J. A. Schiffner, T. H. Wöste, M. Oestreich
FULL PAPER
colourless liquid. Rf = 0.45 (cyclohexane/tert-butyl methyl ether =
(+)-1-Methyl-1-vinyl-2,3-dihydro-1H-pyrrolizine [(+)-42]: According
99:1). IR (ATR): ν = 3053 (w, Ar–H/=C–H), 2928 (s, C–H), 2840
to the general procedure (15 h); yield 12.6 mg, 42% (58%), yellow
˜
1
(m, C–H), 1471 (s, C=C) cm–1. H NMR (300 MHz, CDCl3): δ =
oil. Rf = 0.33 (cyclohexane/tert-butyl methyl ether = 30:1). [α]2D0
=
1.53 (s, 3 H, 1-CH3), 1.68–1.90 (m, 4 H, 2-H, 3-H), 2.73–2.79 (m, +6.7 (c = 1.025, CHCl3, 70% ee, contaminated with cyclization
3
2
1
2 H, 4-H), 3.69 (s, 3 H, 9-CH3), 4.90 (dd, JH,H = 17.4, JH,H
=
precursor). H NMR (500 MHz, C6D6): δ = 1.24 (s, 3 H, 1-CH3),
3
2
2
3
3
1.3 Hz, 1 H, =CH2E), 5.15 (dd, JH,H = 10.5, JH,H = 1.3 Hz, 1 H,
1.80 (ddd, JH,H = 12.2, JH,H = 7.0, JH,H = 7.7 Hz, 1 H, 2-H),
=CH2Z), 6.01 (dd, 3JH,H = 17.4, JH,H = 10.5 Hz, 1 H, =CH), 7.11
1.96 (ddd, JH,H = 12.2, JH,H = 7.2, JH,H = 4.9 Hz, 1 H, 2-H),
3
2
3
3
3
3
4
2
3
3
(ddd, JH,H = 7.9, JH,H = 6.9, JH,H = 1.3 Hz, 1 H, 6-H), 7.20
(ddd, JH,H = 8.1, JH,H = 6.2, JH,H = 1.2 Hz, 1 H, 7-H), 7.27
3.31 (ddd, JH,H = 10.3, JH,H = 7.7, JH,H = 4.9 Hz, 1 H, 3-H),
3
3
4
2
3
3
3.36 (ddd, JH,H = 10.3, JH,H = 7.2, JH,H = 7.0 Hz, 1 H, 3-H),
3
4
5
3
2
(ddd, JH,H = 8.1, JH,H = JH,H = 1.0 Hz, 1 H, 8-H), 7.53 (ddd,
3JH,H = 7.0, 4JH,H = 1.1, 5JH,H = 0.8 Hz, 1 H, 5-H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 19.8, 21.8, 25.2, 31.5, 39.1, 40.9, 108.5,
110.3, 113.3, 118.1, 118.6, 121.0, 126.7, 137.4, 139.1, 145.9 ppm.
HRMS (ESI): calcd. for C16H19NNa [M + Na]+: 248.1410; found
248.1411. The enantiomeric excess was determined by chiral HPLC
analysis (Daicel Chiralcel ODH column, column temperature
20 °C, solvent n-heptane/2-propanol = 100:0, flow rate 0.8 mL/min,
λ = 230 nm): tR = 18.6 min (major enantiomer), tR = 22.4 min
(minor enantiomer).
4.91 (dd, JH,H = 10.3, JH,H = 1.5 Hz, 1 H, =CH2Z), 4.96 (dd,
3JH,H = 17.2, JH,H = 1.5 Hz, 1 H, =CH2E), 5.83 (dd, JH,H = 17.2,
2
3
3JH,H = 10.3 Hz, 1 H, =CH), 6.02 (dd, 3JH,H = 3.4, 4JH,H = 1.3 Hz,
3
4
1 H, 7-H), 6.43 (dd, JH,H = 2.6, JH,H = 1.3 Hz, 1 H, 5-H), 6.46
(dd, 3JH,H = 3JH,H = 2.6 Hz, 1 H, 6-H) ppm. 13C NMR (125 MHz,
C6D6): δ = 25.7, 43.2, 44.4, 44.7, 99.3, 111.9, 112.7, 113.4, 122.1,
144.7 ppm. HRMS (ESI): calcd. for C10H13NNa [M + Na]+:
170.0946; found 170.0940. The enantiomeric excess was determined
by chiral gas liquid chromatography analysis (FS-Cyclodex β-I/P,
column temperature 105 °C isotherm, flow rate 0.6 mL/min): tR
=
29.5 min (minor enantiomer), tR = 30.0 min (major enantiomer).
