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Solubility: sol hydrocarbon and ethereal solvents, but should be used at low temperature in the latter solvent type: half-lives in ethereal solvents have been reported;12 reacts violently with H2O and other protic solvents.
Lithiations employing s-BuLi are most often conducted in electron-donating solvents such as Et2O, THF, and DME which coordinate to lithium much more strongly than do the alkyl groups of hydrocarbon solvents and thus enhance the reactivity of the organolithium species. It is generally agreed that this effect is the consequence of the depolymerization of higher order organolithium aggregates (tetramers) into smaller units (dimers and monomers).1 The increased reactivity of organolithiums in ether solvents can, in fact, lead to a-deprotonation of the solvent molecules at elevated temperatures; in diethyl ether, for example, s-BuLi has a maximum lifetime of about an hour at +20 °C and THF is attacked even more readily.12 Hence, to ensure the integrity of the organolithium reagents in these solvents, the use of low-temperature conditions (typically -78 °C) is imperative.
s-Butyllithium is a commonly used reagent for ortho lithiation of aromatic rings bearing heteroatom-containing substitutents. This methodology has been exploited extensively as a route to a wide variety of polysubstituted aromatic compounds, including natural products53 (eq 22),53e and several excellent reviews have been published on the topic.2,5,54 Included in the list of groups commonly used for s-BuLi-promoted ortho lithiations are OMe,55 CH2NEt2,55 NMe2,56 CONEt2,57 OCONEt2,57 SO2NR2,58 2-oxazolinyl,57 and groups that contain acidic hydrogens and themselves undergo deprotonation prior to ring lithiation, e.g. CONHR57,58 and SO2NHR.57,58 Depending on the substituent, both inductive and coordination effects can be invoked to account for the observed regiochemistry.2,59 Although a large number of ortho lithiations may be conducted with n-BuLi,2 the use of s-BuLi is generally preferred, especially when the reactions involve aromatic tertiary amides or O-aryl carbamates which are susceptible toward nucleophilic additions with the latter. For example, N,N-dimethyl- and -diethylbenzamides have been shown to afford primarily aryl butyl ketones upon treatment with n-BuLi.55,60 The recommended procedure for ortho lithiation involves slow addition of the aromatic substrate in anhydrous THF to a slight excess of 1:1 s-BuLi/TMEDA in THF at -78 °C.55 Under these conditions, the lithiation is usually complete within 5 min.
Lithium-Halogen Interchange and Transmetalation Reactions.
Organolithium compounds are also accessible through the replacement of tin and tellurium by lithium, with the various organotin compounds being particularly important precursors for otherwise inaccessible organolithium derivatives (e.g. a-amino- and a-alkoxy-substituted organolithiums). Although s-BuLi is well suited for these transformations,52,76 most of the synthetic applications exploiting this methodology involve the use of n-BuLi.
Salicylamides are available from various aryl carbamates, including those derived from Pyridine and naphthalene,63 through the s-BuLi-mediated O-C 1,3-carbamoyl migration reactions (Snieckus rearrangement).57 This regiospecific rearrangement is the anionic equivalent of the Fries rearrangement and it involves low-temperature (-78 °C) ortho lithiation of aryl carbamates with s-BuLi/TMEDA/THF followed by warming of the reaction mixture to rt (eq 32).85 Benzylic carbamates rearrange to give products derived from either 1,4- or 1,2-carbamoyl migration (eq 33) following treatment with s-BuLi in THF,86 and lithiated phenolic esters rearrange to furnish acyl phenols even at low temperatures (eq 34).67 s-Butyllithium is also capable of initiating various Wittig rearrangements involving allylic ethers, but these reactions are done more conveniently using the less reactive n-BuLi.
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