- Simple access to β-trifluoromethyl-substituted ketones via copper-catalyzed ring-opening trifluoromethylation of substituted cyclopropanols
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Tertiary cyclopropanols react rapidly with Togni reagent in methanol at room temperature in the presence of catalytic amounts (3 mol%) of CuCl affording β-trifluoromethyl ketones in 65-73% isolated yields. Ring opening in 1,2-dialkylsubstituted cyclopropanols gives a mixture of isomeric β-trifluoromethyl ketones in about 50% combined yield.
- Kananovich, Dzmitry G.,Konik, Yulia A.,Zubrytski, Dzmitry M.,J?rving, Ivar,Lopp, Margus
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- Rhodium(III)-Catalyzed Oxidative Cyclization of Oxazolines with Cyclopropanols: Synthesis of Isoindolinones
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The synthesis of C3-substituted isoindolin-1-ones from oxazolines and cyclopropanols has been achieved with oxazoline as a bifunctional nucleophilic directing group. The reaction proceeds by the cleavage of three chemical bonds and allows the formation of three new chemical bonds, a C-N bond, a C-C bond, and a C-O bond, in a single step.
- Liu, Jidan,Yang, Zhenke,Jiang, Jinyuan,Zeng, Qiaohai,Zheng, Liyao,Liu, Zhao-Qing
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supporting information
p. 5927 - 5931
(2021/07/31)
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- INHIBITORS OF NOROVIRUS AND CORONAVIRUS REPLICATION
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Compounds of Formula (I) and methods of inhibiting the replication of viruses in a biological sample or patient, of reducing the amount of viruses in a biological sample or patient, and of treating a virus infection in a patient, comprising administering to said biological sample or patient an effective amount of a compound represented by Formula (I), a compound of Table A or B or a pharmaceutically acceptable salt thereof.
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Paragraph 00617-00619
(2021/10/15)
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- Catalytic Asymmetric Allylic Substitution with Copper(I) Homoenolates Generated from Cyclopropanols
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By using copper(I) homoenolates as nucleophiles, which are generated through the ring-opening of 1-substituted cyclopropane-1-ols, a catalytic asymmetric allylic substitution with allyl phosphates is achieved in high to excellent yields with high enantioselectivity. Both 1-substituted cyclopropane-1-ols and allylic phosphates enjoy broad substrate scopes. Remarkably, various functional groups, such as ether, ester, tosylate, imide, alcohol, nitro, and carbamate are well tolerated. Moreover, the present method is nicely extended to the asymmetric construction of quaternary carbon centers. Some control experiments argue against a radical-based reaction mechanism and a catalytic cycle based on a two-electron process is proposed. Finally, the synthetic utilities of the product are showcased by means of the transformations of the terminal olefin group and the ketone group.
- Shi, Chang-Yun,Yin, Liang,Zhang, Qi,Zhou, Si-Wei
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supporting information
p. 26351 - 26356
(2021/11/09)
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- Synthesis of γ-Keto Sulfones through a Three-Component Reaction of Cyclopropanols, DABCO ? (SO2)2 and Alkyl Halides
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A route to γ-keto sulfones through a metal-free reaction of cyclopropanols, DABCO ? (SO2)2 and alkyl halides is described. This reaction occurs under mild conditions in the absence of any catalysts, additives, or oxidants. Various functional groups including as ester, amino, methoxy, bromo, trifluoromethyl, nitro and carbonyl are tolerated well in this transformation, and the corresponding γ-keto sulfones are afforded in 35% to 95% yields. The proposed mechanism implies that this reaction proceeds through γ-keto sulfinate intermediate generated in situ, which further undergoes nucleophilic substitution with alkyl halides leading to γ-keto sulfones. (Figure presented.).
- Zhang, Chun,Zhang, Chao,Tang, Jie,Ye, Shengqing,Ma, Mingliang,Wu, Jie
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supporting information
p. 3109 - 3114
(2021/05/03)
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- Rh-Catalyzed cascade C-H activation/C-C cleavage/cyclization of carboxylic acids with cyclopropanols
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Merging both C-H and C-C activation in a tandem process is a marked challenge. A novel Rh(iii)-catalyzed C-H activation/ring opening C-C cleavage/cyclization of carboxylic acids with cyclopropanols was developed for the synthesis of 3-substituted phthalides andα,β-butenolides. This reaction displays excellent functional group tolerance with respect to both carboxylic acids and cyclopropanols and features relatively mild conditions. Remarkably, the utility of this method was highlighted by the rapid construction of bioactive compounds bearing a 3-substituted phthalide frameworkvialate-stage functionalization.
