M. Yus, F. Foubelo / Tetrahedron Letters 42 (2001) 2469–2472
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References
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OH
SH
i
S
4c
7c (74%)
4. Review: Yus, M.; Foubelo, F. Rev. Heteroat. Chem.
OH
OH
1997, 17, 73.
i
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8fc (62%)
6fc
Scheme 2. Reagents and conditions: (i) H3PO4 (85%), PhMe,
110°C, 4 h.
OH
OEt
i
OEt
O
O
6fd
8fd (50%)
Scheme 3. Reagents and conditions: (i) TsOH (cat.), PhMe,
110°C, 4 h.
however, the diol 6fc did not lead to the oxygenated
heterocycle but the conjugate diolefin 8fc resulted from
a double dehydration (Scheme 2).
Similarly, the hydroxy ester 6fd was treated with a
catalytic amount of p-toluenesulfonic acid in toluene at
reflux for 4 h. The expected nine-membered lactone was
not isolated, compound 8fd being the major isolated
reaction product in this case (Scheme 3).
From the results described here, we conclude that sulfe-
nyl alcohols 4 and difunctionalised biphenyls 6 can be
readily accessible from 1,7-dihydrodibenzothiepin (1)
through a tandem monolithiation reaction with elec-
trophiles or a double sequential lithiation reaction with
electrophiles, respectively. It is noteworthy that the
double lithiation process (giving intermediates of type
5) has not been observed for the corresponding oxygen-
or nitrogen-containing heterocyclic compounds of type
1.10 Finally, the sulfenyl alcohols 4 can be precursors of
the corresponding sulfur-containing eight-membered
rings through a dehydration process.
Acknowledgements
This work was financially supported by the DGES from
the Spanish Ministerio de Educacio´n y Cultura (MEC)
(project no. PB-97-0133).