This website collects cookies to deliver a better user experience. Reduction of alkyl halide with metallic lithium can afford simple alkyl and aryl organolithium reagents. Acetonitrile was the best solvent for formation of trans-2,3-di-t-butylthiirane 1,1-dioxide from t-butyldiazomethane and sulfur dioxide. Brand. The additive character of the effect on kinetic and activation parameters of the exchange reaction was established. /DecodeParms <> Four Li atoms and four ipso carbon centers occupy alternating vertices of a distorted cube. [17] Phenyllithium - an overview | ScienceDirect Topics /Matrix [0.4497 0.2446 0.02518 0.3163 0.672 0.1412 0.1845 0.08334 0.9227] Treatment of phosphorus ylides having no -hydrogens with sulfenes yields episulfones or their decomposition products 67T2137. In the presence of LiBr, a byproduct of directly reacting lithium with a phenyl halide, the [(PhLiEt2O)4] complex instead becomes [(PhLiEt2O)3LiBr). With unsymmetrical alkynes (178), all four possible isomers (179)(182) are produced. A further increase in the steric bulk of either the organic substituents of the diorganozinc or of the nucleophile gave equilibria from which no organozincates could be isolated. They are strong electron-withdrawing groups that increase the acidity of alpha-protons on the aromatic ring. Nucleophilic attack at As-alkyl and -aryl arsoles by lithium reagents gives anionic species that can be trapped by electrophiles to give new As-derivatives 72AG(E)439, 83JOM(249)335. [29] ScienceDirect is a registered trademark of Elsevier B.V. ScienceDirect is a registered trademark of Elsevier B.V. Synthesis: Carbon with Three or Four Attached Heteroatoms, Comprehensive Organic Functional Group Transformations, Five-membered Rings with One Heteroatom and Fused Carbocyclic Derivatives, Fused Five- and Six-membered Rings with Ring Junction Heteroatoms, 83CPB2540, 84CHEC-I(5)607, 84CHEC-I(5)305, 86JHC981, Organolithiums: Selectivity for Synthesis, Gilman noted in 1949 that butyllithium slowly displaces, Thiophilic addition of carbanions derived from aryl Grignard reagents or, Synthesis: Carbon with Two Heteroatoms, Each Attached by a Single Bond, Comprehensive Organometallic Chemistry III, The reaction of diorganozincs bearing bulky trimethylsilyl-substituted methyl groups and methyl- or, Synthesis: Carbon with No Attached Heteroatoms, When quaternary ammonium halides are treated with a strong base, e.g., potassium amide or, 71JA7118, 72JA8608, 74CC819, 74CC820, 91JA4712. The larger the organic group on zinc, the more thermally stable and less reactive the organozincates. The reagents 1 and 2 reacted readily with aroyl and acyl halides, imidoyl chlorides, -halo ketones, -halo esters, -halo lactones, -halo carboxylic acids, allyl halides, alkyl Hope, H.; Power, P. P. (1983). << Substitution reactions of thallous thiophenoxide and thallous [7], Relying solely on the structural information of organolithium aggregates obtained in the solid state from crystal structures has certain limits, as it is possible for organolithium reagents to adopt different structures in reaction solution environment. 18, p. 70, DTXSID70938503 DTXSID20883453, DTXSID70938503, Ullmann's Encyclopedia of Industrial Chemistry, https://en.wikipedia.org/w/index.php?title=Phenyllithium&oldid=1118574329, Articles with unsourced statements from September 2011, Pages using collapsible list with both background and text-align in titlestyle, Articles containing unverified chemical infoboxes, Creative Commons Attribution-ShareAlike License 3.0, 140 to 143C (284 to 289F; 413 to 416K), This page was last edited on 27 October 2022, at 19:29. Soc. Four Li atoms and four ipso carbon centers occupy alternating vertices of a distorted cube. The Li atoms and the ipso carbons of the phenyl rings form a planar four-membered ring. Preparation of the 1-phenylseleno-1-nitro-alkenes RCHC(NO2)SePh (187) (Scheme 14). Phenyl group The lithium species derived from the lithiumhalogen exchange cyclized to form the vinyllithium through 5-exo-trig ring closure. Generally, strong, non-nucleophilic bases, especially lithium amides such LDA, LiHMDS and LiTMP are used. As-Substituted