- Compound of dipyrrolopyridine structure Preparation method and medical application
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The invention discloses a compound with a dipyrrolo-pyridine structure as well as a preparation method and medical application thereof. The compound provided by the invention has obvious inhibitory activity on JAK family proteins, is an effective JAK inhibitor, and has the prospect of being developed into drugs for inhibiting JAK and further treating diseases.
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Paragraph 0099-0102
(2021/08/25)
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- Pd-catalyzed sp-sp3cross-coupling of benzyl bromides using lithium acetylides
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Organolithium-based cross-coupling reactions have emerged as an indispensable method to construct C-C bonds. These transformations have proven particularly useful for the direct and fast coupling of various organolithium reagents (sp, sp2, and sp3) with aromatic (pseudo) halides (sp2). Here we present an efficient method for the cross-coupling of benzyl bromides (sp3) with lithium acetylides (sp). The reaction proceeds within 10 min at room temperature and can be performed in the presence of organolithium-sensitive functional groups such as esters, nitriles, amides and boronic esters. The potential application of the methodology is demonstrated in the preparation of key intermediates used in pharmaceuticals, chemical biology and natural products.
- Buter, Jeffrey,Doze, Anna M.,Feringa, Ben L.,Mondal, Anirban,Visser, Paco
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p. 7529 - 7532
(2021/08/05)
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- Pyrazolopyrimidine [3,4-d] compound as well as preparation method and application thereof
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The invention relates to a compound which is a Bruton tyrosine kinase inhibitor. In addition, the invention discloses a pharmaceutical ingredient and a preparation that comprise the compound, and an application of the kinase inhibitor. The compound can be used independently or combined with other compounds for treating kinase mediated or kinase-dependent symptoms.
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Paragraph 0321; 0323; 0324; 0325
(2019/06/10)
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- Propargylsilanes as Reagents for Synergistic Gold(I)-Catalyzed Propargylation of Carbonyl Compounds: Isolation and Characterization of σ-Gold(I) Allenyl Intermediates
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Reported herein is the isolation and characterization, for the first time, of a σ-gold allenyl complex as an intermediate in gold catalysis. This intermediate was captured during the study of a novel gold(I)-catalyzed propargylation of carbonyl compounds with propargylsilanes. Notably, the gold-catalyzed propargylation reaction, which proceeds with aldehydes and ketones, can be driven to the formation of either homopropargyl silyl ethers or the in situ synthesis of corresponding 2-silyl-4,5-dihydrofurans.
- Fernández, Sergio,González, Jairo,Santamaría, Javier,Ballesteros, Alfredo
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supporting information
p. 10703 - 10707
(2019/06/25)
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- Palladium-Catalyzed Coupling of Terminal Alkynes with Benzyl Ammonium Salts
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A highly efficient palladium-catalyzed Sonogashira coupling of benzylic ammonium salts with terminal alkynes is developed. This strategy provides a facile access to a series of internal alkyne derivatives in moderate to excellent yields via C-N bond cleavage and C(sp3)-C(sp) bond formation. The broad substrate scope and high functional group tolerance make this reaction attractive for organic synthesis.
- Xu, Silin,Zhang, Zhenming,Han, Chunyu,Hu, Wenkai,Xiao, Tiwen,Yuan, Yanan,Zhao, Junfeng
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p. 12192 - 12197
(2019/10/11)
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- Bifunctional Biphenyl-2-ylphosphine Ligand Enables Tandem Gold-Catalyzed Propargylation of Aldehyde and Unexpected Cycloisomerization
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Despite extensive studies in gold catalysis, σ-allenylgold species have not been invoked as catalytic intermediates and their reactivities not studied. This work reports for the first time they are generated in situ and undergo nucleophilic addition to activated aldehydes in a bifunctional phosphine ligand-enabled gold catalysis. This development reveals a broad range of opportunities to achieve propargylic C-H functionalization for the first time under catalytic and mild conditions. The homopropargylic alcohols generated undergo ligand-enabled cycloisomerizations involving an unexpected silyl migration.
- Li, Ting,Zhang, Liming
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supporting information
p. 17439 - 17443
(2019/01/04)
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- Regio- and Stereospecific Copper-Catalyzed Substitution Reaction of Propargylic Ammonium Salts with Aryl Grignard Reagents
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We have developed a copper-catalyzed substitution reaction of propargylic ammonium salts with aryl Grignard reagents. The reaction is stereospecific and α-regioselective and proceeds with exceptional functional group tolerance. Conveniently, a stable, inexpensive, and commercially available copper salt is used and no added ligand is required.
