Synthesis and chemistry of 1,4-oxathianes and 1,4-oxathian-3-ones.
The exploration of possible routes towards the synthesis of alkylated
oxathiane and oxathianone systems are presented in this research thesis. The
ultimate objective of these studies was the synthesis of dihydrofurans and
dihydrofuranones via the Ramberg-Backlund rearrangement.
Initially, studies were carried out on the alkylation of the cyclic ether,
1,4-oxathiane S.S-dioxide. It was during investigations with the readily available
cyclic ether that several ring-opened novel compounds were synthesised.
Subsequently, an alkylated epoxide was prepared and two pathways from this
epoxide to the synthesis of an alkylated 1,4-oxathiane S.S-dioxide were examined.
The first involved an examination influencing the regioselectivity of the epoxide
and consequent ring-opening to yield the corresponding hydroxy sulfide. Further
studies explored the possibility of either ring closure of the sulfide followed by
oxidation to the sulfone or oxidation to the sulfone followed by cyclization.
However, these routes were to prove unsuccessful. The second pathway involved
the use of a readily available epoxide for the afore mentioned
The preparation of oxathianones was the second part of these studies and
involved the synthesis of the lactone 1,4-oxathian-3-one S.S-dioxide again with
the aim of alkylating this sulfone for use as the precursor required in the Ramberg-
Backlund reaction. Investigations included acid/alcohol cyclizations and catalytic
Another sequence of reactions available to us was the direct oxidation of a
hydroxy diol and/or lactol oxidation to the lactone. However, it was during this
research towards the synthesis of the sulfone lactone that four unexpected and
novel compounds were synthesised.
The latter part of our studies took us to the preparation of an alkylated
oxotetrahydrothiophene S.S-dioxide with the intention of performing the Baeyer-
Villiger oxidation to the requisite lactone. However, success came with the
double alkylation of the system rather than the mono-alkylation.