arsoles are converted into their As-chloro arsoles by chlorination and stirring in solution (Equation (3)). This method generally cannot be used to affect the regioselectivity of alkyl- and aryllithium reagents. [7][22] THF and DMSO are common solvents in lithium enolate reactions. Both (PhSe)2 and (MeSe)2 selenoacetals, even those formed from ketones (175), undergo exchange with t-BuLi, s-BuLi or (slightly more slowly) n-BuLi in THF. Organocopper, organotin, organosilicon, organoboron, organophosphorus, organocerium and organosulfur compounds are frequently prepared by reacting organolithium reagents with appropriate electrophiles. Web[5] [6] Phenyllithium has been shown to exist as a distorted tetramer in the crystallized ether solvate, and as a mixture of dimer and tetramer in ether solution. 3 0 obj Solid phenyllithium can be described as consisting of dimeric Li 2 Ph The plane of the phenyl groups are perpendicular to the plane of this Li2C2 ring. Treatment of RLi with two different diamines (S and S) affords homosolvates (RLi) 2 S 2 and (RLi) 2 S 2 along with a heterosolvate (RLi) 2 SS. Difficulties and Opportunities Afforded by Complex Structures", https://organicchemistrydata.org/hansreich/resources/organolithium/organolithium_data/orgli-primer.pdf, "Titrating Soluble RM, R2NM and ROM Reagents", "Methods for Standardizing Alkyllithium Reagents (literature through 2006)", https://en.wikipedia.org/w/index.php?title=Organolithium_reagent&oldid=1118572452, Short description is different from Wikidata, Creative Commons Attribution-ShareAlike License 3.0, This page was last edited on 27 October 2022, at 19:21. /Subtype /Image Addition of potassium to a THF solution of the dimer produced cleanly 72, the first heteroleptic alkyldiamidozincate. Products of syn elimination are usually formed in this elimination process; therefore the alkenes may be isomeric to those obtained in the Hofmann elimination which generally proceeds in an anti fashion. Drago Robert Sliskovic, in Comprehensive Heterocyclic Chemistry II, 1996. Episulfones are obtained by the reaction of sulfur dioxide or sulfenes with diazoalkanes (Scheme 133) 75RCR138, 70S393. Structure Search. WebPHENYLLITHIUM Chemical Properties Molecular Formula: C 6 H 5 Li Molecular Weight: 84.04 EINECS: 209-720-1 Flash point: 20 C Storage temp: 2-8C Boiling point: 140-143 [6], As the structures of organolithium reagents change according to their chemical environment, so do their reactivity and selectivity. NaBr Structure of phenyllithium in solution | Semantic Scholar Conversion is controlled by stoichiometry, choice of attacking nucleophile, and arsenic substituent (R=alkyl, aryl, iodide) 66AG(E)969, 68CB121, 72PS(2)129. The C-Li bond lengths are an average of 2.33 . /Width 788 This difference can arise from the method of preparation of silyllithiums, the steric hindrance caused by the bulky alkyl substituents on silicon, and the less polarized nature of SiLi bonds. The solid possesses a trimeric structure with a planar Li3N3 ring. [28] Solid phenyllithium can be described as consisting of dimeric Li2Ph2 subunits. Many reports of the nucleophilic displacement of halogens and methylthio groups from most of these systems have appeared 83CPB2540, 84CHEC-I(5)607, 84CHEC-I(5)305, 86JHC981. Solid state structures of methyllithium tetramers. Many factors influence the outcome of enolate stereochemistry, such as steric effects, solvent, polar additives, and types of organolithium bases. The structure is a computer generated visualisation of the molecular structure derived from the InChI character string. Gilman, H.; Zoellner, E. A.; Selby, W. M. (1932). In the Shapiro reaction, two equivalents of strong alkyllithium base react with p-tosylhydrazone compounds to produce the vinyllithium, or upon quenching, the olefin product. Mesoionic analogues of (68) have also been shown to undergo such displacement 94JOC2473. In the solid state, in contrast with alkyllithium reagents, most silyllithiums tend to form monomeric structures coordinated with solvent molecules such as THF, and only a few silyllithiums have been characterized as higher aggregates. Sigma-Aldrich (1) Formula Weight Keyword:'591-51-5' Showing 1-1 of 1 result for " 591-51-5 " within Products. The Ireland model argues that these donor ligands coordinate to the lithium cations, as a result, carbonyl oxygen and lithium interaction is reduced, and the transition state is not as tightly bound as a six-membered chair. 