Lithium alkoxide

Quantitative Analysis of All llithium Initiator Solutions. Solutions of alkyUithium compounds frequentiy show turbidity associated with the formation of lithium alkoxides by oxidation reactions or lithium hydroxide by reaction with moisture. Although these species contribute to the total basicity of the solution as determined by simple acid titration, they do not react with allyhc and henzylic chlorides or ethylene dibromide rapidly in ether solvents. This difference is the basis for the double titration method of determining the amount of active carbon-bound lithium reagent in a given sample (55,56). Thus the amount of carbon-bound lithium is calculated from the difference between the total amount of base determined by acid titration and the amount of base remaining after the solution reacts with either benzyl chloride, allyl chloride, or ethylene dibromide. 

Other, even milder bases than LDA and LHS, such as lithium methoxide and lithium /-butoxide, may be used in organic syntheses (143,144). Lithium methoxide is available commercially as a 10% solution in methanol and lithium /-butoxide as an 18% solution in tetrahydrofuran (145). Lithium /-butoxide is also soluble in hydrocarbon solvents (146). Both lithium alkoxides are also available as soHds (147) (see Alkoxides, metal). 

Sequential one styrene block is polymerized, then the mid-block monomer is added and polymerized, then more styrene is added and the second styrene block polymerized. This process is used to produce 100% triblock rubbers, for maximum strength [5]. Termination is commonly with alcohols, which produces a lithium alkoxide salt as the by-product. 

Organolithium compounds are sometimes prepared in hydrocarbon solvents such as pentane and hexane, but nonnally diethyl ether is used. It is especially important that the solvent be anhydrous. Even trace amounts of water or alcohols react with lithium to form insoluble lithium hydroxide or lithium alkoxides that coat the surface of the metal and prevent it from reacting with the alkyl halide. Furthennore, organolithium reagents are strong bases and react rapidly with even weak proton sources to fonn hydrocarbons. We shall discuss this property of organolithium reagents in Section 14.5. 

Lithium alkoxides react with PMBMCl to form the ethers. ... 

The exchange of lithium in a dililhium phthalocyanine is a useful tool to prepare metal (e.g., zinc) or metal-free phthalocyanines. For this purpose, the dilithium phthalocyanine is prepared by reaction of phthalonitrile and lithium alkoxide in an alcohol, e.g. pentan-l-ol. In most cases, the lithium phthalocyanine is not separated but directly converted into the respective phthalocyanine by treatment with metal salts or, in the case of metal-free phthalocyanine, with acid or water. 

It is well known today that the SEI on both lithium and carbonaceous electrodes consists of many different materials including LiF, Li2C03, LiC02R, Li20, lithium alkoxides, nonconductive polymers, and more. These materials form simultaneously and precipitate on the electrode as a mosaic of microphases [5, 6], These phases may, under certain conditions, form separate layers, but in general it is more appropriate to treat them as het-eropolymicrophases. We believe that Fig. 13(a) is the most accurate representation of the SEI. 

The spontaneous rearrangement of allyl p-toluenesulphenates to allyl sulphoxides was independently recorded by Mislow and coworkers and Braverman and Stabinsky. Mislow and colleagues201 have demonstrated that simple allyl alcohols such as 149, on conversion to the corresponding lithium alkoxides followed by treatment with arenesulphenyl chlorides, may be smoothly transformed at room temperature via the sulphenate esters into allylic sulphoxides 150 (equation 83). Braverman and Stabinsky202 have found that when the more reactive trichloromethanesulphenyl chloride is treated with allyl alcohol and pyridine in ether at — 70°, it affords trichloromethyl allyl sulphoxide and not allyl trichloromethanesulphenate as reported by Sosnovski203 (equation 84). 

A cyclic trimer, resulting from the facile intramolecular condensation of the linear trimer coupled with elimination of lithium alkoxide, is produced in the early stages of polymerization carried out at ambient temperature U). Similar condensations might... 

