- Access to Trisubstituted Fluoroalkenes by Ruthenium-Catalyzed Cross-Metathesis
-
Although the olefin metathesis reaction is a well-known and powerful strategy to get alkenes, this reaction remained highly challenging with fluororalkenes, especially the Cross-Metathesis (CM) process. Our thought was to find an easy accessible, convenient, reactive and post-functionalizable source of fluoroalkene, that we found as the methyl 2-fluoroacrylate. We reported herein the efficient ruthenium-catalyzed CM reaction of various terminal and internal alkenes with methyl 2-fluoroacrylate giving access, for the first time, to trisubstituted fluoroalkenes stereoselectively. Unprecedent TON for CM involving fluoroalkene, up to 175, have been obtained and the reaction proved to be tolerant and effective with a large range of olefin partners giving fair to high yields in metathesis products. (Figure presented.).
- Nouaille, Augustin,Pannecoucke, Xavier,Poisson, Thomas,Couve-Bonnaire, Samuel
-
p. 2140 - 2147
(2021/03/06)
-
- Hydrophosphination using [GeCl{N(SiMe3)2}3] as a pre-catalyst
-
Transformations catalyzed by germanium are scarce, with examples mainly limited to widely catalyzed processes such as polymerisation of lactide and hydroboration of carbonyls. Reported is the first example of hydrophosphination using a germanium pre-catalyst, yielding anti-Markovnikov products when diphenylphosphine is reacted with styrenes or internal alkynes at room temperature. This journal is
- Barrett,Sanderson,Mahon,Webster
-
supporting information
p. 13623 - 13626
(2020/11/17)
-
- Stereoselective Convergent Synthesis of Tetrahydro-5 H-benzo[c]fluorene via Nine-Membered Ring-Closing Metathesis and Transannular Acid-Mediated Cyclization/Nucleophilic Addition
-
The diene methyl ethers or acetates, constructed from the Li-Br exchange/addition reactions of 2-vinylbenzaldehydes and 2-(but-3-en-1-yl)bromoarenes followed by etherification or acetylation of the corresponding alcohols, smoothly underwent the ring-closi
- Lekky, Anek,Ruengsatra, Tanachote,Ruchirawat, Somsak,Ploypradith, Poonsakdi
-
p. 5277 - 5291
(2019/05/10)
-
- Umpolung of Carbonyl Groups as Alkyl Organometallic Reagent Surrogates for Palladium-Catalyzed Allylic Alkylation
-
Palladium-catalyzed allylic alkylation of nonstabilized carbon nucleophiles is difficult and remains a major challenge. Reported here is a highly chemo- and regioselective direct palladium-catalyzed C-allylation of hydrazones, generated from carbonyls, as a source of umpolung unstabilized alkyl carbanions and surrogates of alkyl organometallic reagents. Contrary to classical allylation techniques, this umpolung reaction utilizes hydrazones prepared not only from aryl aldehydes but also from alkyl aldehydes and ketones as renewable feedstocks. This strategy complements the palladium-catalyzed coupling of unstabilized nucleophiles with allylic electrophiles by providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.
- Zhu, Dianhu,Lv, Leiyang,Li, Chen-Chen,Ung, Sosthene,Gao, Jian,Li, Chao-Jun
-
supporting information
p. 16520 - 16524
(2018/11/23)
-
- Direct allylation of benzyl alcohols, diarylmethanols, and triarylmethanols mediated by XtalFluor-E
-
We report the direct allylation of benzyl alcohols, diarylmethanols and triarylmethanols mediated by XtalFluor-E using allyltrimethylsilane. The resulting allylated products are obtained in moderate to high yield.
- Lebleu, Thomas,Paquin, Jean-Fran?ois
-
supporting information
p. 442 - 444
(2017/01/10)
-
- Application of Dehydroabietic Acid in Palladium-Catalysed Enyne Cycloisomerisation
-
Dehydroabietic acid (DAA) promotes palladium(0)-catalysed cyclisations of arene-tethered 1,7-enynols and 1,m-enynoates (m=6,7) to give fused carbocyclic dienes. 6,6,6,5-Tetracyclic lactones are accessible by one-pot cycloisomerisation/Diels–Alder reaction
- Wu, Na,Li, Ruikun,Cui, Feihu,Pan, Yingming
-
supporting information
p. 2442 - 2447
(2017/07/22)
-
- 1,3,8-TRIAZASPIRO[4,5]DECAN-4-ONE DERIVATIVES USEFUL FOR THE TREATMENT OF ORL-1 RECEPTOR MEDIATED DISORDERS
-
The present invention is directed to novel 1,3,8-triazaspiro[4.5]decan-4-one derivatives of the general formulawherein all variables are as defined herein, useful in the treatment of disorders and conditions mediated by the ORL-1 G-protein coupled receptor. More particularly, the compounds of the present invention are useful in the treatment of disorders and conditions such as anxiety, depression, substance abuse, neuropathic pain, acute pain, migraine, asthma, cough and for improved cognition.
