- Stereoselective Synthesis of Oxacycles via Ruthenium-Catalyzed Atom-Economic Coupling of Propargyl Alcohols and Michael Acceptors
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Synthesis of β-hydroxyenones and its application toward development of tetrahydro-4H-pyran-4-one in an atom-economic fashion is limited. This manuscript describes a ruthenium-catalyzed atom-economic coupling of pent-2-yne-1,5-diols and Michael acceptors as an efficient route for the synthesis of β-hydroxyenones with excellent yields and high regioselectivity. The β-hydroxyenones further undergo a 6-endo trig cyclization under acid-catalyzed conditions to deliver the tetrahydro-4H-pyran-4-ones with high diastereoselectivity. An intramolecular aldol condensation under mild basic conditions and palladium-catalyzed oxidative aromatization was developed for the synthesis of hexahydro-6H-isochromen-6-ones and isochromanols, respectively, from highly substituted tetrahydro-4H-pyran-4-ones with excellent yield and diastereoselectivity. Overall, this work demonstrates the synthetic potential toward the synthesis of oxacycles like tetrahydro-4H-pyran-4-ones, hexahydro-6H-isochromen-6-ones, and isochromanols via an atom-economic catalysis.
- Bera, Nabakumar,Samanta, Shantanu,Sarkar, Debayan
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p. 16369 - 16395
(2021/11/18)
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- NOVEL CYCLIC TREX1 INHIBITORS
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The present invention provides compounds of Formula I: wherein, X, R1, R2, R3 and R4 are as defined herein, or a stereoisomer, tautomer, pharmaceutically acceptable salt, prodrug ester or solvate form thereof, wherein all of the variables are as defined herein. These compounds are effective at modulating the TREX1 protein and thus can be used as medicaments for treating or preventing disorders affected by the inhibition of TREX1.
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Paragraph 00102-00104
(2020/10/21)
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- A Pd-catalyzed ring opening coupling reaction of 2,3-allenylic carbonates with cyclopropanols
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A palladium-catalyzed coupling reaction of 2,3-allenylic carbonates with cyclopropanols was developed, affording valuable 1,3-diene products with different functional groups efficiently under mild reaction conditions. Gram scale synthesis was easily conducted with synthetic transformations demonstrated.
- Lin, Jie,Zhu, Tonghao,Jia, Minqiang,Ma, Shengming
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supporting information
p. 4523 - 4526
(2019/04/26)
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- A method of preparing intermediates of luck sha neiwei
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The invention provides a preparation method for a fosamprenir intermediate. The preparation method comprises the following steps: taking benzyl cyanide as a raw material, and performing steps of nitrile hydrolysis, acylation, reaction with a Grignard reagent, ammonization, cyclizing and the like for synthesizing (2R,3S)-1,2-epoxy-3-t-butyloxycarborylamino-4-phenyl butane. The method is reasonable in process, simple to operate, low in cost and high in yield; with the method, industrialization can be well realized and the production efficiency is improved.
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- Matched Coupling of Propargylic Carbonates with Cyclopropanols
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The ring opening-coupling reaction of cyclopropanols with propargylic carbonates affording synthetically attractive allenyl ketones has been developed. The mechanism involves the ligand-exchange reaction of in situ formed allenyl palladium methoxide with cyclopropanols followed by carbon-carbon bond cleavage and reductive elimination. The reactions proceeded smoothly under mild reaction conditions with Pd(0)/XPhos catalysis in the absence of any external base and displayed a wide scope and application to a steroidal skeleton. The efficiency of chirality transfer and synthetic utility of the allene products have also been demonstrated.
