- Extremely Facile and Stereoselective Preparation of Allylstannanes with Use of Ultrasound
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Various allylstannanes are conveniently prepared in quantitative yields by means of ultrasound-promoted Barbier-type reaction from chlorotributylstannane and allyl halides in a stereoselective manner.
- Naruta, Yoshinori,Nishigaichi, Yutaka,Maruyama, Kazuhiro
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Read Online
- Photoredox-Catalyzed C-F Bond Allylation of Perfluoroalkylarenes at the Benzylic Position
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Site-selective and direct C-F bond transformation of perfluoroalkylarenes was achieved with allylic stannanes via an iridium photoredox catalyst system. The present defluoroallylation proceeds exclusively at the benzylic position through perfluoroalkyl radicals generated by a single-electron transfer from an excited photoredox catalyst to perfluoroalkylarenes. A variety of perfluoroalkyl groups are applicable: linear perfluoroalkyl-substituted arenes such as Ar-nC4F9and Ar-nC6F13and heptafluoroisopropylarenes (Ar-CF(CF3)2) underwent site-selective defluoroallylation. DFT calculation studies revealed that thein situgenerated Bu3SnF traps F-to prevent a retroreaction from the unstable perfluoroalkyl radical intermediate, and the radical intermediate favorably reacts with allylic stannanes. The synthesis of a bis(trifluoromethyl)methylene unit containing compound, which is an analog that is useful as a pharmaceutical agent for the prophylaxis or treatment of diabetes and inflammatory diseases, demonstrated the utility of this reaction.
- Sugihara, Naoki,Suzuki, Kensuke,Nishimoto, Yoshihiro,Yasuda, Makoto
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supporting information
p. 9308 - 9313
(2021/06/28)
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- Novel compound 6,6-dimethyl tetrahydropyran-2-methanol and preparing method thereof
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The invention discloses a novel compound that is 6,6-dimethyl tetrahydropyran-2-methanol and a preparing method thereof. The method includes preparing benzyloxy ethanol by utilizing a sodium alkoxideprocess; then oxidizing the benzyloxy ethanol into benzyloxy acetaldehyde by utilizing a swern oxidation process; reacting the benzyloxy acetaldehyde and allyltributyltin prepared by utilizing a Grignard reaction to obtain 1-(benzyloxy)-4-penten-2-ol; subjecting the 1-(benzyloxy)-4-penten-2-ol and acetone to cyclization under catalysis of trimethylchlorosilane and potassium iodide to obtain 4-iodo-6,6-dimethyl tetrahydropyran-2-methanol; and subjecting the 4-iodo-6,6-dimethyl tetrahydropyran-2-methanol to hydrogenation to remove iodine to obtain the target product that is the 6,6-dimethyl tetrahydropyran-2-methanol. According to the method, reactions are relatively mild, products can be easily treated and purified, and the method is suitable for batch preparation, and therefore the methodhas important application value.
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Paragraph 0014; 0019-0020; 0026; 0032
(2018/04/03)
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- Forging C-C Bonds with Hindered Nucleophiles and Carbonyl Electrophiles: Reactivity and Selectivity of Allylic Tin Reagents/n-BuLi
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Under activation with n-BuLi, trialkylstannanes containing crotyl-, geranyl-, and phenyldienylmethyl appendages were reacted with efficiency and selectivity to various ketone and enone electrophiles with low reactivity. The straightforward process gives access to tertiary alcohols that are vicinal to quaternary carbons. With α,α′-dimethoxy-γ-pyrone, on the other hand, the grafting of a dienyl side chain was effected to prepare dienyl α′-methoxy-γ-pyrone in a stereo- and regioselective and convergent manner. Furthermore, the advantages of this route were highlighted for the preparation of organolithium species at low temperature with the formation of a minimum amount of salts. Synthetic manipulations were demonstrated to illustrate the potential of the chemistry for constructing acyclic and cyclic terpene scaffolds.
- Cormier, Morgan,Ahmad, Maha,Maddaluno, Jacques,De Paolis, Micha?l
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p. 4920 - 4927
(2018/02/07)
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- METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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- Practical Stannylation of Allyl Acetates Catalyzed by Nickel with Bu3SnOMe
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A practical and scalable nickel-catalyzed allylic stannylation of allyl acetates with Bu3SnOMe is described. A variety of acyclic and cyclic allyl acetates, even with base-sensitive moieties, undergoes the stannylation by using NiBr2/4,4′-di-tert-butylbipyridine (dtbpy)/Mn catalyst system to afford highly functionalized allyl stannanes with excellent regioselectivity and yields. Furthermore, the scope of protocol is also extended by the reaction of propargyl acetates, giving rise to propargyl or allenyl stannanes. Additionally, a unique diastereoselectivity using the nickel catalyst different from the palladium was demonstrated for the stannylation of cyclic allyl acetates. In the reaction, inexpensive and stable nickel complexes, abundant reductant (Mn), and atom-economical stannyl source were used.