Among special chemical methods that facilitate the Diels-Alder reaction can be included the temporary metal connection strategy [101] that is illustrated in Table 4.27. Si, Mg and A1 are used as temporary connectors of diene and dienophile moieties. The cycloaddition occurs easily due to its intramolecular nature and because the dienophilic component of reagent is now formally a vinyl carbon ion (i.e. a vinyl carbanion in 154 with M = AlEt ). Thus the metal-tethered 154, prepared from lithium alkoxide of 153 with the suitable metal vinyl halide, gives, by heating, the cycloadducts 156 and 157, through the... 

The details of the mechanism are poorly understood, though the oxygen of the alcohol is certainly attacking the carbon of the isocyanate. Hydrogen bonding complicates the kinetic picture. The addition of ROH to isocyanates can also be catalyzed by metallic compounds, by light, or, for tertiary ROH, by lithium alkoxides ° or n-butyllithium. ° ... 

The key cyclization in Step B-2 was followed by a sequence of steps that effected a ring expansion via a carbene addition and cyclopropyl halide solvolysis. The products of Steps E and F are interesting in that the tricyclic structures are largely converted to tetracyclic derivatives by intramolecular aldol reactions. The extraneous bond was broken in Step G. First a diol was formed by NaBH4 reduction and this was converted via the lithium alkoxide to a monomesylate. The resulting (3-hydroxy mesylate is capable of a concerted fragmentation, which occurred on treatment with potassium f-butoxide. 

While ephedrine derivatives showed some selectivity, the most promising results were obtained with cinchona alkaloids. Lithium alkoxides and lithium acetylides (n-BuLi or LiHMDS used to deprotonate both the acetylene and the alcohol) gave better results than the corresponding sodium or magnesium salts. Higher enan-tioselectivity was obtained in THF (homogeneous) than in toluene or diethyl ether (heterogeneous). 

Introduction Since we had already developed the novel asymmetric addition of lithium acetylide to ketimine 5, we did not spend any time on investigating any chiral resolution methods for Efavirenz . Our previous method was applied to 41. In the presence of the lithium alkoxide of cinchona alkaloids, the reaction proceeded to afford the desired alcohol 45, as expected, but the enantiomeric excess of 45 was only in the range 50-60%. After screening various readily accessible chiral amino alcohols, it was found that a derivative of ephedrine, (1J ,2S) l-phenyl-2-(l-pyrrolidinyl)propan-l-ol (46), provided the best enantiomeric excess of 45 (as high as 98%) with an excellent yield (vide infra). Prior to the development of asymmetric addition in detail, we had to prepare two additional reagents, the chiral modifier 46 and cyclopropylacetylene (37). 

It would be ideal if the asymmetric addition could be done without a protecting group for ketone 36 and if the required amount of acetylene 37 would be closer to 1 equiv. Uthium acetylide is too basic for using the non-protected ketone 36, we need to reduce the nucleophile s basicity to accommodate the acidity of aniline protons in 36. At the same time, we started to understand the mechanism of lithium acetylide addition. As we will discuss in detail later, formation of the cubic dimer of the 1 1 complex of lithium cyclopropylacetylide and lithium alkoxide of the chiral modifier3 was the reason for the high enantiomeric excess. However, due to the nature of the stable and rigid dimeric complex, 2 equiv of lithium acetylide and 2 equiv of the lithium salt of chiral modifier were required for the high enantiomeric excess. Therefore, our requirements for a suitable metal were to provide (i) suitable nucleophilicity (ii) weaker basicity, which would be... 

Many of the papers from Merck reported the 1 1 complex of lithium acetylide and lithium alkoxide of the chiral modifier as monomer and the dimer of the 1 1 complex as tetramer. 

Aging a mixture of lithium acetylide and the lithium alkoxide of 46 at higher temperature (-10 to 0°C) prior to addition of ketone 41 is needed to obtain constantly high enantiomeric excess. 

