- A utility for organoleads: Selective alkyl and aryl group transfer to tin
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Me4Pb and Ph4Pb readily transfer methyl or phenyl groups to an equivalent molar ratio of tin(iv) chlorides in the order SnCl4 > MeSnCl3 > Me2SnCl2 > Me3SnCl, often in a selective manner. Me3PbCl and Ph3PbCl specifically transfer a single methyl/phenyl group under the same reaction conditions to produce recovered yields in >75%. Specific transfer of 2 methyl groups from PbMe4 can be achieved at elevated temperatures and/or a 2:1 molar ratio Pb:Sn.
- Arias-Ugarte, Renzo N.,Pannell, Keith H.
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p. 1703 - 1708
(2018/02/09)
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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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- Preparation method and application of triphenyl methyltin
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The invention discloses a preparation method and application of triphenyl methyltin.Triphenyl methyltin is a compound shown in the following structural formula (I) shown in the description, wherein Me is methyl.The preparation method has the advantages that the yield is high, reaction time is short, and a solvent can be recycled.Triphenyl methyltin prepared through the method can be further used for preparing compounds or products containing phenyl methyl and other alkyl mixed tin.
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Paragraph 0027; 0028; 0029; 0030; 0031; 0032
(2016/12/12)
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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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- Synthesis, structural characterization and antimicrobial activity of mixed aryl-alkyl diorganotin(IV) compounds with quinoline-2-carboxylate (L -): {RR'SnLCl}n and RR'SnL2
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A series of unsymmetrical diorganotin derivatives of quinoline-2-carboxylic acid (LH), namely polymeric {MePhSnClL}n (1) and {EtPhSnClL} n (2), and mononuclear MePhSnL2 (3) and EtPhSnL 2 (4), was synthesized by the reaction of LH with the MePhSnCl 2, EtPhSnCl2, MePhSnO, and EtPhSnO precursors, respectively. The compounds were characterized by elemental analysis and infrared spectroscopy, as well as by 1 H, 13 C and 119Sn NMR. The molecular structures of representative compounds 2 and 4 were determined by single-crystal X-ray crystallography. This study showed that polymeric 2 adopts a distorted octahedral geometry as the carboxylate ligand N,O chelates an Sn atom and at the same time bridges a neighbouring Sn atom via the second O atom, with the remaining sites being occupied by the Cl and two C atoms; the O atoms are trans to each other. The result of the μ2-bridging mode of L- is the formation of a supramolecular helical chain. Compound 4 adopts a skew-trapezoidal bipyramidal geometry with the organo groups lying over the plane of the two N,O-chelating carboxylate ligands and being directed over the weaker Sn-N bonds. The in vitro antimicrobial activities of 1-4 against a Gram-positive bacteria strain (Bacillus subtilis), a Gram-negative bacteria strain (Escherichia coli) and against Candida albicans were studied and compared with the antimicrobial activities of Ph2SnL2 and Me2SnL2, and with the antimicrobial standards gentamicin, tetracycline, ampicillin and penicillin. All organotin compounds displayed remarkable antibacterial activities that were comparable to those of the standard drugs, in particular against B. subtilis, where the activity was correlated with the number of Cl substituents.
- Vafaee, Marzieh,Amini, Mostafa M.,Khavasi, Hamid Reza,Ng, Seik Weng,Tiekink, Edward R. T.
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p. 471 - 477
(2012/11/07)
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- Synthesis and reactivity of new κ2-[P,N]Pt(II) complexes of diisopropylphosphino-substituted 2-dimethylaminoindene
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Treatment of 1-PiPr2-2-NMe2-indene (la[H]) with either czs/trans-(SMe2)2PtCl2 or PtCl2 provided (κ22-P,N-2-NMe2-3-P iPr2-indene)PtCl2 (2) in 84% and 55% yield, respectively, while the reaction of 1a[H] with (η4-COD)PtClMe afforded (κ2-P,N-2-NMe2-3-PiPr 2-indene)PtClMe (3) in 91% yield. Whereas in the formation of 2 and 3 the ligand precursor 1a[H] undergoes a rearrangement to give a coordinated 2-NMe2-3-PiPr2-indene (1b[H]) ligand, 1a[H] reacted cleanly with 0.5 equiv of [(μ-SMe2)PtMe2] 2 to give (κ2-P,N-1a[H])PtMe2 (4a) in 97% yield. The isomerization of 4a to (κ2-P,N-1b[H])PtMe 2 (4b) in a THF/iPrOH mixture is rapid and allowed for the isolation of 4b in 99% yield. Heating of 4a in CH2Cl2 resulted in the quantitative formation of 3, while the thermolysis of 4a in toluene in the presence of SMe2 afforded 5, the apparent product of intramolecular C-H activation of an NMe group. The reactivity of 4a with a variety of other two-electron donors, as well as E-H-containing substrates (E = main group fragment), is reported. Although NMR spectroscopic evidence indicated the formation of an intermediate of the type (κ2-P,N-1[H]) Pt(SnPh3)(Me), as well as Ph6Sn2, in the reaction of 4a with 10 equiv of Ph3SnH, negligible conversion of Ph3SnH to Ph6Sn2 was obtained when employing 1 mol % 4a as a catalyst. Single-crystal X-ray diffraction data for 2 and 5 are reported.
