By Jonathan Clayden
This quantity, quantity 23 within the "Tetrahedron natural Chemistry" sequence, offers organolithium chemistry from the point of view of a man-made natural chemist, drawing from the unreal literature to provide a unified review of the way organolithiums can be utilized to make molecules. the improvement of equipment for the regioselective synthesis of organolithiums has changed their picture of indiscriminate excessive reactivity with one among controllable and refined selectivity. Organolithium chemistry has a relevant position within the selective building of C-C bonds in either basic and complicated molecules, and for instance has arguably overtaken fragrant electrophilic substitution because the strongest process for regioselective functionalisation of fragrant jewelry. the dual issues of reactivity and selectivity run in the course of the e-book, which experiences the methods through which organolithiums can be shaped and the ways that they react. themes comprise advances in directed metallation, reductive lithiation and organolithium cyclisation reactions, in addition to a dialogue of organolithium stereochemistry and the position performed via ligands equivalent to (-)-sparteine.
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Extra info for Organolithiums: Selectivity for Synthesis
Lithioisobutyrophenone reacted with (+)-2(S)iodooctane to give the corresponding enol ether (114) and l-phenyl-2,2,3trimethylnonanone (115). 87 The qualitative result for both solvents is that both C- and O-alkylation proceed with net inversion of configuration. 88 The electron rich C-C double bond of Si-enol ethers is easily attacked by electrophiles to give a trimethylsilyloxy stabilized carbocation. The nucleophilic anion associated with the electrophile attacks the silyl center to give a C-substituted ketone.
86 The activation energy for O-alkylation is lower than that for C-alkylation, even though the latter is favored thermodynamically. These results parallel those found for the reactions of Me - and OH - with MeF and arise from the lower intrinsic barrier for reactions of oxygen-centered nucleophiles (or leaving groups) than carbon-centered nucleophiles in SN2 reactions. The geometry of the transition structures indicates that stereoelectronic factors favor product-like conformations, even for relatively early transition states.
Reaction of the ß-ketosulphone with NaH in THF followed by addition of pivaloyl chloride gave the O-acylated product (122). 95 The trialkylsilyl derivatives of esters (silyl ketene acetals) are readily Cacylated with acid chlorides (eq 6). The less reactive trialkylsilyl derivatives of ketones (silyl enol ethers) are C-acylated only by reactive polyhalogenated acid chlorides (eq 7). Simple acid chlorides either do not react, or react in the presence of catalysts to give O-acylated products (eq 7).
Organolithiums: Selectivity for Synthesis by Jonathan Clayden