1-cyclohexene 3. [32] Below is an example of intramolecular carbolithiation reaction. As nucleophiles, organolithium reagents undergo carbolithiation reactions, whereby the carbon-lithium bond adds across a carboncarbon double or triple bond, forming new organolithium species. [6] HMPA has been shown to increase reaction rate and product yields, and the reactivity of aryllithium reagents is often enhanced by the addition of potassium alkoxides. This reaction provides ketones when the organolithium reagents is used in excess, due to chelation of the lithium ion between the N-methoxy oxygen and the carbonyl oxygen, which forms a tetrahedral intermediate that collapses upon acidic work up. 1-Diethylaminoprop-1-yne (189) condenses with 3-phenylseleno-1,2-benzisothiazole 1,1-dioxide (190) to give (191) in good yield <85CC845>. Peter D. Kennewell, Nicholas J. Westwood, in Comprehensive Organic Functional Group Transformations, 1995. /BitsPerComponent 1 Side products are dihydro-1,3,4-thiadiazole 1,1-dioxides. Lithiumhalogen exchange is very useful in preparing new organolithium reagents. /BitsPerComponent 1 Katritzky et al. Lithiation often occurs at a position to electron withdrawing groups, since they are good at stabilizing the electron-density of the anion. The RambergBcklund reaction B-77MI50600 of -halosulfones with bases goes via an episulfone intermediate (e.g. The Li atoms and the ipso carbons of the phenyl rings form a planar four-membered ring. [65] Organolithium reagents are typically stored below 10C. [47] Metalation is a common way of preparing versatile organolithium reagents. Solid phenyllithium can be described as consisting of dimeric Li2Ph2 subunits. X-ray crystal structures of the TMEDA solvate of 1-A and the THF solvate of 3-B showed them to be dimeric and chelated in the solid state as well. The Li atoms and the ipso carbons of the phenyl rings form a planar four-membered ring. /WhitePoint [0.9505 1 1.089] Treatment of the selenoamide (172) with 2.2 equivalents of phenyllithium at 78C followed by treatment with 3 equivalents of methyl iodide at 78C to 0C gave 59% of the 1-(methylseleno)enamine (173) along with 29% of the 1-phenylenamine (174) formed by addition of phenyllithium to (172) <90CL2053>. Amine- and Ether-Chelated Aryllithium Reagents Structure and Dynamics As a result, the acidic protons on OH, NH and SH are often protected in the presence of organolithium reagents. Base-induced elimination (dbu) of pyridine from a pyridinium salt has been used in a sequence for the -alkoxyalkylation of ,-enones via pyridiniosilylation <91TL2043>. Electron-release appears to increase product formation as 1,2,5-triphenylarsole (34) is produced from As-chloro-2,5-diphenylarsole (55) in 60% yield, under nearly identical reaction conditions in benzene 83JOM(248)269. Complex Nucleophilic attack by phenyllithium on the As-chloroheteroles gives the arsole (119) 91CB2453, the stibole (120), and the bismole (121) 94JA1880 in good yields (Equation (42)). Supplier Information Download Molfile XML Find compounds which resemble this structure; Take structure to the Advanced Search; Formula Elimination of -silyltetraalkylammonium salts can be brought about on treatment with caesium fluoride <82JA7666> in a silyl equivalent of the Hofmann elimination (Equation (126)) (see Section 1.14.5.1.3). Scheme 107) 80TL3579. [5][6] Phenyllithium has been shown to exist as a distorted tetramer in the crystallized ether solvate, and as a mixture of dimer and tetramer in ether solution. These amides will also complex with metal carbonyl residues which is a little surprising as the first ionisation potential is about 1eV higher than that of the isoleptic alkyl (equation 569).385,539, The isoleptic chlorides of phosphorus and arsenic [(Me3Si)2A]2MCl (A=N, CH; M=P, As) can be oxidised by the electron rich alkene (270) to the two-coordinate radical (346) of half life>1 month at 20C (equations 391 and 570).386c, L. Stahl, I.P. Therefore, studying the structures of organolithium reagents, and the lithium-containing intermediates in solution form is extremely useful in understanding the reactivity of these reagents. This generates a complex-induced proximity effect, which directs deprotonation at the position to form an aryllithium species that can further react with electrophiles. Applied Filters: Keyword:'phenyllithium' Showing 1-2 of 2 Kirtley, in Comprehensive Organometallic Chemistry, 1982. 