The structure of the major aggregate was identified by labeling studies. Since the major set has two equal intensity 6Li signals, these signals could be assigned as a 1 1 complex 68 of lithium acetylide and lithium alkoxide or a dimer (such as 69) of the 1 1 complex 68 shown in Figure 1.9. Both structures have two different Li species. In order to discriminate between 68 and 69, a terminal acetylene carbon of 37 was labeled with 13C. In the case of 68, both lithium signals will be a doublet... 

The preparation of a functional segmented block copolymer was also investigated (scheme ll).15 First hydroboration polymerization of the oligomer using thexylborane was carried out. Then the obtained organoboron polymer was subjected to a chain-transformation reaction (DCME rearrangement). DCME and lithium alkoxide of 3-ethyl-3-pentanol in hexane was added to a THF solution of the polymer at 0°C. 

The Michael addition of alkoxides to nitroalkenes gives generally a complex mixture of products due to the polymerization of nitroalkenes.16 The effect of cations of alkoxides has been examined carefully, and potassium- or sodium-alkoxides give pure p-nitro-ethers in 78-100% isolated yield (Eqs. 4.12 and 4.13).17 When lithium-alkoxides are employed, the yields are decreased to 20-40%. 

The most studied catalyst family of this type are lithium alkyls. With relatively non-bulky substituents, for example nBuLi, the polymerization of MMA is complicated by side reactions.4 0 These may be suppressed if bulkier initiators such as 1,1-diphenylhexyllithium are used,431 especially at low temperature (typically —78 °C), allowing the synthesis of block copolymers.432,433 The addition of bulky lithium alkoxides to alkyllithium initiators also retards the rate of intramolecular cyclization, thus allowing the polymerization temperature to be raised.427 LiCl has been used to similar effect, allowing monodisperse PMMA (Mw/Mn = 1.2) to be prepared at —20 °C.434 Sterically hindered lithium aluminum alkyls have been used at ambient (or higher) temperature to polymerize MMA in a controlled way.435 This process has been termed screened anionic polymerization since the bulky alkyl substituents screen the propagating terminus from side reactions. 

Table 8. Reaction of Lithium Alkoxides with (2(3-Benzo-2-Cydohexenylidene)-Chloromethyllithium (24) at Low Temperatures...

Tandem 1,2- and 1,4-additions to quinones.1 The lithium alkoxide formed by 1,2-addition of an alkyllithium to a p-benzoquinone can react as a Michael acceptor with some nucleophiles in the presence of HMPT or DMPU (13, 122). The process involves lithium-metal exchange followed by intramolecular delivery... 

J. P. Leal, J. A. Martinho Simoes. Standard Molar Enthalpies of Formation of Lithium Alkoxides. J. Organometal. Chem. 1993, 460, 131-138. 

The last steps of the synthesis involved i) removal of the TBS group with TASF [21], to give 7-BOM baccatin III (64b) ii) reaction of the corresponding lithium alkoxide with P-lactam 34 from Scheme 13.6.6 iii) desilylation of the resulting product and iv) removal of the C(7) BOM group by hydrogenolysis (H2, Pd/C, EtOH, reflux, Ih) to give taxol in 93% yield from 64b. The synthesis produces (-)-taxol from (-)-bomeol and enr-(+)-taxol from (-)-patchino. The overall yield from 40a is ca. 4-5%. 

A different mode of fragmentation of the lactone ring in 35 occurred to give butyrolactone 38 when anhydrous lithium alkoxides were used in place of metal hydroxides under aqueous conditions (Scheme 10). It is noteworthy that 36, 37 and 38 (R = H) are all formed without racemization. Although we are only in the early stages of development of the chemistry of iodolactones 35, it is already clear that there is considerable potential for utilization of the butenolides derived from 35 as scaffolds for construction of carbocyclic and heterocyclic ring... 

---