Organometallic compounds with anhydrides

Torrence P (2002) Carbonylations synthesis of acetic acid and acetic acid anhydride from methanol. In Cornils B, Herrmann WA (eds) Applied homogeneous catalysis with organometallic compounds, vol 1, 2nd edn. Wiley, Weinheim, p 104... 

The Conversion of Anhydrides, Carboxylic Esters, or Amides to Ketones With Organometallic Compounds... 

This review article is concerned with chemical behavior of organo-lithium, -aluminum and -zinc compounds in initiation reactions of diolefins, polar vinyls and oxirane compounds. Discussions are given with respect to the following five topics 1) lithium alkylamide as initiator for polymerizations of isoprene and 1,4-divinylbenzene 2) initiation of N-carboxy-a-aminoacid anhydride(NCA) by a primary amino group 3) activated aluminum alkyl and zinc alkyl 4) initiation of stereospecific polymerization of methyloxirane and 5) comparison of stereospecific polymerization of methyloxirane with Ziegler-Natta polymerization. A comprehensive interpretation is proposed for chemistry of reactivity and/or stereospecificity of organometallic compounds in ionic polymerizations. 

Many examples of the formation of new six-membered rings containing a nitrogen atom in the reaction of isatoic anhydrides with ketones, diketones, various ether derivatives, lactones, and organometallic compounds are known. Thus, the anhydrides 2 and 34 condense with acetophenones and co-methoxyacetophenones in the presence of lithium diisopropylamide at low temperatures with the formation of derivatives of quinolone 35 [17, 18],... 

Synthesis of homoallylic alcohols through the reaction of organometallic allyl compounds with carbonyl compounds is one of the most important processes in organic synthesis. Sc(OTf)3-catalyzed allylation of aldehydes with tetraallyltin to prepare homoallylic alcohols has been reported. Recently, it was revealed that the addition of acetic anhydride to the reaction mixture dramatically increases the reaction s yields to more than 90% [10]. On the other hand, in the presence of a catalytic amount of Sc(OTf)3 (l-5mol%), benzoylhydrazines reacted with tetraallyltin to give the corresponding homoallylic hydrazines, which were readily converted to homoallylic amines (Scheme 12.6) [11]. Three-component reactions of aldehydes, benzoylhydrazine, and tetraallyltin also proceeded smoothly in the presence of a catalytic amount of Sc(OTf)3. 

Various basic (nucleophilic) initiators can be used to initiate anionic polymerization, including covalent or ionic metal amides, alkoxides, hydroxides, cyanides, phosphines, amines, and organometallic compounds such as butyllithium. The polymerization is initiated by addition of the initiating species to the monomer, typically a vinyl compound with electron-withdrawing moieties. In anionic ROPs, cyclic monomers with electron-deficient carbon atoms such as amides (lactams) and esters (lactones), ethers (oxiranes), or Leuchs anhydrides are used as monomers (Scheme 13). 

The mechanism for organometallics and Lewis acids in phenolic or anhydride cured epoxy molding compounds are still not fully understood. Lewis bases such as imidazoles can be reacted with organic acids to form salts in order to improve latency. Imidazoles are, so far, the most widely accepted as a compatible catalyst family for encapsulating microelectronics. 

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