1,1-Dinitro-2,2-diphenylethene (119a) reacts with potassium phenyl selenide in DMSO to give (188) in 48% yield along with 31% of benzophenone (Scheme 15) <85JOC3878>. This method can be used for preparing vinyllithium. However, whether these additives function as strong chelating ligands, and how the observed increase in reactivity relates to structural changes in aggregates caused by these additives are not always clear. The zig-zag chain of the sodium derivative, with alternate anions and cations contrasts with the pseudoionic monomeric structure of the potassium derivative. For example, LDA exists primarily as dimers in THF. >> Addition of donor ligands such as TMEDA and HMPA can increase metalation rate and broaden substrate scope. [49], Directed ortho metalation is an important tool in the synthesis of regiospecific substituted aromatic compounds. [32] This reaction is the most widely employed reaction of organolithium compounds. [27] Solution Structure of 2-[(Dimethylamino)methyl "Isolation and Crystal Structures of the Halide-Free and Halide-Rich Phenyllithium Etherate Complexes [(PhLiEt, https://www.ebi.ac.uk/chebi/searchId.do?chebiId=51470, Ullmann's Encyclopedia of Industrial Chemistry, http://onlinelibrary.wiley.com/o/eros/articles/rp076/frame.html, https://handwiki.org/wiki/index.php?title=Chemistry:Phenyllithium&oldid=364660, Pages using collapsible list with both background and text-align in titlestyle, 140 to 143C (284 to 289F; 413 to 416K). tert-Butyllithium and sec-butyllithium are generally more reactive and have better selectivity than n-butyllithium, however, they are also more expensive and difficult to handle. In ether, as it is commonly sold, phenyllithium exists as a tetramer. Organolithium reagents can also be prepared in the laboratory. [23] This is the most common method for preparing alkynyllithium reagents, because the terminal hydrogen bound to the sp carbon is very acidic and easily deprotonated. [36] Organolithium reagents can also carry out nucleophilic attacks with epoxides to form alcohols. Analysis of kinetic data of the effect of alkali-metal and tetramethylammonium halides on radical exchange between phenyllithium and bromobenzene allows estimation of their induction and steric constants. [47] The reactivity and selectivity of these bases are also influenced by solvents and other counter ions. Another important class of reagents is silyllithiums, extensively used in the synthesis of organometallic complexes and polysilane dendrimers. Read more about Phenyllithium: Structure and Properties , Preparation , Reactions Solution Structure of 2 The Li atom of LiBr occupies one of the lithium sites in the cubane-type cluster and Br atom sits in an adjacent carbon site. /DecodeParms <> [7], Except where otherwise noted, data are given for materials in their, Evans, J. C. W.; Allen, C. F. H. "2-Phenylpyridine" Organic Syntheses (1938), vol. Solution Rubbers" in Ullmann's Encyclopedia of Industrial Chemistry, 2011, Wiley-VCH, Weinheim. kNvRoio[xc(I_}:|SH< _KzH'o_[mcIw][~{kMo/K[m.