Synthesis Menthadienol
Synthesis Menthadienol
Synthesis Menthadienol
42
Geraniol (1) and nerol (2) undergo a novel cyclization to cis-p-mentha-2,8-dien-1-ol (4) by reaction with tris(pbromophenyl)ammoniumyl radical cation (3) and the reaction mechanism is discussed.
Tris(p-bromophenyl)ammoniumyl
hexachloroantimonate
(TBPA+.SbCl
6 , 3) has been used as a one-electron oxidant in
a variety of electron transfer reactions. Investigations have
shown that 3 can initiate some radical cation cycloadditions,
such as the DielsAlder reaction,1 cyclopropanation2 and
Cope rearrangement.3 We have studied the radical cation
initiated cyclization of squalene with 3.4 In this article, we
wish to report a novel cyclization of the monoterpenol geraniol (1) and nerol (2) to cis-p-mentha-2,8-dien-1-ol (4) by 3,
which is reduced to the neutral tris(p-bromophenyl)amine
(TBPA) (Scheme 1).
Br
Br
+
OH
SbCl6
OH
OH
Br
3 (TBPA+SBCl6)
OH
1 or 2
Scheme 1
3 +
1 or 2
H+
excess of 3 +
+H+
43
We are grateful to the National Natural Science Foundation of China for financial support.
Received, 23rd July 1997; Accepted, 22nd September 1997
Paper E/7/05326F
Scheme 2
References
The radical cation intermediate formed initially undergoes
cyclization, deprotonation and dehydrogenation (by excess of
3+.) to give a cyclic triene, which protonates to form the
carbocationic intermediate 6. Attack by a water molecule at
the cationic centre opposite the isopropenyl group and
deprotonation would produce 4.
Experimental
Melting points were uncorrected. Elemental analyses were
carried out on an Italian-1106 elemental analytical apparatus. IR
spectra were recorded on a Nicolet FT-170SX spectrometer. 1H
and 13C NMR and 13C-DEPT spectra were obtained on a Bruker
DMX-500 spectrometer (500.0 MHz for 1H NMR, 125.0 MHz for
13
C NMR and 13C-DEPT) using [2H6]DMSO as solvent and tetramethylsilane (TMS) as internal reference. Mass spectra were
determined on a VG-ZAB-HS mass spectrometer (EI).
1 and 2 were purchased from TCI Chemical Co. and used without further purification. Compound 3 was synthesized as
described;11 mp 143144 C (decomp.) (Found: C, 26.58; H, 1.46.
C18H12Br3Cl6NSb requires C, 26.50; H, 1.50%). All solvents were
purified and dried according to standard procedures.12
cis-p-Mentha-2,8-dien-1-ol (4). To a solution of 1 or 2 (2.0 mmol)
in anhydrous acetonitrile (35.0 ml) 3 (4.8 mmol) was added. The
mixture was stirred at room temperature for 2 h under argon and
checked by TLC. It was then poured into saturated sodium carbonatemethanol solution (15.0 ml), and extracted with trichloromethane (total 75 ml). The organic layer was washed with water and
dried with anhydrous magnesium sulfate and the solvent was
removed. The oily residue was separated by column chroma-
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