- Komeyama, Kimihiro,Itai, Yuuhei,Takaki, Ken
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supporting information
p. 9130 - 9134
(2016/07/14)
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- Stannyl-Lithium: A Facile and Efficient Synthesis Facilitating Further Applications
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We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.
- Wang, Dong-Yu,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 10488 - 10491
(2015/09/28)
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- Catalytic enantioselective amide allylation of isatins and its application in the synthesis of 2-oxindole derivatives spiro-fused to the α-methylene-γ-butyrolactone functionality
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This article is a full account of the work exploring the potential utility of catalytic enantioselective amide allylation of various isatins using indium-based chiral catalysts. A survey of various isatin substrates and NH-containing stannylated reagents revealed that the reaction has a remarkably wide scope to result in extremely high yields and enantioselectivities (up to >99 %, 99 % ee) of variously substituted homoallylic alcohols. Several mechanistic investigations demonstrated that the substrate-reagent hydrogen-bond interaction plays a critical role in the formation of the key transition states to result in enhanced catalytic reaction. The success of this approach allowed convenient access to chiral 2-oxindoles spiro-fused to the α-methylene- γ-butyrolactone functionality and their halogenated derivatives in almost enantiopure forms, thus highlighting the general utility of this synthetic method to deliver a large variety of antineoplastic drug candidates and pharmaceutically meaningful compounds.
- Takahashi, Masaki,Sengoku, Tetsuya,Yoda, Hidemi,Murata, Yusuke,Yagishita, Fumitoshi,Sakamoto, Masami
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supporting information
p. 11091 - 11100,10
(2014/09/29)
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- Selective green coupling of alkynyltins and allylic halides to trienynes via a tandem double stille reaction
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The palladium-catalyzed reaction of alkynyltin compounds with allylic chlorides leads to a 2:2 coupling to give trienynes by regio- and stereoselective formation of three new C-C bonds. The reaction can be applied to different alkynyl and allylic fragments, providing a wide range of trienynes with different substitution patterns in very good yields. They can be prepared in a green way using recyclable polymeric tin alkynyls. Copyright
- Meana, Isabel,Albeniz, Ana C.,Espinet, Pablo
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supporting information; experimental part
p. 2887 - 2891
(2011/02/21)
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- Hybrid Host Materials For Electrophosphorescent Devices
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Compounds (including polymers) for use in hybrid host materials which can be used in electroluminescent devices. The compounds comprise at least one electron-transporting moiety and at least one hole-transporting moiety which are joined by a flexible linker. Hybrid host materials comprising the compounds exhibit stability against phase separation, elevated glass transition temperature, morphological stability against crystallization, and isolation of the electron transporting moiety and hole transporting moiety π-systems.
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- A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction
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Mono-, di-, tri- and tetra-functional organotin compounds were easily prepared in a sonicated Barbier reaction using ultrasound technology via coupling reaction of organo halides with tin halides (Bu3SnCl, Bu2SnCl2, BuSnCl
- Lamandé-Langle, Sandrine,Abarbri, Mohamed,Thibonnet, Jér?me,Duchêne, Alain
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p. 2368 - 2374
(2009/09/30)
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- Catalytic Homologation of Vinyltributylstannane to Allyltributylstannane by Mo(IV) Complexes in the Presence of Ethylene
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We have found that CH2=CHSnBu3 is converted into CH2=CHCH2SnBu3 catalytically in the presence of Mo(IV) olefin complexes such as Mo(NAr)(CH2CH2)[biphen] (where Ar = 2,6-i-Pr2C6H3 and [biphen]2- = 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2,2′-diolate). The proposed mechanism involves formation of a metalacyclopentane (MC4) complex from ethylene and CH2=CHSnBu3, contraction of this MC4 complex to a metalacyclobutane (MC3) complex, and finally metathesis of the MC3 complex to give CH2=CHCH2SnBu3 and Mo(NAr)(CH2)[biphen]. These new findings suggest (inter alia) that contraction of an MC4 ring to an MC3 ring may be a much more common mode of decomposition of metalacyclopentane rings in d0 complexes than previously believed. Copyright
- Schrock, Richard R.,Duval-Lungulescu,Tsang, W. C. Peter,Hoveyda, Amir H.