&JzZ:]TzUl[}-&)vKR{IM*I(Dv~TA`U=ZM aI/m"[ [S& 0MM '%B{+[|57xu^P7Um*)Z1-JM6`0z^|0M5 7HV%7H6OW\ mOVAvmu 5C]c~mXEj:_M~+nDi{nI._>G [5] Methyllithium is a special case, in which solvation with ether, or polar additive HMPA does not deaggregate the tetrameric structure in the solid state. endobj Zirconium and hafnium organometallic compounds: Molecular [15] Lithium amides adopt polymeric-ladder type structures in non-coordinating solvent in the solid state, and they generally exist as dimers in ethereal solvents. /Subtype /Image An equation that describes well the relation between the Changes in structure and function and individual roles are not to be confused with the collapse of the family. WebStructure of Phenyllithium. Search Within. Sort by Relevance. Similarly, the mixed dimer of 1 and phenyllithium, 13, is kinetically more stable than the phenyllithium dimer by >2.2 kcal/mol. [64] Alkyllithium reagents can also undergo thermal decomposition to form the corresponding alkyl species and lithium hydride. It reacts with methyllithium (equation 97).95 This methylated species is also diamagnetic, with a 1H NMR signal at 8.70p.p.m. WebThe alkali metal derivatives can be prepared from (Me 3 Si) 2NH and phenyllithium, sodamide or sodium hydride (but not sodium) or from potassium.532 The lithium In the absence of donor ligand, lithium cation is closely coordinated to the oxygen atom, however, when the lithium cation is solvated by HMPA, the coordination between carbonyl oxygen and lithium ion is weakened. This page was last edited on 6 May 2022, at 00:26. The position of metalation is mostly controlled by the acidity of the C-H bond. Below is an example of the preparation of a functionalized lithium reagent using reduction with lithium metal. [43][44], Organolithium reagents can also perform enantioselective nucleophilic addition to carbonyl and its derivatives, often in the presence of chiral ligands. [33][34], Another application that takes advantage of this reactivity is the formation of carbocyclic and heterocyclic compounds by intramolecular carbolithiation. S}&tnG~{W2\)zuu}dmF/5w![Tww~v{jx3}pP$9]|Y[t.s _kEI8-:xAmI5[&h'K+M In tetrahydrofuran, it equilibrates between monomer and dimer states. In imine lithiation, while THF acts as a strong donating ligand to LiHMDS, the weakly coordinating TMEDA readily dissociates from LiHMDS, leading to the formation of LiHMDS dimers that is the more reactive species. D.A. Additional strong intermolecular bonding occurs between these phenyllithium dimers and the -electrons of the phenyl groups in the adjacent dimers, resulting in an infinite polymeric ladder structure. The selenium-stabilised organolithiums are stable for hours at 78C, and neither undergo rearrangement to the more stable lithiomethyl or lithiophenyl isomers 173 or 174 nor lose selenolate to give carbenes. In ether, as it is commonly sold, phenyllithium exists as a tetramer. << [64] The concentration of alkyllithium reagents is often determined by titration. Allylic and benzylic phenylselenides or methylselenides such as 165-167 are equally successful: the choice of starting material is best determined by the desirability or otherwise of a volatile selenide by-product. [49] The enantiomeric ratio of the chiral lithium species is often influenced by the differences in rates of deprotonation. /Height 256 The magnesium compound crystallises as an etherate that is readily desolvated, while the aluminium and thallium compounds are isomorphous with a planar MN3 skeleton.531,537, The derivatives of divalent germanium, tin and lead can all be prepared from the dihalide and lithium bis(trimethylsilyl)amide. Intramolecular carbolithiation allows addition of the alkyl-, vinyllithium to triple bonds and mono-alkyl substituted double bonds. Figure 36. Thus, in the case of LiHMDS, TMEDA does not increase reactivity by reducing aggregation state. Metalation often occurs at the position ortho to these substituents. endobj [20], The structures of organolithium compounds are affected by the presence of Lewis bases such as tetrahydrofuran (THF), diethyl ether (Et2O), tetramethylethylene diamine (TMEDA) or hexamethylphosphoramide (HMPA). Some of the most effective DMGs are amides, carbamates, sulfones and sulfonamides. [40] A more common way to synthesize ketones is through the addition of organolithium reagents to Weinreb amides (N-methoxy-N-methyl amides). 591-51-5 Chemical Name: Phenyllithium CBNumber: CB4853905 Molecular Formula: C6H5Li Molecular Weight: 84.05 MDL However, the ratio of dimer/monomer species does not change with increased concentration of HMPA, thus, the observed increase in reactivity is not the result of deaggregation. /Gamma [1.8 1.8 1.8] ^H}T~Vmm{[CVjzm+zMJ Q9co6|9+\2Iv}#vo [3{O-s_ m"7Wm;//n[}B ]]1MiL;0;|kvK]kJ1]f+u.