- Wu, Penglin,Jia, Minqiang,Lin, Weilong,Ma, Shengming
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supporting information
p. 554 - 557
(2018/02/10)
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- Palladium-catalyzed aerobic oxidative coupling of allylic alcohols with anilines in the synthesis of nitrogen heterocycles
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We report herein an unprecedented and expedient Pd-catalyzed oxidative coupling of allyl alcohols with anilines to afford β-amino ketones which are converted into substituted quinolines in a one-pot fashion. The exclusive preference for N-alkylation over N-allylation makes this approach unique when compared to those reported in literature. Detailed mechanistic investigations reveal that the conjugate addition pathway was the predominant one over the allylic amination pathway. The notable aspects of the present approach are the use of readily available, bench-stable allyl alcohols and molecular oxygen as the terminal oxidant, in the process dispensing the need for unstable and costly enones. Further, we explored the synthetic utility of β-amino ketones through an intramolecular α-arylation methodology and a one-pot domino annulation, thereby providing rapid access to indolines and quinolines.
- Kumar, Gangam Srikanth,Singh, Diksha,Kumar, Manish,Kapur, Manmohan
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p. 3941 - 3951
(2018/04/14)
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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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p. 4635 - 4643
(2017/07/10)
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- Traceless Directing-Group Strategy in the Ru-Catalyzed, Formal [3 + 3] Annulation of Anilines with Allyl Alcohols: A One-Pot, Domino Approach for the Synthesis of Quinolines
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A unique, ruthenium-catalyzed, [3 + 3] annulation of anilines with allyl alcohols in the synthesis of substituted quinolines is reported. The method employs a traceless directing group strategy in the proximal C-H bond activation and represents a one-pot Domino synthesis of quinolines from anilines.
- Kumar, Gangam Srikanth,Kumar, Pravin,Kapur, Manmohan
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p. 2494 - 2497
(2017/05/24)
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- Metal Coordination Controlled and Bifunctional H-Bonded Catalysis in Stereoselective Intramolecular Aldol Cyclizations toward Carbocyclic Tertiary β-Ketols
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The principle of bifunctional catalysis is shown in the highly regio- and stereoselective intramolecular aldolization of 2-methyl-1,3-cyclopentanedione, C2-substituted with a methyl ethyl ketone group, to provide [3.2.1]-bicyclooctanol diones in the presence of catalytic amounts of either LiBr and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). Mechanistic investigations corroborated by DFT calculations show that LiBr engages in a bifunctional coordination of two carbonyl moieties and leads to the preorganization of the reactive enolate intermediate for a base-mediated intramolecular aldol cyclization. On the other hand, TBD catalysis of the triketone substrate proceeds through a bifunctional H-bonded mechanism to give the same aldol product as the major diastereomer. The LiBr and TBD-catalyzed highly stereocontrolled intramolecular aldol cyclizations can be extended to other di- and triketones to give carbocyclic and carbobicyclic products as single diastereomers.
- Chen, Bin,Berger, Gilles,Hanessian, Stephen
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supporting information
p. 2631 - 2636
(2017/05/19)
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- Synthesis of isoindolinones via a ruthenium-catalyzed cyclization of N-substituted benzamides with allylic alcohols
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N-Substituted aromatic and heteroaromatic amides reacted with substituted allylic alcohols in the presence of a ruthenium catalyst, AgSbF6 and a Cu(OAc)2·H2O oxidant, affording 3-substituted isoindolinone derivatives with diverse substituents in good to excellent yields. A possible reaction mechanism involving a five-membered ruthenacycle intermediate was proposed and strongly supported by experimental evidence.
- Manoharan, Ramasamy,Jeganmohan, Masilamani
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supporting information
p. 2929 - 2932
(2015/02/19)
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- Highly stereoselective cyclopropanation of α,β-unsaturated carbonyl compounds with methyl (diazoacetoxy)acetate catalyzed by a chiral ruthenium(II) complex
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Tantalizing triangles: The title reaction gives bicarbonyl cyclopropane products that can lead to versatile intermediates with high yields and stereoselectivities. This system was also applied to the enantioselective total synthesis of spiro cyclopropane oxindole, an HIV-1 nonnucleoside reverse transcriptase inhibitor. Copyright
- Chanthamath, Soda,Takaki, Suguru,Shibatomi, Kazutaka,Iwasa, Seiji
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supporting information
p. 5818 - 5821
(2013/07/11)
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- Synthesis of water-tolerant indium homoenolate in aqueous media and its application in the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chloride
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The first water-tolerant, ketone-type indium homoenolate was synthesized via the oxidative addition of In/InCl3 to enones. The reaction proceeds exclusively in aqueous media. Both indium and indium(III) chloride are necessary for the smooth conversion of the reaction. Similar results were obtained when InCl or InCl2 was used in place of In/InCl3. The synthetic utility of the indium homoenolate was demonstrated through the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling of indium homoenolate with acid chloride.
