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The synthesis and unique reactivity of a series of arylsulfonate-based nucleophile assisting leaving groups (NALG) containing oligomeric ether units attached to the arylsulfonyl in the ortho orientation are described. The reactions of a variety of these ether-containing alkyl sulfonates with metal halides proceeded at substantially greater rates ether-electronically similar sulfonates.

A study of the role of base in the isomerization of manganese-coordinated conjugated alkynyl carbonyls to the corresponding allenyl carbonyls is described. A series of amine bases is also examined for their efficacy in the isomerization revealing a strong dependence on pK(sub a).

A series of arylsulfonate nucleophile assisting leaving groups (NALGs) are prepared in which the metal chelating unit is attached to the aryl ring via an ether linker. The NALGs have displayed significant rate enhancements in halogenation reactions using metal halides and the studies have shown that rate enhancements of these nucleophilic halogenation reactions are facilitated by stabilization of charge in the transitions state rather than through strong precomplexation with metal cation.

The stereospecificity and utility of the sulfonate/TiCl4 technique in the synthesis of a variety of alkyl chlorides are demonstrated. This technique offers an important alternative to existing methods for the synthesis of secondary alkyl chlorides with retention of configuration.