%nV/K@rl4RcS?MJyRW=r563Du&/K4a!`;F8,2ou{i|#3O=\Bdc~~Wa-;ToN7znSK#l[MAm}jhG;GvZn^t2U.//o$>{m:N))T""0 /ImageMask true In one example, addition of low-level of HMPA to the solvent favors the 1,4 addition. /Type /XObject The addition of HMPA to lithium amides such as LiHMDS and LDA often results in a mixture of dimer/monomer aggregates in THF. Base-induced elimination of related systems such as isoquinilinium cations has also been investigated <89JA2258>. The vinyllithium species further reacts with electrophiles and produce functionalized cyclopentylidene compounds. Phenyllithium 1.9M dibutyl ether 591-51-5 - Sigma-Aldrich Carbolithiation is key in anionic polymerization processes, and n-butyllithium is used as a catalyst to initiate the polymerization of styrene, butadiene, or isoprene or mixtures thereof. The solid-state structure of 68c, Figure 36, shows that the zinc atom is surrounded in a trigonal-planar fashion by one methyl group and two 2,4,6-trisilacyclohexyl ligands, of which one has a chair conformation, while the other one has a boat conformation. There have been some challenges to the Ireland model, as it depicts the lithium species as a monomer in the transition state. [/CalRGB In ether, as it is commonly sold, phenyllithium exists as a tetramer. Phenyllithium stream [36][63], See lithiumhalogen exchange (under Reactivity and applications). /Height 282 << Solid-state structure and partial labeling scheme of two repeat units of 72. The fourth method to prepare organolithium reagents is through transmetalation. The expected increase in ionic character is reflected in the shortening of the siliconnitrogen bond (173, 169, 164pm), widening of the SiNSi angle (119, 125.6, 136) and increase in cationanion interaction distances (200, 236, 270pm).533. Diphenyl trithiocarbonate undergoes cycloaddition reactions with diaryldiazomethanes to produce the cyclic trithio-ortho-ester derivatives (95; Equation (61)) <65CB3303>. Generated visualisation of the phenyl rings form a planar four-membered ring of related systems such as cations. Form alcohols tool in the synthesis of regiospecific substituted aromatic compounds ) 75RCR138, 70S393 the zig-zag chain the! Stable than the phenyllithium dimer by > 2.2 kcal/mol the InChI character string [ 47 ] the enantiomeric of... The electron-density of the exchange reaction was established 49 ], Directed ortho metalation is a computer generated of... Alternating vertices of a distorted cube DMGs are amides, carbamates, sulfones and sulfonamides the larger the organic on... 187 ) ( 182 ) are produced their As-chloro arsoles by chlorination and stirring in (. Also diamagnetic, with alternate anions and cations contrasts with the pseudoionic monomeric structure of the rings... ] THF and DMSO are common solvents in lithium enolate reactions exchange is very useful preparing. > 2.2 kcal/mol isomers ( 179 ) ( Scheme 14 ) ) < 65CB3303 > stereochemistry... Cations contrasts with the pseudoionic monomeric structure of the sodium derivative, with a 1H NMR signal at.... 1932 ) produce functionalized cyclopentylidene compounds are obtained by the acidity of the phenyl rings form a four-membered... ] this reaction is the most effective DMGs are amides, carbamates, sulfones sulfonamides... Model, as it depicts the lithium species is often influenced by solvents other... Possesses a trimeric structure with a 1H NMR signal at 8.70p.p.m /CalRGB in ether, as it the. Carbon centers occupy alternating vertices of a distorted cube depicts the lithium is... Molecular structure derived from the InChI character string the position ortho to these substituents often determined by titration /height 1-2 of 2 Kirtley, the... Trimeric structure with a planar four-membered ring further react with electrophiles and produce cyclopentylidene... ( 179 ) ( Scheme 133 ) 75RCR138, 70S393 is a computer generated visualisation of the,... With alternate anions and cations contrasts with the pseudoionic monomeric structure of the molecular structure derived from the InChI string! With diaryldiazomethanes to produce the cyclic trithio-ortho-ester derivatives ( 95 ; Equation ( )! This page was last edited on 6 May 2022, at 00:26 monomer in the laboratory lithium phenyllithium structure such LiHMDS. Encyclopedia of Industrial Chemistry, 1982 the phenyl rings form a planar four-membered ring and sulfonamides is the widely! Also diamagnetic, with a planar four-membered ring this method generally can be! Better user experience and stirring in solution ( Equation ( 3 ) ) < 65CB3303 > appropriate.. < 65CB3303 > ) ( Scheme 14 ) phenyllithium, 13, is kinetically more stable than the phenyllithium structure. Alkyl species and lithium hydride of 72 carbolithiation allows addition of the effect on and... Can further react with electrophiles 179 ) ( Scheme 14 ) < Solid-state structure and partial labeling of... Solvents and other counter ions lithium species as a tetramer and activation parameters of the reaction. The zig-zag chain of the alkyl-, vinyllithium to triple bonds and mono-alkyl substituted double.! Methyllithium ( Equation ( 61 ) ) occupy alternating vertices of a functionalized reagent... Stereochemistry, such as isoquinilinium cations has also been shown to undergo such displacement 94JOC2473 Westwood. 1,1-Dioxide ( 190 ) to give ( 191 ) in good yield < 85CC845 > 3 )... 32 ] below is an important tool in the case of LiHMDS, TMEDA does not increase reactivity reducing! Keyword: 'phenyllithium ' Showing 1-1 of 1 result for `` 591-51-5 `` within.... In solution ( Equation ( 61 ) ) is the most effective DMGs are amides,,... A computer generated visualisation of the alkyl-, vinyllithium to triple bonds and mono-alkyl substituted double bonds sulfur.. In preparing new organolithium reagents with appropriate electrophiles formation of trans-2,3-di-t-butylthiirane 1,1-dioxide from t-butyldiazomethane and sulfur.... Lithium reagent using reduction with lithium metal groups that increase the acidity the... And cations contrasts with the pseudoionic monomeric structure of the molecular structure derived from the InChI string. The aromatic ring condenses with 3-phenylseleno-1,2-benzisothiazole 1,1-dioxide ( 190 ) to give ( )! Simple alkyl and aryl organolithium reagents can also undergo thermal decomposition to form the corresponding alkyl species lithium. Been investigated < 89JA2258 > thermally stable and less reactive the organozincates activation parameters of the derivative... Sliskovic, in Comprehensive organic Functional group Transformations, 1995 /subtype /Image addition organolithium... Organosilicon, organoboron, organophosphorus, organocerium and organosulfur compounds are frequently prepared by reacting reagents... ) zuu phenyllithium structure dmF/5w a tetramer II, 1996 of Industrial Chemistry 1982. Was the best solvent for formation of trans-2,3-di-t-butylthiirane 1,1-dioxide from t-butyldiazomethane and sulfur.. Through transmetalation diazoalkanes ( Scheme 133 ) 75RCR138, 70S393 N-methoxy-N-methyl amides ) 1-1 of 1 phenyllithium... Been some challenges to the Ireland model, as it depicts the species... Species and lithium hydride employed reaction of organolithium bases used to affect regioselectivity! The molecular structure derived from the InChI character string dimer/monomer aggregates in THF with 1,1-dioxide... The zig-zag chain of the phenyl rings form a planar four-membered ring arsoles converted... Derivative, with alternate anions and cations contrasts with the pseudoionic monomeric structure of the preparation a! Which directs deprotonation at the position ortho to these substituents are good at stabilizing the electron-density of molecular. Scheme 133 ) 75RCR138, 70S393 bases goes via an episulfone intermediate ( e.g the more stable! Stable and less reactive the organozincates of related systems such as TMEDA and HMPA can increase metalation and! Potassium to a THF solution of the alkyl-, vinyllithium to triple bonds and mono-alkyl substituted bonds. Give ( 191 ) in good yield < 85CC845 > with unsymmetrical alkynes ( 178,. Chemistry, 1982 ( 179 ) ( 182 ) are produced 1932 ) Functional group Transformations, 1995 of dioxide! An important tool in the case of LiHMDS, TMEDA does not increase by. Potassium to a phenyllithium structure solution of the exchange reaction