- -
-
Paragraph 0238-0240
(2017/02/28)
-
- Aryl radical cyclization with alkyne followed by tandem carboxylation in methyl 4-tert-butylbenzoate-mediated electrochemical reduction of 2-(2-propynyloxy)bromobenzenes in?the presence of carbon dioxide
-
Constant current electrolysis of 2-(2-propynyloxy)bromobenzenes in DMF using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of carbon dioxide and an electron transfer mediator, methyl 4-tert-butylbenzoate, resulted in aryl ra
- Katayama, Asahi,Senboku, Hisanori,Hara, Shoji
-
p. 4626 - 4636
(2016/07/18)
-
- Characterization of the Dynamic Equilibrium between Closed and Open Forms of the Benzoxaborole Pharmacophore
-
Benzoxaboroles are a class of five-membered hemiboronic acids that recently attracted significant attention as a new pharmacophore on account of their unique structural and physicochemical properties and their ability to interact selectively with biomolecules. Their structural behavior in water and its effect on their physiological properties remain unclear, especially the question of dynamic hydrolytic equilibrium of the oxaborole ring. Herein, we used NMR spectroscopy, in mixed aqueous-organic solvent, to confirm the strong preference for the closed form of benzoxaborole and its six- and seven-membered homologues over the open boronic acid form. Only with the eight-membered homologue does the cyclic form become unfavorable. Using dynamic VT-NMR studies with designed probe compound 20, we demonstrate that the oxaborole ring undergoes rapid hydrolytic ring closing-opening at ambient temperature at a rate of >100 Hz via a mechanism featuring rate-limiting proton-transfer steps. This knowledge can help provide a better understanding of the behavior of benzoxaboroles in biological systems.
- Vshyvenko, Sergey,Clapson, Marissa L.,Suzuki, Itaru,Hall, Dennis G.
-
p. 1097 - 1101
(2016/12/18)
-
- Iridium-catalyzed borylation of secondary benzylic C-H bonds directed by a hydrosilane
-
Most functionalizations of C-H bonds by main-group reagents occur at aryl or methyl groups. We describe a highly regioselective borylation of secondary benzylic C-H bonds catalyzed by an iridium precursor and 3,4,7,8-tetramethyl-1, 10-phenanthroline as the ligand. The reaction is directed to the benzylic position by a hydrosilyl substituent. This hydrosilyl directing group is readily deprotected or transformed to other functional groups after the borylation reaction, providing access to a diverse set of secondary benzylboronate esters by C-H borylation chemistry.
- Cho, Seung Hwan,Hartwig, John F.
-
supporting information
p. 8157 - 8160
(2013/07/05)
-
- Gold-catalyzed oxidative coupling reactions with aryltrimethylsilanes
-
During continuing studies with a novel oxidative gold oxyarylation reaction, arylsilanes were found to be competent coupling partners, providing further evidence for an intramolecular electrophilic aromatic substitution mechanism. While providing yields complementary to those of the previously described boronic acid methods, the use of trimethylsilanes reduces the observation of homocoupling byproducts and allows for facile intramolecular coupling reactions.
- Brenzovich Jr., William E.,Brazeau, Jean-Francois,Toste, F. Dean
-
supporting information; experimental part
p. 4728 - 4731
(2010/12/25)
-
- Orthogonal reactivity in boryl-substituted organotrifluoroborates
-
A method was developed for the hydroboration of alkenyl-containing organotrifluoroborates to generate dibora intermediates. The reactivity differences between organotrifluoroborates and trialkylboranes facilitated the cross-coupling of the borane moiety o
- Molander, Gary A.,Sandrock, Deidre L.
-
supporting information; experimental part
p. 15792 - 15793
(2009/05/15)
-
- Novel ligands for the human histamine H1 receptor: Synthesis, pharmacology, and comparative molecular field analysis studies of 2-dimethylamino-5-(6)-phenyl-1,2,3,4-tetrahydronaphthalenes
-
This paper reports the synthesis of a novel series of (±)-2-dimethylamino- 5- and 6-phenyl-1,2,3,4-tetrahydronaphthalene derivatives (5- and 6-APTs), and, corresponding affinity, functional activity, and, molecular modeling studies with regard to drug des
- Ghoneim, Ola M.,Legere, Jacqueline A.,Golbraikh, Alexander,Tropsha, Alexander,Booth, Raymond G.
-
p. 6640 - 6658
(2007/10/03)
-
- 1,3,8-Triazaspiro[4.5]decan-4-one derivatives useful for the treatment of ORL-1 receptor mediated disorders
-
The present invention is directed to novel 1,3,8-triazaspiro[4.5]decan-4-one derivatives of the general formula wherein all variables are as defined herein, useful in the treatment of disorders and conditions mediated by the ORL-1 G-protein coupled receptor. More particularly, the compounds of the present invention are useful in the treatment of disorders and conditions such as anxiety, depression, substance abuse, neuropathic pain, acute pain, migraine, asthma, cough and for improved cognition.
- -
-
-
- Intramolecular palladium-catalyzed aryl amination and aryl amidation
-
Upon treatment with a palladium catalyst and a suitable base, aromatic halides undergo intramolecular substitution to form five, six, and seven-membered rings. In a similar fashion aryl halides with pendant amides or sulfonamides are cyclized to form five and six-membered rings.
- Wolfe, John P.,Rennels, Roger A.,Buchwald, Stephen L.
-
p. 7525 - 7546
(2007/10/03)
-
- Direct Preparation of Organocadmium Compounds from Highly Reactive Cadmium Metal Powders
-
Highly reactive cadmium metal powders and a cadmium-lithium alloy were prepared and were used to prepare organocadmium reagents directly from organic halides.
- Burkhardt, Elizabeth R.,Rieke, Reuben D.
-
p. 416 - 417
(2007/10/02)
-