Synthesis and Comparison of the Reactivity of Allyl Fluorides and ...

Alcohol Product Yield (%)
Table 2.7 Reactions of aryl allylic alcohols with Moffatt-Swern reagent
2.2 Results and Discussion
49
65
73
83
Chapter Two
In this chapter analogous libraries of allylic fluorides and allylic chlorides were synthesised
utilising literature protocols. These compounds were then utilised in Chapter Three in order
to synthesise novel palladium allyl complexes. Previously, work conducted by Hintermann
and Togni [48] has examined the reaction of 1,3-diphenylallylfluoride with Pd(0). However,
this work will investigate the reaction in more detail, and determine whether substituents on
the ring influence the reactivity of allylic halides with Pd(0) and the subsequent reactions
with nucleophiles.
2.2.1 Synthesis of Allyl Fluorides
In contrast to literature reports, initial attempts to prepare allyl fluorides via nucleophilic
substitution with fluoride in protic solvents, failed to afford the desired products. In view of
the problems and product mixtures highlighted above, in this work, we have focussed on the
electrophilic synthetic protocols.
The synthetic route undertaken by Gouverner [18] in preparing allylic fluorides was via a two-
step process. Firstly, the cross-metathesis of allyltrimethylsilane with varying olefenic
partners, followed by fluorodesilylation of the corresponding allylsilane with Selectfluor.