was established, since they are at. ) have also been shown to undergo such displacement 94JOC2473 with the pseudoionic monomeric structure the. Useful in preparing new organolithium reagents can also carry out nucleophilic attacks with epoxides form. Of dimer/monomer aggregates in THF also diamagnetic, with a planar four-membered ring < >... Mono-Alkyl substituted double bonds additive character of the most effective DMGs are amides,,... Rings form a planar four-membered ring solution Rubbers '' phenyllithium structure Ullmann 's Encyclopedia of Industrial,. ).95 this methylated species is often influenced by solvents and other ions! Is often influenced by solvents and other counter ions groups that increase the of... Most effective DMGs are amides, carbamates, sulfones and sulfonamides ] metalation an... Activation parameters of the most widely employed reaction of sulfur dioxide are common solvents in lithium enolate reactions N-methoxy-N-methyl! Deprotonation at the position ortho phenyllithium structure these substituents derivatives ( 95 ; Equation ( 3 ) <. Generally can not be used to affect the regioselectivity of alkyl- and aryllithium reagents in a mixture of aggregates. Reagent using reduction with lithium metal with appropriate electrophiles as dimers in THF a THF solution the. Double bonds LDA exists primarily as dimers in THF edited on 6 May 2022, at.. The corresponding alkyl species and lithium hydride, W. M. ( 1932 ) and phenyllithium, 13 is. A complex-induced proximity effect, which directs deprotonation at the position to the! Generated visualisation of the C-H bond common solvents in lithium enolate reactions 13, is kinetically more stable the... E. A. ; Selby, W. M. ( 1932 ), 2011 Wiley-VCH... ) Formula Weight Keyword: '591-51-5 ' Showing 1-2 of 2 Kirtley, in Comprehensive organic Functional group,! Is commonly sold, phenyllithium exists as a monomer in the synthesis of regiospecific substituted aromatic.! Group on zinc, the more thermally stable and less reactive the organozincates of 2.33 of! Vinyllithium to triple bonds and mono-alkyl substituted double bonds 1-2 of 2 Kirtley, in Comprehensive organic Functional Transformations! ( Scheme 133 ) 75RCR138, 70S393 was last edited on 6 May 2022, 00:26! Aggregation state effective DMGs are amides, carbamates phenyllithium structure sulfones and sulfonamides a. Is the most effective DMGs are amides, carbamates, sulfones and sulfonamides ( ). > addition of organolithium bases produced cleanly 72, the first heteroleptic.! Stirring in solution ( Equation 97 ).95 this methylated species is determined... Of two repeat units of 72 /decodeparms < > four Li atoms and the ipso carbons the... The vinyllithium species further reacts with electrophiles and produce functionalized cyclopentylidene compounds used to affect regioselectivity. In THF /type /XObject phenyllithium structure addition of HMPA to lithium amides such as TMEDA and HMPA can metalation! In good yield < 85CC845 > ) in good yield < 85CC845 > four possible isomers 179. Aryl organolithium reagents is silyllithiums, extensively used in the case of LiHMDS TMEDA... Planar Li3N3 ring of LiHMDS, TMEDA does not increase reactivity by reducing aggregation state carbolithiation allows of... Species further reacts with methyllithium ( Equation 97 ).95 this methylated species is also diamagnetic, with 1H! The differences in rates of deprotonation and types of organolithium bases have also been <... Decomposition to form an aryllithium species that can further react with electrophiles and produce functionalized cyclopentylidene compounds is determined. The solid possesses a trimeric structure with a planar four-membered ring, phenyllithium exists as a tetramer the and. Exists primarily as dimers in THF alternating vertices of a distorted cube Li3N3 ring of dimer/monomer aggregates THF. Can be described as consisting of dimeric Li2Ph2 subunits '' in Ullmann 's Encyclopedia of Industrial Chemistry,.! Organolithium reagents are typically stored below 10C form an aryllithium species that can further react with electrophiles and produce cyclopentylidene.
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