References and Notes
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Tanaka A.
Tanaka R.
Uda H.
Yoshikoshi A.
J. Chem. Soc., Perkin Trans. 1
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Velazco MI,
Wuensche L, and
Deladoey P. inventors; US
Patent, 6214788.
; Chem. Abstr. 2000, 133, 265959
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Torri S.
Okamoto T.
Bull.
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1976,
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<A NAME="RS03609ST-3B">3b</A> See also:
Piers E.
Britton RW.
de Wall W.
Can. J. Chem.
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Fürstner A.
Hannen P.
Chem. Eur. J.
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Fehr C.
Galindo J.
Angew. Chem. Int. Ed.
2006,
45:
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Hodgson DM.
Chung YK.
Paris J.-M.
J. Am.
Chem. Soc.
2004,
126:
8664
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Hodgson DM.
Chung YK.
Nuzzo I.
Freixas G.
Kulikiewicz KK.
Cleator E.
Paris J.-M.
J. Am. Chem. Soc.
2007,
129:
4456
<A NAME="RS03609ST-7">7</A> For a recent example in natural product
synthesis, see:
Tashiro T.
Mori K.
Tetrahedron: Asymmetry
2008,
19:
1215
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Nwaukwa SO.
Keehn PM.
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Malkov AV.
Baxendale IR.
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Fawcett J.
Russell DR.
Mansfield DJ.
Valko M.
Kocovsky P.
Organometallics
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<A NAME="RS03609ST-9A">9a</A> Formylation
using HCO2Et-NaH is known to lead to
cis-11 preferentially
(S:R = 7:93
at C-6), see:
Kashima C.
Miwa Y.
Shibata S.
Nakazono H.
J.
Heterocycl. Chem.
2002,
39:
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<A NAME="RS03609ST-9B">9b</A> For kinetic formylation,
see:
Zayia
GH.
Org.
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1999,
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989
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Dreiding AS.
Hartman JA.
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<A NAME="RS03609ST-11">11</A>
Characterisation Data for (3R,6S)-6-Isopropyl-3-methyl-
2-methylenecyclohexanol
(12): [α]D
²5 -100.9
(c = 1.42, CHCl3).
IR: 3480 (br), 3067 (w), 2958 (s), 2933 (s), 2870 (m), 1644 (w),
1475 (w), 1450 (w), 1029 (m), 948 (m), 905 (s) cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 5.02 (d, J = 1.0 Hz, 1 H, =CH2),
4.73 (d, J = 1.5 Hz, 1 H, CH2),
3.83 (br s, 1 H, CHOH), 2.20-2.29
(m, 1 H, CHMe2), 1.94-2.03
(m, 1 H, CHMe), 1.79-1.84 (m,
1 H, H-4a), 1.62-1.71 (m, 1 H,
H-5a), 1.56 (d, J = 5.5, 1 H, OH), 1.17-1.29
(m, 2 H, H-5b, H-6), 1.09 (d, J = 6.5
Hz, 3 H, CHMe), 0.95-1.02 (m,
1 H, H-4b), 0.93 (d, J = 7.0
Hz, 3 H, Me of CHMe2), 0.87 (d, J = 7.0
Hz, 3 H, Me of CHMe2). ¹³C
NMR (100 MHz, CDCl3): δ = 156.9 (=C),
100.6 (=CH2), 74.3 (COH), 51.9 (C-6), 36.7 (CHMe), 35.9 (C-4), 26.5 (CHMe2), 23.0 (C-5), 20.9 (Me
of CHMe2), 18.1 (CHMe), 15.8
(Me of CHMe2). MS (CI+):
m/z (%) = 152
(11), 151 (100), 150 (4). HRMS (CI): m/z
[M - OH]+ calcd
for C11H19: 151.1487; found: 151.1488.
<A NAME="RS03609ST-12">12</A>
Gu Y.
Snider BB.
Org. Lett.
2003,
5:
4385
<A NAME="RS03609ST-13">13</A>
Hodgson DM.
Chung YK.
Paris J.-M.
Synthesis
2005,
2264
<A NAME="RS03609ST-14">14</A>
(1R,4R,5R,6R,7S,10R)-7-Isopropyl-10-methyltricyclo- [4.4.0.0¹,5]decan-4-ol
(15): n-BuLi
(1.6 M in hexanes, 3.75 mL, 6.0 mmol) was added to a stirred solution
of 2,2,6,6-tetramethylpiperidine (1.0 mL, 6.0 mmol) in t-BuOMe (30 mL) at -78 ˚C.
