Allylic substitution miscellaneous reactions

The categories of sequentially Pd-catalyzed processes in this chapter are based upon the initial process. These are Heck reactions, allylic substitutions, aminations, Sonogashira couplings, metallations, CH activations, cycloisomer izations and miscellaneous processes. 

Miscellaneous.- A simple method to resolve racemic l,l -binaphthalene-2,2 -diol involves reaction with menthyl phosphorodichloridite (139) and separation of the diastereomeric phosphites by crystallisation from ether. The new cyclic chlorodiaminophosphine (140), prepared in and two new cyclic triaminophosphines (141) have been used to determine the enantiomeric purity of chiral alcohols, thiols, and amines by means of Ip n.m.r. New optically pure phosphites used for Rh catalysed asymmetric hydroformylation reactions are (142), two diastereomers of (143), and (144) the diphosphinite (145) was similarly employed. Some new cyclic aminophosphines (146) were prepared for use as ligands in asymmetric Pd catalysed allylic substitution reactions. 

Miscellaneous Copper-Catalyzed Allylic Substitution Reactions... 

With Miscellaneous Compounds. Several mechanistic studies have been performed recently on reactions of "auxiliary stabilizers with 4-chloro-2-hexene, both in the presence and in the absence of metal salts (82,87,88, 89,90). The stabilizers used were phosphites (82,87), phosphines (82,87), epoxides (88), 2-phenylindole (89), and the bis(j8-aminocrotonate) ester of 1,4-butanediol (90). Important mechanistic features delineated in this work included substitutive removal of allylic... 

Miscellaneous Applications. The chemoselective oxidation of alcohols and diols using T 0-i- r)Jt-Butyl Hydroperoxide has been reported. The title reagent has also been employed as a catalyst in Diels-Alder reactions and as an additive in the palladium-catalyzed reaction of aryl-substituted allylic alcohols with zinc enolates of p-dicarbonyl compounds (eq 24). The latter... 

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