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p. 1948 - 1949
(2007/10/03)
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- Palladium complex-catalyzed germylation of allylic halides using (germyl)stannanes
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(Triethylgermyl)tributylstannane reacts metal-selectively with allylic halides at room temperature (r.t.) in the presence of tris(dibenzylideneacetone)dipalladium, Pd2(dba)3CHCl3, to provide an alternative route to allylge
- Nakano, Taichi,Ono, Kazuyoshi,Senda, Yoshiya,Migita, Toshihiko
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p. 313 - 317
(2007/10/03)
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- The effect of CO on the reaction of (tributyltin)lithium with alkyl and aryl bromides
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The reaction of (tributyltin)lithium with alkyl and aryl bromides in THF was studied in the presence of CO and of p-dinitrobenzene under several reaction conditions. The observed results indicate that electron transfer is involved in the substitution reac
- Nudelman, N. Sbarbati,Carro, Cecilia
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- 6-substituted mycophenolic acid and derivatives
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The disclosed 6-substituted derivatives of mycophenolic acid are therapeutic agents advantageous in the treatment of disease states indicated for mycophenolic acid and/or mycophenolate mofetil.
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- Wurtz-type reductive coupling reaction of allyl bromides and haloorganotins in cosolvent/H2O(NH4Cl)/Zn media as a route to allylstannanes and hexaaryldistannanes
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Twenty-one allylstannanes have been prepared via a simple Wurtz-type coupling reaction of allyl bromides and R3SnX compounds (R = Me, Et, Pr, Bu, Ph; X = Cl, I, OH), Bu2SnCl2, and (Bu2SnCl)2O in cosolvent/H2O (NH4Cl saturated) media under the mediation of zinc powder. Also R3SnSnR3 compounds (R = Ph, p- and m-Tol) have been prepared via coupling of triaryltin chlorides. The stereochemical course of the reaction between R3SnCl and (C4H7)Br (C4H7 = α-methylallyl, trans- and cis-crotyl) has been extensively studied. Two distinct reactions are involved in the overall process: (i) the coupling reaction, which gives rise stereoselectively to the sole R3SnCH(CH3)CH=CH2 (α-isomer), and (ii) the subsequent isomerization of the α-isomer furnishing mixtures of (α, trans, cis)-isomers. The occurrence of reaction ii depends upon the nature either of the R group or the employed cosolvent. In cyclohexane, the α-isomer is exclusively obtained with R = Bu, while with R = Me, Et, and Pr it is found as a major component in the ternary isomeric mixture. In tetrahydrofuran, 2-propanol, acetonitrile, and pyridine, the isomerization occurs to an extent which depends on the polarity and the coordinating ability of the cosolvent itself. The observed stereoselection has been hypothesized to occur through one-electron transfer from the zinc metal to the (C4H7)Br to form stereoselectively an adsorbed CH2=CHCH(CH3)Br?-Zn?+ radical ion which is trapped by the R3SnCl reactant to form the α-isomer. Similarly, ditin compounds are thought to be formed by interaction of R3SnCl?-Zn?+ radical ions with R3SnCl molecules.
- Von Gyldenfeldt, Friederike,Marton, Daniele,Tagliavini, Giuseppe
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p. 906 - 913
(2008/10/08)
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- New simple route to allylstannanes by zinc-mediated coupling of allyl bromides with Bu3SnCl or Bu2SnCl2 in an H2O (NH4Cl)/THF medium
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A new zinc-mediated coupling reaction of allyl and allyl-like bromides with Bu3SnCl (1) or Bu2SnCl2 (2), performed in H2O (NH4Cl)/THF medium, represents an easy route to the following organostannanes: Bu3SnCH2CH=CH2 (3) and Bu2Sn(CH2CH=CH2)2 (4), Bu3Sn(C4H7) (5) and Bu2Sn(C4H7)2 (6) (where C4H7 stands for trans-crotyl, cis-crotyl, or α-methylallyl), and Bu3SnCH=C=CH2 (7). This striking one-pot procedure successfully improves the already general routes where Grignard or other conventional organometallic reagents are used.