- Guisán-Ceinos, Manuel,Martín-Heras, Victor,Tortosa, Mariola
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p. 8448 - 8451
(2017/07/06)
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- Direct Synthesis of α-Allenols from TMS-Protected Alkynes and Aldehydes Mediated by Tetrabutylammonium Fluoride
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A unique chemoselective synthesis of α-allenic alcohols is presented. Tetrabutylammonium fluoride (TBAF) mediated this transformation under mild reaction conditions. A range of functional groups is well-tolerated in this reaction, while affording adducts
- Huang, Xiaojun,Bugarin, Alejandro
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supporting information
p. 12696 - 12700
(2016/08/30)
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- Regioselective Allylation of Carbon Electrophiles with Alkenyl-silanes under Dual Catalysis by Cationic Platinum(II) Species
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In the presence of catalytic amounts of platinum(II) chloride and silver(I) hexafluoroantimonate, (Z)-alkenylsilanes reacted with various carbon electrophiles (acetals, aminals, carboxylic anhydrides, alkyl chlorides, etc.) at the γ-position to give allylation products. A plausible mechanism for the platinum-catalyzed allylation involves alkene migration of alkenylsilanes to allylsilanes and subsequent allylation of carbon electrophiles, both of which are catalyzed by a cationic platinum(II) species.
- Kinoshita, Hidenori,Kizu, Ryosuke,Horikoshi, Masahiro,Inoue, Gen,Fujimoto, Masayuki,Saito, Masanori,Ichikawa, Junji,Hosomi, Akira,Miura, Katsukiyo
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supporting information
p. 520 - 534
(2016/02/16)
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- Preparation of Tri- and tetrasubstituted allenes via regioselective lateral metalation of benzylic (Trimethylsilyl)alkynes using TMPZnCl·LiCl
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The zincation of various 1-(trimethylsilyl)-3-aryl-1-propynes with TMPZnCl·LiCl followed by a Pd-catalyzed coupling with aryl halides provides arylated allenes in 52-92% yield. Subsequent metalation with TMPZnCl·LiCl and cross-coupling with a second different aryl halide provides regioselectively tetrasubstituted allenes in 42-70% yield. This sequence can be performed in a one-pot procedure. DFT calculations and NMR studies support the formation of allenylzinc and propargyllithium intermediates starting from 1-(trimethylsilyl)-3-phenyl-1-propyne.
- Quinio, Pauline,Franois, Cyril,Escribano Cuesta, Ana,Steib, Andreas K.,Achrainer, Florian,Zipse, Hendrik,Karaghiosoff, Konstantin,Knochel, Paul
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supporting information
p. 1010 - 1013
(2015/06/11)
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- Synthesis of Multinuclear Copper Complexes Bridged by Diquinolylamidinates and Their Application to Copper-Catalyzed Coupling of Terminal Alkynes and Aryl, Allyl, and Benzyl Halides
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A dinuclear copper complex containing N,N′-diquinolylformamidinate and a tetranuclear copper complex containing N,N′-diquinolylacetamidinate were synthesized. The structure of complexes was confirmed by X-ray analysis, showing that copper atoms were bridg
- Nakane, Takayuki,Tanioka, Yuta,Tsukada, Naofumi
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p. 1191 - 1196
(2015/04/27)
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- Platinum-catalyzed allylation of carbon electrophiles with alkenylsilanes
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In the presence of catalytic amounts of PtCl2 and AgSbF6, (Z)-alkenylsilanes react with various carbon electrophiles at the γ-position to give allylation products. A plausible mechanism for the Pt-catalyzed allylation involves alkene migration of alkenylsilanes to allylsilanes and subsequent allylation of carbon electrophiles.
- Kinoshita, Hidenori,Kizu, Ryosuke,Inoue, Gen,Fujimoto, Masayuki,Saito, Masanori,Ichikawa, Junji,Hosomi, Akira,Miura, Katsukiyo
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supporting information
p. 713 - 716
(2015/01/30)
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- Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors
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Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C-C bonds, one C-H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti-alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotropic shift, and stereoselective protonation of the penultimate allylic organometallic intermediate. Several examples are given to demonstrate the compatibility of this reaction with substrates bearing aromatic and aliphatic substituents, and an empirical model is presented to accompany the stereochemical observations.
