trifluoromethyl ketones.
- Cheng, Huicheng,Pei, Yu,Leng, Faqiang,Li, Jingya,Liang, Apeng,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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p. 4483 - 4486
(2013/07/26)
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- PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
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This document discloses molecules having the following formula (“Formula One”): and processes associated therewith.
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Page/Page column 68-69
(2013/02/28)
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- KYNURENINE PRODUCTION INHIBITOR
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Provided is a kynurenine production inhibitor comprising a nitrogen-containing heterocyclic compound represented by formula (I): (wherein R50 and R51 may be the same or different and each represent a hydrogen atom or the like, G1 and G2 may be the same or different and each represent a nitrogen atom or the like, X represents formula (III): (wherein m1 and m2 may be the same or different and each represent an integer of 0 or 1, Y represents an oxygen atom or the like, and R6 and R7 may be the same or different and each represent a hydrogen atom or the like), R1 represents optionally substituted lower alkyl or the like, R2 represents a hydrogen atom or the like, and R3 represents optionally substituted lower alkyl or the like), and the like.
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Page/Page column 137
(2011/10/12)
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- Magnesium metal-mediated reductive trifluoromethylation of aldehydes with phenyl trifluoromethyl sulfone
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An unprecedented reductive nucleophilic trifluoromethylation of aldehydes by using phenyl trifluoromethyl sulfone is reported. Mercury(II) chloride efficiently activates magnesium metal to induce the desulfonylative trifluoromethylation process. The new r
- Zhao, Yanchuan,Zhu, Jieming,Ni, Chuanfa,Hu, Jinbo
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experimental part
p. 1899 - 1904
(2010/08/19)
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- Sodium trifluoroacetate: An efficient precursor for the trifluoromethylation of aldehydes
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In a convenient and efficient procedure, the nucleophilic trifluoromethylation of aldehydes with sodium trifluoroacetate was achieved, using copper(I) halides as the catalyst.
- Chang, Ying,Cai, Chun
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p. 3161 - 3164
(2007/10/03)
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- MECHANISMS OF FREE-RADICAL REACTIONS. XIII. MECHANISM AND SELECTIVITY OF THE FREE-RADICAL HALOGENATION OF ALKYL AROMATIC HYDROCARBONS WITH FLUOROALKYL SUBSTITUENTS
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The free-radical chlorination and bromination of 1-fluoro-2-arylethanes and 1,1,1-trifluoro-2-arylethanes was studied by the method of competing reactions.In all cases a good correalation between log krel and the Brown ?+ constants was observed.The variation of the selectivity in the transition from one reaction series to the other indicates that two independent factors which determine the reactivity (the change in the dissociation energy of the C-H bond and the polar effect of the substituents) have a simultaneous effect.
- Dneprovskii, A. S.,Eliseenkov, E. V.,Mil'tsov, S. A.
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p. 317 - 324
(2007/10/02)
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- The reduction of aryl trifluoromethyl ketones by N-carbamoylmethyl-1,4-dihydronicotinamide
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The reaction of 15 aryl trifluoromethyl ketones with N-carbamoylmethyl-1,4-dihydronicotinamide has been studied in aqueous sulfolane buffer.The unsubstituted ketone and those containing electron-withdrawing groups in the ring have the following reaction characteristics: (a) a high yield of alcohol is obtained, (b) the observed reaction rate is independent of ring substituent; however, when corrections are made for degree of hydration of the ketones the rate is correlated with Hammett ? values with a rho of 1.98, (c) a secondary isotope effect of approximately 1.08 and primary isotope effects of 1.45-1.62 are observed at 43.4 deg C for the reaction of the dihydronicotinamide containing one or two atoms of deuterium at C-4, (d) ΔH = 15.2 kcal mol-1, and ΔS = -27.0 cal deg-1 mol-1 for the unsubstituted compound, uncorrected for ketone hydration; ΔS for reaction of the unhydrated ketone and dihydronicotinamide is estimated to be -45 to -50 cal deg-1 mol-1.The mechanism for the reduction is consistent with hydride transfer from reductant to oxidant, very possibly accompanied by blind-alley formation of an adduct between ketone hydrate and dihydronicotinamide.Ketones containing electron-donating groups in the ring react with the dihydronicotinamide in some undetermined way, giving little or no alcohol as product.
- Stewart, Ross,Teo, K. C.,Ng, L. K.
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p. 2497 - 2503
(2007/10/02)
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