- Carofiglio, Tommaso,Marton, Daniele,Tagliavini, Giuseppe
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p. 2961 - 2963
(2008/10/08)
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- The effect of ligands, solvent and temperature on the reactions of allyltin(IV) compounds with singlet oxygen
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The reaction of singlet oxygen with a variety of allyltin compounds CH2=CHCH2SnR3 (R3 = Me3, Bu3, allyl3, (cyclo-C6H11)3, Ph3, allylBu2, Bu2Cl, Bu2OAc, allylCl2, allylCl2bipy) has been investigated, and the allylperoxytin compounds, 3-stannylallyl hydroperoxides, and 4-stannyl-1,2-dioxolanes which result from M-ene, H-ene and cycloaddition processes, respectively, have been identified by NMR spectroscopy.As the tin centre becomes more electropositive, as indicated by the 13C NMR shift of the allylic CH2 group, the proportion of the M-ene reaction increases, and when δCH2 is above about 23.7, the allylperoxytin compound is the only product.An exception to this rule is tetraallyltin, δCH2 16.13, which similarly shows only the M-ene reaction.This is tentatively ascribed to the special effect of hyperconjugation between the C-Sn ?-bond and the remaining ?-systems.A polar solvent favours the M-ene reaction.The cycloaddition reaction is favoured by low temperature, and at -70 deg C in a non-polar solvent it may become the major route.Diallylmercury and allylmercury chloride react with singlet oxygen to show only the M-ene reaction, but also undergo extensive photosensitized decomposition.With 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), allylmercury chloride shows only the M-ene reaction.
- Dang, H.-S.,Davies, A. G.
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p. 287 - 298
(2007/10/02)
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- Synthesis of Allylstannanes and Vinylstannanes by the Stannyl-cupration of Allenes
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Stannyl-cupration of allenes followed by electrophilic attack gives allyl- and vinyl-stannanes with a variety of substitution patterns.The regiochemistry of the reaction depends upon the temperature at which the intermediate cuprate is quenched with an electrophile.With allene itself, the allylstannane-vinylcuprate 1-(tributylstannylmethyl)vinylcuprate 5, is the product of kinetically controlled addition, but the vinylstannane-allylcuprate 2-(tributylstannyl)allylcuprate 6, is thermodynamically lower in energy.The equilibrium between these isomers begins to take place between -100 and -78 deg C.
- Barbero, Asuncion,Cuadrado, Purificacion,Fleming, Ian,Gonzalez, Ana M.,Pulido, Francisco J.
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p. 327 - 332
(2007/10/02)
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- Metal-ion-catalyzed Fluxionality of Pentadienyltins and Its Application to the Diels-Alder Reaction
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(Z)-Pentadienyltins (PDT) as well as (Z)-allylic tins are isomerized to (E)-isomers most effectively by alkaline earth metal ions.The resulted (E)-PDT is trapped by 1,4-naphthoquinone to give the Diels-Alder adducts efficiently behaving as a reactive equivalent of 1,3-pentadiene.
- Nishigaichi, Yutaka,Takuwa, Akio,Iihama, Kenji,Yoshida, Naofumi
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p. 693 - 696
(2007/10/02)
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- The Synthesis of Allylstannanes and Vinylstannanes by the Stannyl-cupration of Allenes
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Stannyl-cupration of allenes followed by electrophilic attack gives allyl- and vinylstannanes with a variety of substitution patterns; the regiochemistry of the reaction depends upon the temperature and the nature of the stannyl-cuprate reagent.
- Barbero, Asuncion,Cuadrado, Purificacion,Fleming, Ian,Gonzalez, Ana M.,Pulido, Francisco J.
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p. 1030 - 1031
(2007/10/02)
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- Electron-transfer processes. 43. Attack of alkyl radicals upon 1-alkenyl and 1-alkynyl derivatives of tin and mercury
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Alkyl radicals, obtained by reaction of Bu3Sn? or ClHg? with alkylmercury halides, will undergo regioselective and in some cases stereospecific substitution by a free radical chain addition-elimination mechanism with 1-alkenylstannanes or -mercurials. The chain reaction is also observed for 1-alkynyl derivatives and in the photostimulated demercuration of mixed alkyl and 1-alkenyl- or 1-alkynylmercurials. Chain propagation with alkyl radical formation is also observed to occur in the reactions of β-eliminated ClHg? with Grignard reagents in PhH-THF solution. In competitive reactions of Bu3Sn? or ClHg? with pairs of alkylmercury chlorides, it is observed that a tert-butylmercurial is >1000 times more reactive than a n-butylmercurial, suggesting a concerted dissociate electron-transfer process not involving the intermediacy of RHg? species.
- Russell, Glen A.,Ngoviwatchai, Preecha,Tashtoush, Hasan I.