- Wile, Bradley M.,McDonald, Robert,Ferguson, Michael J.,Stradiotto, Mark
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p. 1959 - 1965
(2008/10/09)
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- Strategies for the synthesis of bi- and triarylic materials starting from commercially available phenols
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A series of arylstannanes have been synthesized, through an SRN1 mechanism, in good to excellent yields (74%-99%) by the photostimulated reaction of trimethyl stannyl ion with substrates supporting different nucleofugal groups. The arylstannanes thus obtained were suitable intermediates for Stille cross-coupling reactions leading to asymmetric bi- and triaryl compounds in acceptable global yields. An attractive feature of this route is that simple commercially available benzenediols, chloro- and methoxy phenols might be useful starting substrates, leading the latter to higher global yields of products in fewer steps. The strategies proposed open a broad synthetic tool.
- Chopa, Alicia B.,Silbestri, Gustavo F.,Lockhart, María T.
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p. 3865 - 3877
(2007/10/03)
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- Synthesis of chiral organotin reagents: Synthesis of enantiomerically enriched bicyclo[2.2.1]hept-2-yl tin hydrides from camphor. X-Ray crystal structures of (dimethyl)[(1R,2S,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]tin chloride and methyl(phenyl)bis[(
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2-Iodo-1,7,7-trimethylbicyclo[2.2.1]hept-2-ene 27 was prepared in two steps from camphor 23. Halogen-metal exchange using butyllithium followed by addition of the appropriate tin halide gave the corresponding bicyclo[2.2.1]-hept-2-en-2-ylstannanes 26, 35-
- Helliwell, Madeleine,Thomas, Eric J.,Townsend, Linda A.
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p. 1286 - 1296
(2007/10/03)
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- Reaction of trimethylaluminium with main group hydroxides: A non-hydrolysis route to methylalumoxane
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Reaction of AlMe3 with [(tBu)2Ga(μ-OH)]3 or Ph3EOH (E = Sn, Pb) yields catalytically active MAO, [MeAlO]n, along with (tBu)2GaMe and Ph3EMe, respectively, in contrast, the reaction with Ph3EOH (E = C, Si, Ge) yields [Me2Al(μ-OEPh3)]2; the formation of MAO is proposed to occur via hydroxide exchange and the formation of unstable [Me2Al(μ-OH)]n; the propensity towards alkane elimination versus hydroxide exchange is controlled by the relative Bronsted acidity of the main group hydroxide.
- Obrey,Barron
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p. 2456 - 2458
(2007/10/03)
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- Alkyl-substituted allylic lithium compounds: Structure and dynamic behavior
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Several methyl-substituted allylic lithium compounds have been prepared by CH3Li cleavage of their corresponding bis(methyl)bis(allylic)stannanes. Low-temperature 13C and proton NMR studies of 1:1 complexes of these allylic lithium compounds with TMEDA establish their structures. NMR line shape changes with temperature provide barriers to rotation. Results are listed in order as follows (allyl substituents, compound number, barrier to rotation in kcal·mol-1, and bonds undergoing rotation): 1,1-dimethyl, 26, 18, 2-3; endo-1-methyl, 27, 19, 2-3; endo-1-exo-3-dimethyl, 28, 21, 1-2 and 2-3. These observations together with the allylic 13C NMR chemical shifts indicate that in the case of unsymmetrical alkyl substitution at the termini the allyl C-C bond to the more substituted terminus is of higher bond order than that to the less substituted terminus. Unsymmetrical substitution is proposed to reduce the degree of delocalization compared to the symmetrically substituted allylic lithium compounds. A mechanism is proposed for the rotation process which is consistent with the Eyring activation parameters.
- Fraenkel,Qiu
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p. 12806 - 12812
(2007/10/03)
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- Reactions of organolanthanide compounds RLnI (Ln = Yb, Eu, Sm) with organic derivatives of silicon, tin, lead, and antimony
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Reactions of compounds RLnI (R = Alk, Ar; Ln = Yb, Eu, Sm) with hexaalkyl(aryl)-distannanes, trimethylsilyltriphenyltin, and lead and antimony acetates were studied. The reactions with Sn-Sn and Si-Sn organic derivatives result in cleavage of Sn-Sn amd Sn-Si bonds with formation of tetrasubstituted stannanes and reactive organometallic derivatives with an Sn-Ln or Si-Ln bond. The reactions of RYbI with lead and antimony acetates and with tetraethoxysilane cause cleavage of the Pb-O, Sb-O, or Si-O bond with formation of tetrasubstituted derivatives of lead and silicon or trisubstituted antimony derivatives.
