Organolithium compounds lead structures

The use of sterically hindered secondary organolithium reagents, such as (CgH jCH Li, drastically favors the O-alkyl scission of thejbster group (37) finally, organolithium compounds leading to non enolizable keto functions in the first step of substitution, such as C H Li, promote competitive and consecutive reactions resulting in complex copolymers of poorly defined structure (38,39) ... 

The interaction between pyridine and organolithium compounds in benzene was first reported by Ziegler and Zeiser129 and was attributed to the formation of 1 1 adducts. Indirect evidence for intermediates of this kind was based on the formation of dihydropyridines by treatment of the reaction mixture with water. More definite evidence was obtained with quinoline, isoquinoline, and acridine.130 Phenyllithium reacts quantitatively with quinoline in ether to yield an adduct as a yellow powder that can be recrystallized. In order to define the site of attachment, the adducts were hydrolyzed to dihydro derivatives and the latter dehydrogenated. Because this treatment leads mainly to 2-phenyIquinoIine and l-phenylisoquinoline from quinoline and isoquinoline, respectively, the related adducts can be assumed to have structures 80 and 81. Isolation and characterization of the dihydro derivatives have been carried out, as well as in the case of the reaction of acridine with phenyllithium. 

The crystal structures of numerous organolithium compounds and complexes with 0—Li bonds are now available (2-5). Table IV lists a number of these species, as well as two derivatives of heavier alkali metals. As with the C—Li derivatives just discussed (Tables II and III), clustered (ROLi) tetramers and hexamers, as well as ring dimers, are prevalent. Note that (OLi)2,3 ring systems also are pseudoplanar (Fig. 21a). However, extensive stacking leading to polymers will only occur if the substituents on 0 are small and if polar ligands are absent. Otherwise, limited (double) stacks or unstacked rings form. 

Organomagnesium and organolithium compounds can add both 1,2 and 1,4 to alkenones, and the relative importance of each mode of addition depends on the structure of the reactants. This sort of dual behavior can be a nuisance in synthetic work because it leads to separation problems and low yields. Organocopper compounds are a great help in this situation because they show a very high selectivity for 1,4 addition and add to unsaturated ketones in excellent yield ... 

The tetraalkyltins show little tendency to increase their coordination with an external ligand. The exception is the organic nucleophile from organolithium compounds which gives, reversibly, the 5-coordinate tin anion which can be observed by NMR spectroscopy, and which leads to the exchange of alkyl groups (equation 5-6). These reactions are discussed in Sections 5.3.5 and 22.1. An NMR study of the product from treating tribu-tyl(hydroxymethyl)tin with butyllithium implied that it had the 6-coordinate structure 5-2.25... 

Stey T, Stalke D (2004) Lead structures in lithium organic chemistry. In Rappoport Z, Marek I (eds) The chemistry of organolithium compounds (Patai Series The Chemistry of functional groups), chap 2. Wiley, Chichester, pp 47-120... 

The products obtained from the reaction of (chloromethyl)trimethylsilane with organolithium reagents depend very much on the structure of the lithium compound. While lithium 2,2,6,6-tetramethylpiperidide initiates an a-elimination as described above, the treatment with sec-butyllithium leads to the formation of chloro(trimethylsilyl)methyllithium (11). This reagent cyclopropanates an electron-deficient alkene through sequential Michael addition and intramolecular ring closure (MIRC reaction), for example, the formation of cyclopropane 12. 

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