- Jeso, Valer,Aquino, Claudio,Cheng, Xiayun,Mizoguchi, Haruki,Nakashige, Mika,Micalizio, Glenn C.
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supporting information
p. 8209 - 8212
(2014/06/24)
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- Removal of human ether-à-go-go related gene (hERG) K+ channel affinity through rigidity: A case of clofilium analogues
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Cardiotoxicity is a side effect that plagues modern drug design and is very often due to the off-target blockade of the human ether-à-go-go related gene (hERG) potassium channel. To better understand the structural determinants of this blockade, we design
- Louvel, Julien,Carvalho, Jo?o F.S.,Yu, Zhiyi,Soethoudt, Marjolein,Lenselink, Eelke B.,Klaasse, Elisabeth,Brussee, Johannes,Ijzerman, Adriaan P.
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supporting information
p. 9427 - 9440
(2014/01/06)
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- Solvent-induced selectivity switching: Intermolecular allylsilylation, arylsilylation, and silylation of alkynes over montmorillonite catalyst
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Proton-exchanged montmorillonite showed catalytic activity for intermolecular allylsilylation, arylsilylation, and terminal silylation of alkynes with allylsilanes. The reaction selectivity greatly depended on the solvent used. Reactions proceeded with va
- Motokura, Ken,Matsunaga, Shigekazu,Miyaji, Akimitsu,Yashima, Tatsuaki,Baba, Toshihide
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experimental part
p. 6687 - 6692
(2012/01/03)
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- Synthesis of substituted anthracenes, pentaphenes and trinaphthylenes via alkyne-cyclotrimerization reaction
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The [2+2+2] cycloaddition reaction of 1,6-diynes 3 with 4-aryl-2-butyn-1-ols 4 and the following oxidation of the resulting benzylic alcohols to the aldehydes 1 and then treatment with an acid catalyst provided annulated anthracenes 2 in good yields.
- Saino, Naoko,Kawaji, Tsuyoshi,Ito, Taichi,Matsushita, Yuko,Okamoto, Sentaro
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scheme or table
p. 1313 - 1316
(2010/04/29)
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- Diastereodivergent addition of allenylzincs to aryl glyoxylates
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A diastereodivergent addition of allenylzincs to aryl glyoxylates was observed depending on the method used for the preparation of the allenylzinc reagent. The allenylzincs were prepared from propargylic benzoates in the presence of a palladium catalyst o
- Hameury, Thomas,Guillemont, Jerome,Hijfte, Luc Van,Bellosta, Veronique,Cossy, Janine
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supporting information; experimental part
p. 2397 - 2400
(2009/10/10)
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- Preparation, structure, and reactivity of nonstabilized organoiron compounds. Implications for iron-catalyzed cross coupling reactions
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A series of unprecedented organoiron complexes of the formal oxidation states -2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)] [Li(OEt2)]2 (3) and [Ph4Fe][Li(Et 2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4) 4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)] 2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4) 2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe-Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C-C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(-2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively.
- Fuerstner, Alois,Martin, Ruben,Krause, Helga,Seidel, Guenter,Goddard, Richard,Lehmann, Christian W.
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p. 8773 - 8787
(2008/12/23)
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- Stereocontrol in ene-dimerisation and trimerisation of 1-trimethylsilyl-3- phenylcyclopropene
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1-Trimethylsilyl-3-phenylcyclopropene undergoes a highly stereocontrolled ene-reaction to give a dimer and further reaction leads to one or more trimers derived through two ene-reactions.
- Sheshenev, Andrey E.,Baird, Mark S.,Croft, Anna K.,Starikova, Zoya A.,Shashkov, Alexandre S.,Zhuze, Alexey L.,Bolesov, Ivan G.
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p. 2839 - 2843
(2007/10/03)
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- Cobalt-catalyzed benzyl-alkynyl coupling
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Benzylic halides coupled with 1-alkynylmagnesium halides in the presence of a catalytic amount of Co(acac)3 to provide 1-aryl-2-alkynes in moderate to good yield.
- Kuno, Akiko,Saino, Naoko,Kamachi, Taku,Okamoto, Sentaro
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p. 2591 - 2594
(2007/10/03)
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- Indium tribromide-catalyzed deacetoxylation of propargylic acetate with triethylsilane
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Indium(III) bromide catalyzed the deacetoxylation of propargylic acetates with Et3SiH to produce the corresponding internal alkynes containing a variety of functional groups in good yields.
