Organolithium compounds carbene complexes

Chromium carbene complexes like 13, which are called Fischer carbene complexes, can conveniently be prepared from chromium hexacarbonyl 11 and an organolithium compound 12, followed by an O-alkylation step ... 

J-Oxygen-functionalised sp3 organolithium compounds react with alkenyl-carbene complexes to generate the corresponding cyclic carbene complexes in a formal [3+3] process (see Sect. 2.8.1). In those cases where the organolithium derivative contains a double bond in an appropriate position, tricyclic ether derivatives are the only products isolated. These compounds derive from an intramolecular cyclopropanation of the corresponding cyclic carbene complex intermediate [89] (Scheme 83). 

Elimination to yield alkenes can be induced thermally or by treatment with acids or bases (for one possible mechanism, see Figure 3.39) [138,206]. Less common thermal demetallations include the thermolysis of arylmethyloxy(phenyl)carbene complexes, which can lead to the formation of aryl-substituted acetophenones [276]. Further, (difluoroboroxy)carbene complexes of molybdenum, which can be prepared by treating molybdenum hexacarbonyl with an organolithium compound and then with boron trifluoride etherate at -60 °C, decompose at room temperature to yield acyl radicals [277]. 

A further synthetic approach to carbon-metal double bonds is based on the acid-catalyzed abstraction of alkoxy groups from a-alkoxyalkyl complexes [436 -439] (Figure 3.11). These carbene complex precursors can be prepared from alk-oxycarbene complexes (Fischer-type carbene complexes) either by reduction with borohydrides or alanates [23,55,63,104,439-445] or by addition of organolithium compounds (nucleophilic addition to the carbene carbon atom) [391,446-452]. 

The reaction of transition-metal carbonyls with organolithium compounds to give metal carbene complexes is now well known it can also take place when the metal is linked to a group IV atom, as in the following series of reactions (426). 

The exact formulation of the reactive intermediate in a-elimination reactions using organolithium compounds as bases has been difficult. Apart from the free carbene, various carbenoids are possible, including the a-haloorganolithium formed on metalation, and carbene-lithium halide complexes of various degrees of association. In the case of the dichlorocarbene-trichloromethyllithium equilibrium, the... 

Addition of organolithium compounds, RLi, to carbene compounds of structure 71 results in the formation of p-substituted aldehydes with high e.e. (80-97%). 1,5-addition of iodine to the cyclopropyl carbene complexes, [(OC)5Cr=C(SPh)(PrC)], proceeds with a high degree of stereo-and regio-control to form an alkenyl iodide. 5... 

Scheme 4-51. Synthesis of neutral (carbene)iron complexes by subsequent reaction of pentacarbonyliron with an organolithium compound and an alkyl fluorosulfonate.

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