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<A NAME="RG15908ST-21">21</A>
General Procedure
for Fujiwara-Moritani Cyclization
A flame-dried
reaction vessel equipped with a magnetic stir bar is charged with
Pd(OAc)2 (10 mol%) as well as the indicated
ligand L2-8 (30
mol%) and subsequently evacuated and then backfilled with
O2 if used as oxidant (three cycles). Otherwise, a solution
of the indole and tert-amyl alcohol (0.125
M) and AcOH (0.25 mL per mL of tert-amyl
alcohol) are consecutively added. The reaction mixture is maintained
at r.t. until a homogeneous tawny solution forms. Then, the oxidant
(1.0 equiv), PhCO3
t-Bu or
1,4-benzoquinone, is added, and the resulting reaction mixture is heated
at 80 ˚C for 15 h (under O2 atmosphere
with O2 as the oxidant). After cooling to r.t., the reaction
mixture is diluted with MTBE and poured into H2O. The
organic layer is separated and washed with sat. aq NaHCO3 and
brine. The aqueous phase is extracted with MTBE and the combined organic
extracts are dried over Na2SO4. The solvents
are evaporated under reduced pressure, and the residue is purified
by flash column chromatography on SiO2 using cyclohexane-MTBE
solvent mixtures.
Detailed procedures and characterization
data will be reported elsewhere. See:
<A NAME="RG15908ST-22A">22a</A>
L2:
Bolm C.
Weickhardt K.
Zehnder M.
Ranff T.
Chem.
Ber.
1991,
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L3-8 were prepared on the basis of a reported
sequence:
Oila MJ.
Tois JE.
Koskinen AMP.
Tetrahedron
2005,
61:
10748
<A NAME="RG15908ST-23A">23a</A>
Analytical Data for (
Z
)- or (
E
)-1-Methyl-3-(3-methylpent-3-enyl) indole [(
Z
)-1 or (
E
)-1]
¹4a
(Z)-1 (Z/E > 99:1): ¹H
NMR (300 MHz, CDCl3): δ = 1.62
(d, J = 6.7
Hz, 3 H), 1.82-1.86 (m, 3 H), 2.48 (br t, J = 8.4
Hz, 2 H), 2.83-2.91 (m, 2 H), 3.78 (s, 3 H), 5.32 (q, J = 6.7 Hz, 1
H), 6.90 (s, 1 H), 7.13-7.20 (m, 1 H), 7.24-7.31
(m, 1 H), 7.31-7.36 (m, 1 H), 7.68 (ddd, J = 7.8,
1.7, 0.9 Hz, 1 H) ppm. ¹³C NMR (75
MHz, CDCl3): δ = 13.3,
23.4, 23.5, 32.5, 32.5, 109.1, 115.3, 118.5, 118.9, 119.2, 121.4,
125.8, 127.9, 136.1, 137.0 ppm.
(E)-1 (E:Z > 99:1): ¹H
NMR (300 MHz, CDCl3): δ = 1.67 (dq, J = 6.7, 1.0
Hz, 3 H), 1.77 (m, 3 H), 2.39-2.49 (m, 2 H), 2.87-2.94
(m, 2 H), 3.78 (s, 3 H), 5.37 (qq, J = 6.8,
1.3 Hz, 1 H), 6.88 (s, 1 H), 7.16 (ddd, J = 8.0,
6.8, 1.3 Hz, 1 H), 7.27 (ddd, J = 8.2,
6.8, 1.2 Hz, 1 H), 7.33 (ddd, J = 8.2,
1.1, 0.9 Hz, 1 H), 7.66 (ddd, J = 7.8,
0.9 Hz, 1 H) ppm. ¹³C NMR (75 MHz,
CDCl3): δ = 13.4,
15.8, 24.0, 32.5, 40.5, 109.0, 115.3, 118.4, 118.4, 119.0, 121.3,
125.8, 127.9, 135.9, 136.9 ppm.
<A NAME="RG15908ST-23B">23b</A>
Analytical
Data for (-)-3,4-Dimethyl-3-vinyl-1,2,3,4-tetrahydrocyclopenta[
b
]indole [(-)-2]
[α]D
²0 -17.7
(c 0.565, CHCl3) for 44% ee
(Table
[³]
, entry
2). HPLC (Daicel Chiralcel IB column using n-heptane
at 15 ˚C): t
R = 13.9
min (minor enantiomer) and 16.1 min (major enantiomer). IR (film):
3052 (m), 2926 (s), 2854 (s), 1465 (s) cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 1.50
(s, 3 H), 2.36 (ddd, J = 13.0,
7.1, 6.1 Hz, 1 H), 2.47-2.58 (m, 1 H), 2.83 (m, 2 H), 3.64
(s, 3 H), 4.98 (dd, J = 17.4,
1.3 Hz, 1 H), 5.06 (dd, J = 10.5,
1.2 Hz, 1 H), 6.09 (dd, J = 17.4,
10.5 Hz, 1 H), 7.09 (ddd, J = 7.5,
7.1 Hz, 1.3 Hz, 1 H), 7.16 (ddd, J = 8.2,
7.0, 1.4 Hz, 1 H), 7.26 (ddd, J = 8.1,
0.9, 0.8 Hz, 1 H), 7.47 (ddd, J = 7.6,
1.3, 0.7 Hz, 1 H) ppm. ¹³C NMR (75 MHz,
CDCl3): δ = 22.5,
23.7, 30.0, 46.0, 46.3, 109.3, 111.8, 117.3, 118.8, 119.0, 120.2,
123.9, 141.6, 145.1, 148.7 ppm. ESI-HRMS: m/z calcd
for C15H17NNa: 234.1259; found: 234.1253.
Anal. Calcd for C15H17N: C, 85.26; H, 8.11;
N, 6.63. Found: C, 84.97; H, 8.20; N, 6.54.