- Wang, Siqi,Miao, Erfei,Wang, Hao,Song, Bichao,Huang, Wei,Yang, Weibo
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supporting information
p. 5929 - 5932
(2021/06/18)
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- General Synthesis of Cyclopropanols via Organometallic Addition to 1-Sulfonylcyclopropanols as Cyclopropanone Precursors
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The addition of organometallic reagents to ketones constitutes one of the most straightforward synthetic approaches to tertiary alcohols. However, due to the absence of a well-behaved class of cyclopropanone surrogates accessible in enantioenriched form, such a trivial synthetic disconnection has received very little attention in the literature for the formation of tertiary cyclopropanols. In this work, we report a simple and high-yielding synthesis of 1-substituted cyclopropanols via the addition of diverse organometallic reagents to 1-phenylsulfonylcyclopropanols, acting here as in situ precursors of the corresponding cyclopropanones. The transformation is shown to be amenable to sp-, sp2-, or sp3-hybridized organometallic C-nucleophiles under mild conditions, and the use of enantioenriched substrates led to highly diastereoselective additions and the formation of optically active cyclopropanols.
- Jang, Yujin,Lindsay, Vincent N. G.,Poteat, Christopher M.,Rivera, Roger Machín
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supporting information
(2020/09/02)
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- Copper-mediated tandem ring-opening/cyclization reactions of cyclopropanols with aryldiazonium salts: Synthesis of: N -arylpyrazoles
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A general method for the synthesis of structurally diverse N-arylpyrazoles from readily available cyclopropanols and aryldiazonium salts is disclosed. The reaction was conducted at room temperature within minutes with a broad substrate scope and excellent regioselectivity.
- Liu, Jidan,Xu, Erjie,Jiang, Jinyuan,Huang, Zeng,Zheng, Liyao,Liu, Zhao-Qing
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supporting information
p. 2202 - 2205
(2020/02/26)
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- Metal-Free Direct C–H β-Carbonyl Alkylation of Heteroarenes with Cyclopropanols Mediated by K2S2O8
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Direct C–H β-carbonyl alkylation of heteroarenes under metal-, acid- and photo-catalyst free conditions has been achieved. A wide scope of substrates, such as various substituted quinolines and isoquinolines, pyridines, pyridazine, benzo[d]thiazole and phenanthroline, underwent the β-carbonyl alkylation efficiently via K2S2O8-mediated ring-opening of cyclopropanols. The corresponding β-heteroarylated ketones were obtained in moderate to excellent yields and gram-scale experiments further demonstrated the practicality of this synthetic protocol. The readily available reagents, mild and environmentally benign conditions make the method extremely attractive. The reaction mechanism is also proposed.
- Liu, Qiang,Wang, Qiang,Xie, Guanqun,Fang, Zeyang,Ding, Shujiang,Wang, Xiaoxia
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supporting information
p. 2600 - 2604
(2020/05/05)
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- Manganese-Catalyzed Ring-Opening Coupling Reactions of Cyclopropanols with Enones
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A manganese-catalyzed ring-opening coupling reaction of cyclopropanols with enones for the facile and efficient preparation of 1,6-diketones is described. A wide array of synthetically important 1,6-diketones bearing manifold functional groups are obtained with up to 93% yield. These reactions feature broad substrate scopes, environmentally benign conditions, inexpensive catalyst, and operational simplicity.
- Zhang, Yong-Hui,Zhang, Wen-Wei,Zhang, Ze-Yu,Zhao, Kai,Loh, Teck-Peng
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supporting information
p. 5101 - 5105
(2019/07/03)
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- Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates
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Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.
- Mills, L. Reginald,Zhou, Cuihan,Fung, Emily,Rousseaux, Sophie A. L.
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supporting information
p. 8805 - 8809
(2019/11/03)
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- Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
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A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
- Allen, Benjamin D. W.,Hareram, Mishra Deepak,Seastram, Alex C.,McBride, Tom,Wirth, Thomas,Browne, Duncan L.,Morrill, Louis C.
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supporting information
p. 9241 - 9246
(2019/11/19)
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- Palladium-Catalyzed Hydroalkylation of Alkynes with Cyclopropanols: Access to γ,δ-Unsaturated Ketones
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A palladium-catalyzed hydroalkylation of alkynes with cyclopropanols has been developed. This reaction provided a straightforward way to the synthesis of γ,δ-unsaturated ketones in moderate to good yields, exhibiting high atom economy and Z/E selectivity. Deuterated tri-substituted alkenes could also be expediently produced by using deuterium oxide as a co-solvent. (Figure presented.).