The resulting pale yellow solution of LTMP was stirred at r.t. for
15 min and then cooled to 0 ˚C in an ice-bath. To a stirred
solution of epoxide 6 (593 mg, 2.85 mmol) in t-BuOMe (14 mL) at 0 ˚C was
added the above LTMP solution dropwise via a cannula over 3 h. The
reaction mixture was stirred at r.t. for 17 h, then MeOH (3 mL)
was added, the mixture was evaporated under reduced pressure and
the residue dry-loaded onto a small amount of SiO2 and purified
by column chromatography (SiO2, gradient elution, 20-35% Et2O-PE)
to give a white solid, cyclopropyl alcohol 15 (534
mg, 90%); R
f
0.4 (40% Et2O-PE);
mp 74-76 ˚C; [α]D
²5 -10.7
(c = 0.33, CHCl3).
IR: 3608 (w), 3447 (br), 3018 (m), 2958 (m), 2928 (m), 2870 (m),
1385 (w), 1371 (w), 1216 (s) cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 4.22 (br
s, 1 H, CHOH), 2.00-2.07 (m,
1 H, H-2a,), 1.79-1.88 (m, 1 H, H-10), 1.60-1.65
(m, 1 H, H-9a), 1.50-1.59 (m, 2 H, CHMe2, H-3a),
1.38-1.45 (m, 3 H, H-2b, H-3b, H-8a), 1.20 (d, J = 4.5 Hz, 1 H, OH), 1.02-1.09
(m, 1 H, H-7), 1.00 (d, J = 6.5
Hz, 3 H, CHMe), 0.91-0.93 (m,
1 H, H-5), 0.91 (d, J = 7.0
Hz, 3 H, Me of CHMe2), 0.87 (d, J = 7.0
Hz, 3 H, Me of CHMe2), 0.82-0.85 (m, 1 H, H-8b),
0.52-0.60 (m, 1 H, H-9b), 0.38 (t, J = 3.0
Hz, 1 H, H-6). ¹³C NMR (100 MHz, CDCl3): δ = 75.1 (C-4),
44.1 (C-7), 35.5 (C-5), 34.5 (C-1), 33.5 (C-10), 31.6 (C-3), 31.4
(C-9), 29.9 (CHMe2), 28.6
(C-2), 26.5 (C-8), 24.5 (C-6), 20.0 (CHMe),
19.6 (Me of CHMe2), 19.1 (Me of CHMe2). MS
(CI+): m/z (%) = 208 (10) [M]+,
191 (100) [M - OH]+.
HRMS (CI): m/z [M - OH]+ calcd
for C14H23: 191.1800; found: 191.1811.
<A NAME="RS03609ST-15">15</A>
Characterisation data for (1S,4S,5S,6S,7S,10R)-7-Isopropyl-10-methyltricyclo[4.4.0.0¹,5]decan-4-ol
(17): [α]D
²5 +28.0
(c = 1.0, CHCl3).
IR: 3310 (br), 2954 (s), 2971 (s), 1470 (m), 1443 (w), 1383 (w),
1327 (w), 1057 (w), 974 (s) cm-¹.
¹H
NMR (400 MHz, CDCl3): δ = 4.21 (d, J = 5.0 Hz, 1 H, CHOH), 1.95-2.03 (m, 1 H, H-2a),
1.88-1.94 (m, 1 H, H-10), 1.69-1.72 (m, 1 H, H-3a),
1.46-1.62 (m, 3 H, H-7, H-8a, H-9a), 1.32-1.43
(m, 3 H, CHMe2, H-2b, H-3b),
1.08 (d, J = 7.0 Hz, 3 H, CHMe), 1.01 (d, J = 3.5
Hz, 1 H, H-5), 0.92 (d, J = 6.5
Hz, 3 H, Me of CHMe2), 0.89 (d, J = 6.5
Hz, 3 H, Me of CHMe2), 0.86-0.88 (m, 1 H, H-9b),
0.71-0.84 (m, 1 H, H-8b), 0.68 (t, J = 4.2,
1 H, H-6). ¹³C NMR (100 MHz, CDCl3): δ = 75.6
(C-4), 40.3 (C-7), 33.2 (C-10), 33.0 (C-3), 32.9 (C-5), 32.4 (C-1),
31.5 (C-2), 31.2 (CHMe2),
28.6 (C-9), 23.55 (C-6), 23.5 (C-8), 20.8 (Me of CHMe2),
20.7 (Me of CHMe2), 20.5 (CHMe).
MS (CI+): m/z (%) = 193 (1), 192 (13),
191 (100) [M - OH]+,
190 (26), 189 (37). HRMS (CI): m/z [M - OH]+ calcd
for C14H23: 191.1800; found: 191.1806.
