AlkylAryl Halides

Arbusov reactions have been observed with many different types of reactive halogeno compounds, e.g. with polyhalogeno-alkanes, esters of haJogenocarboxylic acids, alkylaryl halides and certain heterocyclic halides. Acetyl chloride and benzoyl chloride react at room temperature to give esters of the corresponding acetyl and benzoyl phosphonic esters. ... 

Organophosphorus compounds. Phosphorus-carbon bond fonnation takes place by the reaction of various phosphorus compounds containing a P—H bond with halides or tritlates. Alkylaryl- or alkenylalkylphosphinates are prepared from alkylphosphinate[638]. The optically active isopropyl alkenyl-methylphosphinate 778 is prepared from isopropyl methylphosphinate with retention[639]. The monoaryl and symmetrical and asymmetric diarylphosphi-nates 780, 781, and 782 are prepared by the reaction of the unstable methyl phosphinate 779 with different amounts of aryl iodides. Tnmethyl orthoformate is added to stabilize the methyl phosphinate[640]. 

In a Kumada-Corriu reaction, an aryl halide is oxidatively coupled with a homogeneous nickel(ll)-phosphine catalyst [2], This species reacts with a Grignard reagent to give biaryl or alkylaryl compounds. Later, palladium-phosphine complexes were also successfully applied. By this means, stereospecific transformations were achieved. 

Carbon monoxide rapidly inserts into the carbon—zirconium bond of alkyl- and alkenyl-zirconocene chlorides at low temperature with retention of configuration at carbon to give acylzirconocene chlorides 17 (Scheme 3.5). Acylzirconocene chlorides have found utility in synthesis, as described elsewhere in this volume [17]. Lewis acid catalyzed additions to enones, aldehydes, and imines, yielding a-keto allylic alcohols, a-hydroxy ketones, and a-amino ketones, respectively [18], and palladium-catalyzed addition to alkyl/aryl halides and a,[5-ynones [19] are examples. The acyl complex 18 formed by the insertion of carbon monoxide into dialkyl, alkylaryl, or diaryl zirconocenes may rearrange to a r 2-ketone complex 19 either thermally (particularly when R1 = R2 = Ph) or on addition of a Lewis acid [5,20,21]. The rearrangement proceeds through the less stable... 

Tertiary phosphines form a wide range of complexes of the type PtX2(PR3)2 (X - halide, pseudohalide R = alkyl, aryl or mixed alkylaryl). Space limitations preclude this chapter becoming a compendium of known compounds, therefore for each individual complex the reader is directed to Chemical Abstracts, Gmelin or the book by McAuliffe which contains extensive tabulations of compounds.1225 In this chapter we outline the general methods of synthesis, the properties, and the structures and spectral features which we expect to be found with this class of compounds. 

---