- Liu, Hao,Fu, Zhiyuan,Gao, Shang,Huang, Yue,Lin, Aijun,Yao, Hequan
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supporting information
p. 3171 - 3175
(2018/08/01)
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- Two-step conversion of carboxylic esters into distally fluorinated ketones: Via ring cleavage of cyclopropanol intermediates: Application of sulfinate salts as fluoroalkylating reagents
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Tertiary cyclopropanols easily available from carboxylic esters have been used in the synthesis of distally fluorinated ketones. Cyclopropane ring cleavage reactions in methanol with aqueous tert-butyl hydroperoxide in the presence of a copper(ii) acetate catalyst and sodium triflinate (Langlois reagent) afford β-trifluoromethyl ketones in 16-74% isolated yields. Sodium triflinate serves as a precursor of reactive trifluoromethyl copper species, enabling ring-opening trifluoromethylation, as evidenced by mechanistic studies. We also demonstrate here that other sulfinate salts, such as sodium 1,1-difluoroethanesulfinate, sodium 2-(4-bromophenyl)-1,1-difluoroethanesulfinate and sodium 1-(trifluoromethyl)cyclopropanesulfinate, can be used as fluoroalkylation reagents, resulting in the corresponding fluorinated ketones.
- Konik, Yulia A.,Kudrjashova, Marina,Konrad, Nele,Kaabel, Sandra,J?rving, Ivar,Lopp, Margus,Kananovich, Dzmitry G.
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supporting information
p. 4635 - 4643
(2017/07/10)
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- Enantioselective One-Pot Synthesis of α,β-Epoxy Ketones via Aerobic Oxidation of Cyclopropanols
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An efficient, mild, and environmentally benign method was developed for the asymmetric synthesis of 2-oxyranyl ketones from easily available tertiary cyclopropanols. The one-pot protocol includes the aerobic oxidation of cyclopropanol derivatives catalyzed by Mn(III) complexes followed by the poly-l-leucine-assisted stereoselective elimination of water from the intermediate peroxides with DBU to afford the corresponding epoxy ketones in high yields and good-to-excellent enantioselectivities (up to 97%).
- Elek, Gábor Zoltán,Borovkov, Victor,Lopp, Margus,Kananovich, Dzmitry G.
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supporting information
p. 3544 - 3547
(2017/07/17)
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- Synthesis of γ-keto sulfones by copper-catalyzed oxidative sulfonylation of tertiary cyclopropanols
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Tertiary cyclopropanols undergo ring-opening oxidative sulfonylation to afford γ-keto sulfones when reacting with sulfinate salts in the presence of a copper(ii) acetate catalyst and an oxidant (tert-butyl hydroperoxide or atmospheric oxygen). Various fluoroalkyl, aryl and alkyl sulfinate salts are successfully employed as sulfonylation reagents, affording the corresponding sulfones in up to 94% yields. The experimental protocol is mild and tolerates a number of functionalities in the cyclopropanol substrate. The reaction proceeds via a one-pot oxidation-Michael addition mechanism and can serve as a useful addition to the existing methods for the preparation of γ-keto sulfones based on the sulfa-Michael reaction.
- Konik, Yulia A.,Elek, Gábor Zoltán,Kaabel, Sandra,J?rving, Ivar,Lopp, Margus,Kananovich, Dzmitry G.
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supporting information
p. 8334 - 8340
(2017/10/23)
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- Copper-Catalyzed Cyclopropanol Ring Opening Csp3-Csp3 Cross-Couplings with (Fluoro)Alkyl Halides
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Novel and general copper-catalyzed cyclopropanol ring opening cross-coupling reactions with difluoroalkyl bromides, perfluoroalkyl iodides, monofluoroalkyl bromides, and 2-bromo-2-alkylesters to synthesize various β-(fluoro)alkylated ketones are reported.
- Ye, Zhishi,Gettys, Kristen E.,Shen, Xingyu,Dai, Mingji
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supporting information
p. 6074 - 6077
(2016/01/09)
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- Iron- or silver-catalyzed oxidative fluorination of cyclopropanols for the synthesis of β-fluoroketones
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The FeIII- or AgI-catalyzed oxidative fluorination of cyclopropanols via radical rearrangement is disclosed. This process features a straightforward and highly effective protocol for the site-specific synthesis of β-fluoroketones and represents an expedient method for the synthesis of γ-, δ- and ε-fluoroketones. Notably, this reaction proceeds at room temperature and tolerates a diverse array of cyclopropanols.
