O. Temmem et al. / Tetrahedron Letters 43 (2002) 3169–3173
3173
336-033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
7. The geranyl and the neryl esters described in this letter
were prepared quantitatively by dropwise addition at 0°C
of the acid chloride to an ether solution of geraniol (res.
nerol; Fluka®) and pyridine (7b–c), or DMAP (7a), and
were freshly purified prior to use by either distillation
(7b–c) or chromatography (7a). Protocol for ‘kinetic’ IC
conditions: To the cooled (ca. −78°C) mixture resulting
from addition of 1.6 M (in hexane) n-BuLi (1.1 equiv.) to
a solution of i-propyl-cyclohexylamine (0.5 ml) in THF (5
ml) at 0°C was added TMSCl (2.6 ml; 8 equiv.) diluted
with THF (5 ml), followed immediately by the ester (2.5
mmol) in the same solvent (5 ml). After stirring (ca. 2
min), excess triethylamine (5 ml) was added. The tempera-
ture was maintained at −78°C for 10 min, then allowed to
rise gradually to ca. 20°C followed by refluxing for 5 h.
After cooling, the reaction mixture was added dropwise to
iced 10% HCl (50 ml), and extracted with ether (3×20 ml).
The combined organic layers were extracted with 1N
NaOH (3×20 ml). The aqueous phases thus generated were
combined, acidified to pH 1 with 5N HCl, then back-
extracted with CH2Cl2 to afford, after drying (MgSO4) and
evaporation, the rearranged acid as a pale yellow oil.
Protocol for the ‘thermodynamic’ conditions: strictly identi-
cal to that described by Ireland in Ref. 4.
www.ccdc.cam.ac.uk).