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p. 696 - 702
(2008/10/08)
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- Process for carbon-carbon bond formation at the C-4 position of 3-acylaminoazetidinones and products and starting materials therefor
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The invention encompasses a process for stereoselective carbon-carbon bond formation at C-4 position of a 3-(acylamino)azetidinone. The process is carried out under free radical conditions using a (2-substituted or unsubstituted allyl)tin reagent. Also encompassed by the invention are certain 4-(substituted selenyl)azetidinone starting materials and the corresponding 4-(2'-substituted or unsubstituted allyl)-azetidinone products.
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- Synthesis of Homoallylic Alcohols from Allylic Phosphates and Aldehydes with Organoaluminum Reagent Containing Al-Sn Linkage
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Treatment of allylic phosphates with the reagent prepared from n-Bu3SnLi and Et2AlCl or from SnF2 and Et2AlCl affords allyltin compounds which react with aldehydes to produce homoallylic alcohols in good yields.The formation of allyltin compounds requires the catalytic amount of Pd(PPh3)4 and proceeds with inversion of the stereochemistry predominantly.
- Matsubara, Seijiro,Wakamatsu, Kuni,Morizawa, Yoshitomi,Tsuboniwa, Noriyuki,Oshima, Koichiro,Nozaki, Hitosi
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p. 1196 - 1199
(2007/10/02)
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α-Ethoxybutenyl)tributyltins are obtained from the reaction of appropriate allylic Grignard reagents with (α-chloro-α-ethoxymethyl)tributyltin, which is easily obtained from diethoxymethyltributyltin. Upon transmetallation (BuLi/THF/- 70°C), these new rea
- Quintard, Jean-Paul,Elissondo, Bernard,Hattich, Thomas,Pereyre, Michel
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p. 149 - 162
(2007/10/02)
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- SYNTHESIS OF ORGANOTRIALKYLSTANNANES. THE REACTION BETWEEN ORGANIC HALIDES AND HEXAALKYLDISTANNANES IN THE PRESENCE OF PALLADIUM COMPLEXES
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The aryl halides YC6H4X (X=Br or I) have been shown to react with the distannanes (R3Sn)2 (R=n-Bu or Me) in toluene in the presence of or to give the compounds YC6H4SnR3 for (a) R=n-Bu, Y=H, p-OMe, o-Me, p-Me, m-Cl, p-Cl, m-CN, p-COCH3 and m-NO2, and (b) R=Me, Y=H, p-OMe, p-Me, p-CN, p-COCH3, m-NO2 and p-NO2.Benzyl halides YC6H4CH2X (X=Cl or Br) similarly give YC6H4CH2SnR3 for (a) R=n-Bu, Y=H, m-OMe, p-OMe, m-Cl, m-CN, and m-NO2, and (b) R=Me, Y=m-Cl, m-CN, p-CN and m-NO2.These reactions are of special value as preparative procedures in cases in which Grignard or organolithium reagents cannot be used.Allyl chloride and bromide were likewise shown to react with (n-Bu3Sn)2 to give CH2=CHCH2SnBu3, but n-BuCl and n-BuBr gave only a trace of n-Bu4Sn.The mixed dimetallo species n-Bu3SnSiMe3 was shown to react with aryl bromides YC6H4Br (X=H, p-OMe, p-Me, or p-Cl) to give the arylsilicon compounds YC6H4SiMe3, with no aryltin products.
- Azizian, Hormoz,Eaborn, Colin,Pidcock, Alan
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- ALLYLBORONSAEUREESTER AUS ALLYLZINN-VERBINDUNGEN
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Allylboronic esters are obtained in good yield by the reaction of allyltrialkyltin derivatives with 2-chloro-1,3,2-dioxaborolane.In the case of tributylprenyltin, 4(S)-7-triethylstannyl-p-menthene and tri-n-butylcrotyltin the boron/tin-exchange leads to a
- Hoffmann, Reinhard W.,Feussner, Giso,Zeiss, Hans-Joachim,Schulz, Sabine
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p. 321 - 329
(2007/10/02)
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- REACTIVITE DU TETRAALLYLETAIN ET D'ALLYLTRIALKYLETAINS VIS A VIS D'ALDEHYDES, DE CETONES ET D'EPOXYDES
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Tetraallyltin reacts readily with non activated ketones and exothermically with aldehydes contrary to other allylic organotins such as allyltributyltin.Homoallylic alcohols are obtained after acidolysis of the adducts.Upon extended heating, allylic organotins and epoxides form products which correspond to addition products of isomeric carbonyl compounds.However, starting from cis- and trans-1-phenyl-1,2-epoxypropanes, direct regiospecific but non-stereospecific ring opening is observed with poor yields.
- Daude, Gerard,Pereyre, Michel
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