- Ren, Shichao,Feng, Chao,Loh, Teck-Peng
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supporting information
p. 5105 - 5109
(2015/05/13)
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- γ-carbonyl quinones: Radical strategy for the synthesis of evelynin and its analogues by C-H activation of quinones using cyclopropanols
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Cyclopropanols, on oxidative ring opening with AgNO3-K 2S2O8 in DCM-H2O at room temperature and under open flask conditions, produced β-keto radicals which were successfully added to quinones to furni
- Ilangovan, Andivelu,Saravanakumar, Shanmugasundar,Malayappasamy, Subramani
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supporting information
p. 4968 - 4971
(2013/10/22)
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- Cyclopropyl building blocks for organic synthesis, part 100.[?] Advanced syntheses of cyclopropylideneacetates - Versatile multifunctional building blocks for organic synthesis
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A well reproducible and inexpensive preparation of the cyclopropylideneacetates 2-4 has been developed. The key intermediate 2-(1′-mesyloxycyclopropyl)acetic acid (8), produced either from methyl phenylacetate (1) or 3,3-dimethoxypropionate (5-Me) and 3,3-diethoxypropionate (5-Et) in a sequence of Kulinkovich reductive cyclopropanation, mesylation and oxidative cleavage or cleavage and oxidation, respectively, was either converted to the benzyl ester 11b, or chlorinated (brominated) via the in situ formed acid chloride. The α-chloro- 12a and α-bromo ester 12b were dehydromesylated by treatment with triethylamine to furnish methyl 2-chloro-2-cyclopropylideneacetate (3-Me) and the 2-bromo analogue 4-Me with an overall yield of 68% (65%, 68%) and 52% (49%, 51%) respectively, starting from 1 (5-Me, 5-Et). The parent benzyl cyclopropylideneacetate 2-Bn was obtained by dehydromesylation of 11b with potassium t-butoxide in t-butyl methyl ether with an overall yield of 60% (57%, 9%) from 1 (5-Me, 5-Et).
- Limbach, Michael,Dalai, Suryakanta,De Meijere, Armin
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p. 760 - 766
(2007/10/03)
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- Reactions of 2-substituted epichlorohydrins
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2-Substituted epichlorohydrins have been synthesized by starting with 1,2-dichloro acetone and various alkyl and aryl halides via dichlorohydrins followed by cyclization. The reactive 2-substituted epichlorohydrins were subjected to nucleophilic attacking of azide and cyanide ions to afford corresponding β-azido alcohols and α,β-unsaturated nitriles.
- Tanyeli,Demir,Akhmedov,Ozgul,Kandemir
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p. 2967 - 2980
(2007/10/03)
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- Reactions of Carbonyl Compounds with Benzyl Chloromethyl Ether of Diiodomethane in the Presence of Samarium(II) Iodide or Metallic Samarium. New Routes to 1,2-Diols, Iodohydrins and Cyclopropanols
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Carbonyl compounds react with benzyl chloromethyl ether in the presence of samarium(II) iodide to afford the corresponding addition products which, when subsequently hydrogenolysed, yield 1,2-diols.Simple aldehydes and ketones react with diiodomethane in the presence of samarium metal to give iodohydrins in good yields.Under similar reaction conditions, α-halogeno substituted ketones and aromatic 1,4-diketones are converted into cyclopropanols.These cyclopropanations have been shown to rpoceed through the initial generation of samarium enolates, followed by the Simmons-Smith type reaction.A novel transformation of esters to cyclopropanols via tandem one-carbon homologation is also described.
- Imamoto, Tsuneo,Hatajima, Toshihiko,Takiyama, Nobuyuki,Takeyama, Toshiaki,Kamiya, Yasuo,Yoshizawa, Takeshi
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p. 3127 - 3135
(2007/10/02)
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- TANDEM ONE-CARBON HOMOLOGATION OF ESTERS TO CYCLOPROPANOLS
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Esters react with diiodomethane in the presence of samarium to afford 1-substituted cyclopropanols in good yields.
- Imamoto, Tsuneo,Kamiya, Yasuo,Hatajima, Toshihiko,Takahashi, Harumi
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p. 5149 - 5152
(2007/10/02)
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