(+)-1-Methyl-1-vinyl-2,3-dihydro-1H-pyrrolo[1,2-a]indole [(+)-40]:
According to the general procedure (18 h); yield 10.5 mg, 38%
(76%), colourless liquid. Rf = 0.56 (cyclohexane/tert-butyl methyl
ether = 49:1). [α]2D0 = +3.6 (c = 0.585, CHCl3, 47% ee, contaminated
rac-8-Methyl-8-vinyl-5,6,7,8-tetrahydroindolizine (rac-43): Accord-
ing to the general procedure (15 h); yield 6.3 mg, 20% [obtained
with L1 (R1 = Me)], yellow oil. Rf = 0.37 (cyclohexane/tert-butyl
methyl ether = 30:1). 1H NMR (400 MHz, C6D6): δ = 1.32 (s, 3 H,
8-CH3), 1.45–1.77 (m, 6 H, 5-H, 6-H, 7-H), 4.88 (dd, 3JH,H = 17.1,
with cyclization precursor). IR (ATR): ν = 3052 (w, Ar–H/=C–H),
˜
2965, 2928 (s, C–H), 2871 (m, C–H), 1457 (s, C=C) cm–1. 1H NMR
(300 MHz, CDCl3): δ = 1.51 (s, 3 H, 1-CH3), 2.40–2.50 (m, 1 H,
2-H), 2.54–2.64 (m, 1 H, 2-H), 4.02–4.15 (m, 2 H, 3-H), 5.01 (dd,
3
2
2JH,H = 1.7 Hz, 1 H, =CH2E), 4.97 (dd, JH,H = 10.3, JH,H
=
3
3
1.7 Hz, 1 H, =CH2Z), 5.77 (dd, JH,H = 17.1, JH,H = 10.3 Hz, 1
3
4
H, =CH), 6.15 (dd, JH,H = 3.4, JH,H = 1.9 Hz, 1 H, 1-H), 6.37
(dd, 3JH,H = 3.2, 4JH,H = 1.9 Hz, 1 H, 3-H), 6.39 (dd, 3JH,H = 3JH,H
= 3.2 Hz, 1 H, 2-H) ppm. 13C NMR (100 MHz, C6D6): δ = 23.3,
28.9, 29.7, 35.3, 39.1, 105.5, 108.3, 108.7, 112.8, 118.9, 147.7 ppm.
HRMS (ESI): calcd. for C11H15NNa [M + Na]+: 184.1102; found
184.1097.
2
3
3JH,H = 17.1, JH,H = 1.2 Hz, 1 H, =CH2E), 5.05 (dd, JH,H = 10.5,
2JH,H = 1.1 Hz, 1 H, =CH2Z), 6.06 (dd, JH,H = 17.2, JH,H
=
3
3
10.5 Hz, 1 H, =CH), 6.17 (d, 4JH,H = 0.8 Hz, 1 H, 9-H), 7.08 (ddd,
3
4
3JH,H = 7.8, JH,H = 7.2, JH,H = 1.4 Hz, 1 H, 7-H), 7.15 (ddd,
3
4
3JH,H = 8.3, JH,H = 7.1, JH,H = 1.3 Hz, 1 H, 6-H), 7.26 (ddd,
4
5
3JH,H = 8.0, JH,H = 2.0, JH,H = 0.9 Hz, 1 H, 5-H), 7.58 (ddd,
3JH,H = 7.6, 4JH,H = 1.4, 5JH,H = 0.8 Hz, 1 H, 8-H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 25.4, 42.2, 42.9, 44.6, 92.0, 109.3, 112.5,
119.1, 120.4, 120.6, 132.5, 132.7, 143.4, 149.7 ppm. HRMS (ESI):
calcd. for C14H15NH [M + H]+: 198.1277; found 198.1275. The
enantiomeric excess was determined by chiral HPLC analysis
(Daicel Chiralcel ODH column, column temperature 12 °C, solvent
n-heptane/2-propanol = 100:0, flow rate 0.8 mL/min, λ = 230 nm):
tR = 25.7 min (minor enantiomer), tR = 27.6 min (major enantio-
mer).