- Shen, Zhi-Liang,Goh, Kelvin Kau Kiat,Cheong, Hao-Lun,Wong, Colin Hong An,Lai, Yin-Chang,Yang, Yong-Sheng,Loh, Teck-Peng
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supporting information; experimental part
p. 15852 - 15855
(2011/01/10)
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- Synthesis and evaluation of novel pyrazolidinone analogs of PGE2 as EP2 and EP4 receptors agonists
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Replacement of the hydroxy cyclopentanone ring in PGE2 with chemically more stable heterocyclic rings and substitution of the unsaturated α-alkenyl chain with a metabolically more stable phenethyl chain led to the development of potent and selective analogs of PGE2. Compound 10f showed the highest potency and selectivity for EP4 the receptor.
- Zhao, Zhong,Araldi, Gian Luca,Xiao, Yufang,Reddy, Adulla P.,Liao, Yihua,Karra, Srinivasa,Brugger, Nadia,Fischer, David,Palmer, Elizabeth
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p. 6572 - 6575
(2008/09/16)
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- Vinyl ketones to allenes: Preparation of 1,3-dien-2-yl triflates and their application in Pd-catalyzed reactions with soft nucleophiles
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(Chemical Equation Presented) A general route of converting alkenyl ketones to functionalized allenes was developed. Substituted 1,3-dien-2-yl triflates, which were prepared from the alkenyl ketones via silyl dienol ethers, were excellent substrates for t
- Ogasawara, Masamichi,Ge, Yonghui,Uetake, Koichi,Takahashi, Tamotsu
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p. 5697 - 5700
(2007/10/03)
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- Stereoselective synthesis of substituted N-heterocycles via sequential cross metathesis-reductive cyclization
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A diastereoselective synthesis of substituted piperidine and pyrrolidine derivatives is presented, employing a highly selective cross metathesis (CM) reaction followed by a domino reduction-cyclization process. A diastereoselective synthesis of substituted mono- and bicyclic-piperidine and pyrrolidine derivatives is presented, employing a highly selective cross metathesis (CM) reaction followed by a domino reduction-cyclization process.
- Gebauer, Julian,Dewi, Purnama,Blechert, Siegfried
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- Total synthesis of (±)-aspidospermidine
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(±)-Aspidospermidine (1) has been synthesized from readily available methyl 3-ethyl-2-oxocylopentanecarboxylate (17) in 5.9% yield over 13 steps. The key step of the synthesis is an intramolecular cascade reaction that simultaneously forms the B, C, and D rings of 1. A high-yielding method of closing the remaining E ring is also described.
- Toczko, Matthew A.,Heathcock, Clayton H.
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p. 2642 - 2645
(2007/10/03)
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- The Addition of 1-Lithio-1-(phenylthio)alkanes to 2-(N-Methylanilino)acrylonitrile: An Easy Access to 3-(Phenylthio)ketones and 2-Enones
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A simple and versatile strategy for the synthesis of the title compounds is described.The key-step consists in the addition of 1-lithio-1-(phenylthio)alkanes to 2-(N-methylanilino)acrylonitrile, the nucleophilic phenylthioalkylation of an enol-cation equivalent.Alkylation of the adducts and hydrolysis give 3-(phenylthio)ketones, which can be isolated, or without further purification can be transformed into 2-enones via the well known oxidation-elimination procedure.These reactions are possible with allylic derivatives too, therefore the homologous vinylic compoundscan be prepared by the same way.Pyrolysis of the 1-lithioaminonitriles formed within the first step gives aminonitriles of cyclopropanones via cyclization.