9. Selected data: (R,S/S,R)-7c: H NMR: 1.07 (s, 3H), 1.11
1
(d, J=7 Hz, 3H), 1.32–1.52 (m, 2H), 1.58 (s, 3H), 1.67 (s,
3H), 1.75–2 (m, 2H), 2.45 (q, J=7 Hz, 1H), 4.92–5.13 (m,
3H), 5.89 (dd, J=11, 17.5 Hz, 1H; Hv); 13C NMR: 12.4,
17.5, 18.9, 22.7, 25.6, 38.8, 41.6, 48.3, 113.6, 124.5, 131.3,
1
143.3, 181.9; (R,R/S,S)-7c: H NMR: 1.09 (m, 6H), 1.35–
1.5 (m, 2H), 1.58 (s, 3H), 1.67 (s, 3H), 1.84–1.98 (m, 2H),
2.48 (q, J=7 Hz, 1H), 4.94–5.16 (m, 3H), 5.68 (dd, J=11,
1
17.5 Hz, 1H; Hv); 11: H NMR: 0.84 (s, 3H), 1.1 (d, J=7
Hz, 3H), 1.53–1.57 (m, 4H), 2.47 (q, J=7 Hz, 1H), 3.13–
3.36 (m, 2H), 3.45–3.5 (m, 2H), 4.37 (dd, J=3.5, 9.5 Hz,
1H), 4.51 (s, 2H), 7.29–7.37 (m, 5H); (R,S–S,R)-7b: 1H
NMR: 0.95 (d, J=6.7 Hz, 3H), 1.05 (d, J=7 Hz, 3H), 1.14
(s, 3H), 1.32–1.54 (m, 2H), 1.57 (s, 3H), 1.66 (d, J=1 Hz,
3H), 1.81–1.95 (m, 2H), 1.97–2.07 (m, 1H), 2.24 (d, J=4.4
Hz, 1H), 4.97 (dd, J=1.4, 17.5 Hz, 1H), 5.03–5.12 (m,
2H), 6.07 (dd, J=10.9, 17.5 Hz, 1H; Hv); 13C NMR: 17.6,
20.2, 20.8, 22.8, 24.3, 25.7, 27.5, 39.6, 42, 60.9, 113.2,
124.6, 131.3, 144.1, 180.5; (R,R-S,S)-7b: 1H NMR: 0.95
(d, J=6.7 Hz, 3H), 1.01 (d, J=7 Hz, 3H), 1.19 (s, 3H),
1.34–1.46 (m, 2H), 1.66 (d, J=0.9 Hz, 3H), 1.81–2.04 (m,
3H), 2.25 (d, J=4.4 Hz, 1H), 4.95–5.13 (m, 1H), 5.77 (dd,
1
J=10.9, 17.5 Hz, 1H; Hv); Z-8a: H NMR: 0.95 (d, J=7
8. Crystal data for 11 (mp 58–60°C): C17H23IO3, mol.
weight=402.28, triclinic, space group P-1, a=7.267(2),
Hz, 3H), 1–1.1 (m, 21H), 1.6 (s, 3H), 1.68 (s, 3H), 1.76 (d,
J=1 Hz, 3H), 2.03–2.17 (m, 6H), 2.45–2.57 (m, 1H), 3.49
(dd, J=6, 9.5 Hz, 1H), 3.63 (dd, J=5.3, 9.5 Hz, 1H), 4.56
(d, J=7.2 Hz, 2H), 5.08–5.13 (m, 1H), 5.35 (dt, J=1, 7.2
Hz, 1H); 13C NMR: 12, 16.8, 17.7, 18.1, 23.6, 25.7, 26.7,
32.3, 33.4, 38.3, 60.7, 67.7, 119.4, 123.7, 131.8, 142.4,
174.4; (R,S)-7a, methyl ester: 1H NMR: 1.01–1.18 (m,
24H), 1.12 (s, H), 1.23–1.36 (m, 2H), 1.56 (s, 3H), 1.65 (s,
3H), 1.83–2.02 (m, 3H), 2.35 (d, J=5 Hz, 1H), 3.2–3.35
(m, 1H), 3.6 (s, 3H), 3.8 (dd, J=3.5, 9.7 Hz, 1H), 4.9–5.11
(m, 3H), 6.03 (dd, J=17.5, 10.9 Hz, 1H); 13C NMR: 12,
17, 18.1, 19, 20.1, 22.8, 25.7, 35.3, 39.6, 42.2, 50.8, 58.6,
66.6, 113.1, 124.6, 131.4, 144.1, 174.1; 14: (400 MHz, in
C6D6): 0.52 (d, J=7 Hz, 3H), 0.92 (s, 3H), 1.23–1.42 (m,
4H), 1.6 (s, 3H), 1.68 (s, 3H), 1.7–1.83 (m, 2H), 1.92 (d,
J=5 Hz, 1H), 1.97–2.11 (m, 1H), 3.06 (dd, J=5.5, 8.5 Hz,
1H), 3.66 (t, J=8.5 Hz, 1H), 4.78–4.96 (m, 2H), 5.19–5.24
(m, 1H), 5.7 (dd, J=17.5, 10.9 Hz, 1H). Excepted as
,
b=10.183(3), c=12.322(3) A, h=79.54(2), i=78.82(2),
3
k=87.40(2)°, V=882.5(4) A , Z=2, Dcalcd=1.51 g cm−3
,
,
v(Mo Ka)=1.82 mm−1. Data were collected using a Non-
ius Mach3 diffractometer, graphite monochromated
,
MoKa radiation (u=0.7173 A) at room temperature. 3781
reflections were collected using a crystal of 0.40×0.40×0.38
mm3. Absorption corrections based on c-scans were
applied. The structure was solved using direct methods
and refined with 2022 reflections having I>3|(I). Atom C7
is disordered over two positions in the ratio 1/1. Hydrogen
atoms were introduced as fixed contributors at their com-
,
puted coordinates (d(C–H)=0.95 A, B(H)=1.3) with the
exception of the C7 protons, omitted. Full matrix refine-
,
ments against ꢀFꢀ. Final results: R(F)=0.039 A, Rw(F)=
0.060, GOF=1.24, largest peak in final difference=0.83 e
−3. Crystallographic data for the structural analysis have
,
A
1
otherwise stated, H and 13C NMR at 200 and 50 MHz in
been deposited with the Cambridge Crystallographic Data
Centre for compound 11. Copies of this information may
be obtained free of charge from the Director, CCDC, 12
Union Road, Cambridge, CN2 1EZ, UK (fax: +44-1223-
CDCl3, respectively. The results presented in this letter are
taken in part from the thesis dissertation of Olivier
Temmem (Strasbourg, December 2000).