(–)-1-Phenyl-1-vinyl-2,3-dihydro-1H-pyrrolizine [(–)-44]: According
to the general procedure (15 h); yield 6.8 mg, 16% (33%), yellow
oil. Rf = 0.57 (cyclohexane/tert-butyl methyl ether = 10:1). [α]2D0
=
–11.1 (c = 0.425, CHCl3, 68% ee, contaminated with cyclization
1
3
precursor). H NMR (500 MHz, C6D6): δ = 2.32 (dd, JH,H = 6.6,
3JH,H = 6.5 Hz, 2 H, 2-H), 3.25 (ddd, JH,H = 10.1, JH,H = 6.5,
2
3
3JH,H = 5.0 Hz, 1 H, 3-H), 3.33 (ddd, JH,H = 10.1, JH,H = 6.7,
2
3
3JH,H = 6.4 Hz, 1 H, 3-H), 4.95 (dd, JH,H = 17.1, JH,H = 1.3 Hz,
1 H, =CH2E), 4.99 (dd, 3JH,H = 10.4, 2JH,H = 1.3 Hz, 1 H, =CH2Z),
6.09 (dd, 3JH,H = 17.1, 3JH,H = 10.4 Hz, 1 H, =CH), 6.14 (dd, 3JH,H
3
2
4
3
4
= 3.5, JH,H = 1.5 Hz, 1 H, 7-H), 6.46 (dd, JH,H = 2.7, JH,H
=
rac-9-Methyl-9-vinyl-6,7,8,9-tetrahydropyrido[1,2-a]indole (rac-41):
According to the general procedure (26 h); yield 5.0 mg, 17%
(27%), colourless viscous oil. Rf = 0.50 (cyclohexane/tert-butyl
methyl ether = 9:1). 1H NMR (400 MHz, CDCl3): δ = 1.50 (s, 3
H, 9-CH3), 1.72–1.80 (m, 1 H, 8-H), 1.88–1.93 (m, 1 H, 8-H), 2.00–
2.20 (m, 2 H, 7-H), 3.86–3.94 (m, 1 H, 6-H), 4.14–4.19 (m, 1 H, 6-
3
3
1.4 Hz, 1 H, 5-H), 6.48 (dd, JH,H = 3.3, JH,H = 2.8 Hz, 1 H, 6-
H), 7.00–7.21 (m, 5 H, C6H5) ppm. 13C NMR (75 MHz, C6D6): δ
= 43.3, 44.4, 44.7, 102.0, 110.8, 112.8, 113.1, 121.9, 126.7, 127.1,
128.7, 137.4, 142.8 ppm. HRMS (ESI): calcd. for C15H15NNa [M
+ Na]+: 232.1102; found 232.1097. The enantiomeric excess was
determined by chiral HPLC analysis (Daicel Chiralcel OD-RH col-
umn, column temperature 20 °C, solvent MeCN/H2O = 60:40, flow
rate 0.6 mL/min, λ = 230 nm): tR = 15.4 min (minor enantiomer),
tR = 16.5 min (major enantiomer).
2
H), 4.81 (dd, 3JH,H = 17.2, JH,H = 1.3 Hz, 1 H, =CH2E), 5.04 (dd,
3JH,H = 10.4, 2JH,H = 1.3 Hz, 1 H, =CH2Z), 5.94 (dd, 3JH,H = 17.2,
3JH,H = 10.4 Hz, 1 H, =CH), 6.31 (s, 1 H, 10-H), 7.10–7.13 (m, 1
3
3
4
H, 2-H), 7.16 (ddd, JH,H = 8.3, JH,H = 7.1, JH,H = 1.3 Hz, 1 H,
3
4
5
3-H), 7.28 (ddd, JH,H = 8.2, JH,H = 1.5, JH,H = 0.9 Hz, 1 H, 4-
Supporting Information (see also the footnote on the first page of
3
4
5
H), 7.58 (ddd, JH,H = 7.7, JH,H = 1.0, JH,H = 0.7 Hz, 1 H, 1-H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 19.5, 28.5, 34.6, 39.3, 42.2,
98.1, 108.9, 113.3, 119.6, 119.9, 120.4, 128.0, 136.2, 142.6,
146.3 ppm. HRMS (ESI): calcd. for C15H17NNa [M + Na]+:
234.1253; found 234.1249. The enantiomeric excess was determined
by chiral HPLC analysis (Daicel Chiralcel OJ-RH column, column
temperature 20 °C, solvent MeCN/H2O = 70:30, flow rate 0.5 mL/
min, λ = 230 nm): tR = 19.9 min (major enantiomer), tR = 25.3 min
(minor enantiomer).
this article): Analytical data of all new compounds.
Acknowledgments
The research was supported by the University of Münster. J. A. S.
is indebted to the Fonds der Chemischen Industrie (predoctoral
fellowship, 2008-2010) and M. O. to the Aventis Foundation (Karl-
Winnacker-Stipendium, 2006–2008). The authors thank Dr. Axel
180
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 174–182