- Sakai, Norio,Hirasawa, Maki,Konakahara, Takeo
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p. 6407 - 6409
(2007/10/03)
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- Palladium-catalyzed cross-coupling reaction of alkynylzincs with benzylic electrophiles
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The reaction of alkynylzinc bromides with benzyl bromides or chlorides in the presence of a catalytic amount of Pd(DPEphos)Cl2 in THF at 23°C cleanly produces the corresponding benzylated alkynes in 73-97% yields. With 10-3 mol % of Pd(DPEphos)Cl2, the maximum turnover number of 7.1 × 104 has been observed for the formation of PhCCCH2Ph.
- Qian, Mingxing,Negishi, Ei-Ichi
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p. 2927 - 2930
(2007/10/03)
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- Cross-coupling of alkyl halides with aryl Grignard reagents catalyzed by a low-valent iron complex
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A striking reversal of the usual reactivity pattern of aryl Grignard reagents is observed for reactions in the presence of catalytic amounts of the "bare" ferrate complex [Li(tmeda)]2[Fe(C2H 4)4] (1). Highly reduced iron-magnesium clusters may play a decisive role in the exceptionally facile and chemoselective cross-coupling reaction with alkyl halides (see scheme).
- Martin, Ruben,Fuerstner, Alois
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p. 3955 - 3957
(2007/10/03)
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- Tuning of regioselectivity in the coupling reaction involving allenic/propargylic palladium species
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Two different types of coupling patterns for the Pd(O)-catalyzed coupling reaction of allenic/propargylic zinc reagents with organic halides or propargylic carbonates (acetate) with the corresponding organometallic reagents were observed. After studying the controlling factors on the regioselectivity of this reaction, we demonstrated that the steric hindrance of both reactants and the types of organic halides determine the regioselectivity of this coupling reaction. By subtle choosing of the substrates, the regioselectivity can be tuned. On the basis of these results, new methodologies for the highly regio- and stereoselective synthesis of 6-substituted hex-5-yn-2-enoates and 4,6-dialkylhexa-2,4,5-trienoates have been developed. Some of the products synthesized by the carbonate protocol cannot be prepared by the lithiation protocol because the regioselectivity of lithiation of dialkyl-substituted internal alkynes is an intrinsic problem.
- Ma, Shengming,Zhang, Aibin
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p. 2287 - 2294
(2007/10/03)
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- Atom-efficient metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles
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The novel metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles is described. Triorganoindium compounds (R3In) containing alkyl, vinyl, aryl, and alkynyl groups are efficiently prepared from the correspond
- Perez,Sestelo,Sarandeses
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p. 4155 - 4160
(2007/10/03)
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- Synthesis and structure of cationic η3-allenyl/propargylpalladium complexes
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Treatment of η1-allenyl- or η1-propargylpalladium bis(triphenylphosphine) chloride with AgBF4 or NaBPh4 afforded cationic η3-allenyl/propargylpalladium complexes.The molecular structure and some properties of the η3/
- Ogoshi, Sensuke,Tsutsumi, Ken,Kurosawa, Hideo
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p. C19 - C21
(2007/10/02)
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- (Z)-α-(Trimethylsilyl) α,β-Unsaturated Esters. Their Stereoselective Conversion into α,β- and β,γ-Unsaturated Esters and β,γ-Unsaturated Ketene Acetals
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Deprotonation of methyl (Z)-α-(trimethylsilyl) α,β-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the interm
- Najafi, M. Ramin,Wang, Mei-Ling,Zweifel, George
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p. 2468 - 2476
(2007/10/02)
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- BIS(TRMETHYLSILYL)-1,3 ALCYNES-1 : PREPARATION A PARTIR DE SILANES PROPARGYLIQUES ET APPLICATION A LA SYNTHESE DE SILANES ALLENIQUES α-FONCTIONNELS
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1,3-bis(trimethylsilyl)-1-alkynes may be obtained from trimethylsilylpropargylsilanes by metallation with n-butyllithium following by reaction with trimethylsilylchloride ; these silanes easily react with acetals, in presence of titanium tetrachloride, to produce α-functional allenyltrimethylsilanes.
- Pornet, Jacques,Mesnard, Danielle,Miginiac, Leone
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p. 4083 - 4086
(2007/10/02)
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