- Rybakova,Syutkina,Petrov
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p. 244 - 246
(2007/10/03)
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- Transmetalation of tetraalkynyltin compounds with Grignard reagents: Access to mono- and dialkyltin products
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Monoalkyltrialkynyl- and dialkyldialkynyltin compounds can be selectively synthesized by transmetalation of tetraalkynyltin compounds with Grignard reagents; an example is given in Equation (1). This reaction provides a route to mono- and dialkyltin compounds that avoids the use of strongly electrophilic reagents. The labile tin-alkynyl bonds allow the transmetalation products to be converted into alkyltin oxides, chlorides, and alkoxides.
- Jaumier, Pascale,Jousseaume, Bernard,Lahcini, Mohammed
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p. 402 - 404
(2007/10/03)
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- Reactions of Organoytterbium Compounds RYbI (R = Me, Et, Ph) with Organotin Oxides and Acetates
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Reactions of RYbI (R = Me, Et, Ph) with organotin oxides and acetates) involve cleavage of the Sn-O bonds to form tetrasubstituted stannanes mostly as single or main reaction products (yields 65-96 percent). A similar results was obtained in reaction of PhYbI with diphenyltin sulfide (yield 93 percent). However, reactions of RYbI (R = Me, Et, Ph) with Bu2SnO, followed by hydrolysis of the reaction mixtures lead to hydroxystannanoxanes Bu2RSnOH in 66-75 percent yields.
- Rybakova, L. F.,Syutkina, O. P.,Novgorodova, M. N.,Petrov, E. S.
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- Synthesis of chiral organotin reagents: Synthesis of bicyclo[2.2.1]heptan-2-yl(diphenyl)tin hydrides with cis-disposed, oxygen-containing substituents
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Alkylation of the methyl 3-triphenylstannylbicyclo[2.2.1]hept-5-ene-2-carboxylate 3 using lithium diethylamide and either methyl iodide or benzyl bromide at -78°C is stereoselective in favour of the endo-alkylated products 10 and 11. Methylation of the saturated ester 12 is also endo-selective in favour of 13. If the unsaturated ester 3 is deprotonated at 0°C rather than at -78°C, the rearranged stannane 17 is obtained as a side-product. The endo-triphenylstannylbicyclo[2.2.1]heptane-2-carboxylate 22 has been prepared from the ester 12 by phenylselenylation, oxidative elimination and reduction using diimide. The triphenylstannanes 13, 17 and 20 have been converted into the alkyl(diphenyl)tin hydrides 27, 28 and 29 and the methoxyalkyltin hydride 36 has also been prepared and characterized. These tin hydrides accelerate the reduction of aryl methyl ketones to 1-arylethanols by phenylsilane, but the reduction product is racemic. Syntheses of the aminobicycloalkyl(triphenyl)stannanes 44, 45 and 48 are described.
- Pratt, Robert M.,Thomas, Eric J.
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p. 727 - 736
(2007/10/03)
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- Cleavage of Sn-Sn Bonds in Hexaalkyl(aryl)stannanes under the Action of Yb(II) Derivatives
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Ytterbium(II) derivatives MeYbI, PhYbI, and YbI2 cleave the Sn-Sn bond in distannanes R′3-SnR′3 (R′ = n-Bu, Ph) to give heterobimetallic derivatives R′3SnYbI, which were identified by products of their hydrolysis, exchange with R″3EHlg (R″ = Ph, Me; E = Ge, Si, Sn) and cross coupling with MeI in the presence of NiCl2(Ph3P)2.
- Syutkina,Rybakova,Novgorodova,Petrov
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- Synthesis of asymmetrical aryl-tin compounds by cleavage of alkyl-tin bonds with sodium metal in liquid ammonia followed by SRN1 reactions with chloroarenes
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One methyl-tin bond was selectively cleaved from aryltrimethyltin compounds by sodium metal in liquid ammonia. The triorganylstannyl anions thus obtained are arylated by chloroarenes by means of photostimulated SRN1 reactions. Such reactions ca
- Yammal, Carlos C.,Podesta, Julio C.,Rossi, Roberto A.