- Ahlbrecht, Hubertus,Ibe, Marcellinus
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p. 210 - 214
(2007/10/02)
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- α,β-Epoxy Sulfoxides as Useful Intermediates in Organic Synthesis. IX. A Novel Synthesis of Alkyl Vinyl Ketones and Divinyl Ketones from Carbonyl Compounds and 1-Chloro-3-phenylthiopropyl Phenyl Sulfoxide as a Three-Carbon Homologating Agent
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The α,β-epoxy sulfoxides easily derived from carbonyl compounds and 1-chloro-3-phenylthiopropyl phenyl sulfoxide were treated with sodium benzeneselenolate to give β-phenylthio carbonyl compounds in excellent yields.The phenylthio group was oxidized to the sulfinyl group and was then treated with a base to afford alkyl vinyl ketones in quite good yields.This reaction presents a novel method for the preparation of alkyl vinyl ketones from carbonyl compounds by three-carbon homologation.The treatment of α,β-epoxy sulfoxides mentioned above with benzenethiolate gave α,β'-bis(phenylthio) ketones.The elimination of the both thio groups afforded divinyl ketones.
- Satoh, Tsuyoshi,Kumagawa, Takumi,Sugimoto, Atsushi,Yamakawa, Koji
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p. 301 - 310
(2007/10/02)
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- A NOVEL SYNTHESIS OF ALKYL VINYL KETONES AND DIVINYL KETONES FROM CARBONYL COMPOUNDS BY THREE-CARBON HOMOLOGATION
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Alkyl vinyl ketones and divinyl ketones are synthesized from carbonyl compounds and 1-chloro-3-phenylthiopropyl phenyl sulfoxide as a three-carbon homologating agent in good overall yileds.
- Satoh, Tsuyoshi,Kumagawa, Takumi,Yamakava, Koji
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p. 2471 - 2474
(2007/10/02)
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- CONVENIENT SYNTHESIS OF VINYL KETONES VIA A NEW THREE CARBON HOMOLOGATING AGENT
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Syntheses of vinyl ketones and the himachalene skeleton from 4-phenylthio-N,N-dimethylaminobutyronitrile were demonstrated.
- Tuchinda, Patoomratana,Prapansiri, Vichukorn,Naengchommong, Waree,Reutrakul, Vichai
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p. 1427 - 1430
(2007/10/02)
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- A NEW ELONGATION REACTION OF THREE CARBON UNITS
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A new modification of Peterson reaction leading to elongation of three carbon units by treatment of aldehydes with titanium ate complex, prepared from 1-lithio-1-(1-alkoxy)allyltrimethylsilane and titanium(IV) isopropoxide, is described.
- Murai, Akio,Abiko, Atsushi,Shimada, Naoki,Masamune, Tadashi
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p. 4951 - 4954
(2007/10/02)
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- Palladium-Catalyzed Acylation of Unsaturated Halides by Anions of Enol Ethers
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Zinc salts of enol ether anions are coupled to aryl and alkenyl halides by using palladium catalysts, effecting a direct acetylation of aryl and alkenyl halides.Zinc salts of allenic ethers are coupled with aryl and alkenyl halides under similar conditions to give α,β-unsaturated ketones, the allenic ether serving as a source of the acryloyl group.Allenic ethers were γ arylated in a palladium-catalyzed coupling with aryl halides to give β,β-diaryl-α,β-unsaturated aldehydes.
- Russell, Charles E.,Hegedus, Louis S.
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p. 943 - 949
(2007/10/02)
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- PALLADIUM-CATALYZED ACYLATION OF ORGANOZINCS AND OTHER ORGANOMETALLICS AS A CONVENIENT ROUTE TO KETONES
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The reaction of organozincs with acyl chlorides catalyzed by palladium-phosphine complexes, e.g., Pd(PPh3)4, provides a highly general and convinient route to ketones.
- Negishi, Ei-ichi,Bagheri, Vahid,Chatterjee, Sugata,Luo, Fen-Tair,Miller, Joseph A.,Stoll, A. Timothy
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p. 5181 - 5184
(2007/10/02)
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