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- Nucleophilic Addition of Triorganotin Anions to Carbon Disulfide, IX. - Synthesis and Complexation of Novel Triphenylstannane Dithioesters
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The known alkyl esters Ph3SnC(S)SR (1: R = Me, 2: R = CH2Ph) and the novel stannyl(methyl) esters (3: R = SnPh3, 4: R = CH2SnPh3) were obtained by the reaction of the dioxane adduct Ph3SnCS2Li*2C4H8O2 with appropriate organo(element) halides.As the first derivative of a homologous stannylalkanedithiocarboxylic acid, the 3-(triphenylstannyl)propane dithioester Ph3SnC(S)SMe (5) was synthesized by Grignard reaction of (3-chloropropyl)triphenylstannane with activated magnesium (addition of anthracene, ultrasound).The new η1-coordinated pentacarbonylchromium and -tungsten complexes LM(CO)5 (1a: L = 1, M = Cr; 2a: L = 2, M = Cr; 2b: L = 2, M = W; 3b: L = 3, M = W; 5b: L = 5, M = W) were prepared by modification of previously reported methods.
- Kunze, Udo,Tischer, Reinhard
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p. 1099 - 1104
(2007/10/02)
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- Reactions of organotin hydrides with lithium diisopropylamide and organolithiums. Reactivities of the intermediates and of the lithium hydride produced
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Equimolar lithium diisopropylamide (LDA) and trimethyltin hydride (TMTH) react in tetrahydrofuran (THF) to form diisopropylamine and (trimethylstannyl)lithium, but in diethyl ether or hexanes 2 mol of TMTH is required for complete reaction and the products are diisopropylamine, hexamethylditin, and lithium hydride. When organic halides are present in this reacting system, reduction to alkane or substitution to form the trimethylalkyltin may occur depending on the nature of the halide. These and other observations suggest that (trimethylstannyl)lithium is formed as an intermediate yielding the tetraalkyltin. Studies on the products and stoichiometries of the reductions of alkyl bromides in ether and hexanes suggest that three reducing agents may be involved: TMTH, [Me3Sn(H)N-i-Pr2]-, and [Me3SnSn(H)Me3]-. The latter predominates in ether, and either or both of the others predominate in hexanes. Formation of methylcyclopentane from 1-bromo-5-hexene suggests involvement of a free radical mechanism. When methyllithium is used instead of LDA in the reaction with TMTH, the products are tetramethyltin and lithium hydride. This reaction can also be diverted to reduction by the presence of primary bromides. Aryl bromides react in both systems, but the yields of either substitution or reduction products are low. The lithium hydride formed in these reactions is extremely reactive as a base as shown by a brief study of its reaction with weak carbon acids and amines and as a nucleophile by its reaction with hexamethylditin to form (trimethylstannyl)lithium in THF.
- Reimann, Werner,Kuivila, Henry G.,Farah, Dan,Apoussidis, Theodorus
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p. 557 - 565
(2008/10/08)
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- Coupurs par transfert d'electrons de la liaison Sn-CH2 dans les composes R3SnCH2X
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In the presence of nucleophiles , the Sn-CH2 bond in organotin iodides R3SnCH2I with R=Me, Et and Ph is cleaved by an ionic mechanism or by an electron-transfer involving R3SnCh2., R3SnCH2CN(1). and R3Sn. radicals which can be induced electrochemically.Dimerisation, reoxydation of reduction of the R3Sn. radical occur depending on the potential, the solvent and the substituent.A complete description of the mechanism led us to study the electrochemical behaviour of R3SnCH2I iodides and resulted in a simple preparation of bis mercury compounds.
- Devaud, Marguerite,Lecat, Jean-Luc
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p. 1187 - 1190
(2007/10/02)
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- New Reagents, XX. (Triphenylstannyl)methyllithium and Analogous Trialkylstannyl Compounds, Synthesis and Reactions
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(Triphenylstannyl)methyllithium (1a) and analogous trialkylstannyl compounds (1b, c) were synthesized by halogen-lithium exchange reactions from 3a - c.As shown by high yields, stannyl groups are capable of stabilizing a carbanionic centre. 1a reacts with aldehydes and ketones to give β-hydroxystannanes 5 which tend to form olefins.
- Kauffmann, Thomas,Kriegesmann, Reinhard,Altepeter, Bruno,Steinseifer, Fritz
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p. 1810 - 1817
(2007/10/02)
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- ORGANOMETALLIC COMPOUNDS. LXXII. REACTIONS OF RACEMIC TETRAORGANOTIN COMPOUNDS WITH BUTYLLITHIUM AND WITH LITHIUM ALUMINUM HYDRIDE
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Racemic methylneophylphenyltrityltin (I) reacts with an excess of butyllithium to give dibutylmethylneophyltin (II) in high yield, whereas bifluorenyl-9-ylmethylneophylphenyltin is converted with an excess butyllithium into butylmethylneophylphenyltin (II
- Gielen, Marcel,Tondeur, Yves
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p. 371 - 376
(2007/10/02)
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