Supporting Information
Wiley-VCH 2009
69451 Weinheim, Germany
Intramolecular Alkynylcyclopropanation of Olefins Catalyzed by Bi(OTf)3 : Stereoselective Synthesis of 1-Alkynyl-3-azabicyclo[3.1.0]hexanes**
Kimihiro Komeyama,* Natsuko Saigo, Motoyoshi Miyagi, and Ken Takaki*
ange_200904610_sm_miscellaneous_information.pdf
General. Nuclear magnetic resonance spectra were taken on JEOL EX-270 (270.05 MHz for 1H
NMR and 67.8 MHz for 13C NMR) spectrometer or JEOL Lambda-400 (395.75 MHz for 1H NMR
and 99.5 MHz for 13C NMR) spectrometer using residual chloroform (7.26 ppm for 1H NMR) and
CDCl3 (77.0 ppm for 13C NMR) as an internal standard. Low-resolution mass spectra (EI) were
obtained at 70 eV on a Shimazu QP-5050. High-resolution mass spectra (EI) were performed on
JEOL-SX102A at Hiroshima University. Melting points were recorded on YANAKO micro melting
point apparatus and uncorrected. Column chromatography and TLC monitoring were performed
with silica gel Merck 60 (Merck, type 60, 230-400 mesh) and silica gel aluminium sheets (Merck,
type 60 F254), respectively.
Materials. 1,4-Dioxane, toluene, and benzene were distilled from Na/benzophenone ketyl.
Nitromethane were distilled from P2O5 and stored over molecular sieves. Dichloroethane were
distilled from CaH2. Bi(OTf)3, Fe(OTf)2, BF3·OEt2, Sc(OTf)3, Cu(OTf)2, PtCl2, AgOTf, and TfOH
were purchased and used as received. Fe(OTf)3 was prepared by literature method.[1]
Product Data
Ts
N
H
2a
Ph
3-Aza-1-phenylethynyl-3-tosylbicyclo[3.1.0]hexane (2a). Isolated as a white solid (Mp.: 119–122
ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.25; 1H NMR (CDCl3, 270.05 MHz) δ 1.09 (1H, t, J = 5.1
Hz), 1.12 (1H, dd, J = 8.0, 5.1 Hz), 1.79–1.84 (1H, m), 2.45 (3H, s), 3.12 (1H, d, J = 9.4 Hz), 3.15
(1H, dd, J = 9.4, 3.9 Hz), 3.57 (1H, d, J = 8.9 Hz), 3.73 (1H, d, J = 8.9 Hz), 7.24–7.36 (7H, m), 7.70
(2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.8 MHz) δ 16.6, 17.8, 21.5, 25.9, 49.4, 52.5, 79.3, 88.8,
122.8, 127.6, 128.1, 128.3, 129.7, 131.6, 133.0, 143.8; HRMS (EI) Calcd. for C20H19NO2S
337.1136, Found 337.1132.
Ts
N
H
Me
Ph
3-Aza-6-methyl-1-phenylethynyl-3-tosylbicyclo[3.1.0]hexane (2b). Isolated as a white solid
(Mp.: 96.0–96.5 ºC); Rf (SiO2, Hexane:EtAOc = 5:1) = 0.28; 1H NMR (CDCl3, 270.05 MHz) δ
1.22 (3H, t, J = 5.9 Hz), 1.29–1.35 (1H, m), 1.45 (1H, t, J = 4.1 Hz), 2.45 (3H, s), 3.12 (1H, dd, J =
9.2, 4.1 Hz), 3.15 (1H, d, J = 9.1 Hz), 3.59 (1H, d, J = 9.1 Hz), 3.71 (1H, d, J = 9.1 Hz), 7.27–7.36
(7H, m), 7.69 (2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.6, 21.3, 21.5, 23.9, 32.8,
49.6, 52.9, 81.2, 87.0, 123.0, 127.6, 128.0, 128.2, 129.7, 131.6, 133.0, 143.7; HRMS (EI) Calcd. for
1
C21H21NO2S, 351.1293, Found 351.1300.
Ts
N
H
Pr 2c
Ph
3-Aza-1-phenylethynyl-6-propyl-3-tosylbicyclo[3.1.0]hexane (2c). Isolated as a yellow oil; Rf
(SiO2, Hexane:EtOAc = 5:1) = 0.35; 1H NMR (CDCl3, 270.05 MHz) δ 0.93 (3H, t, J = 7.1 Hz),
1.19–1.25 (1H, m), 1.37–1.56 (5H, m), 2.44 (3H, s), 3.13 (1H, dd, J = 9.2, 4.0 Hz), 3.15 (1H, d, J =
9.2 Hz), 3.59 (1H, d, J = 9.1 Hz), 3.72 (1H, d, J = 9.1 Hz), 7.25–7.36 (7H, m), 7.71 (2H, d, J = 7.9
Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.9, 21.5, 22.0, 23.3, 26.7, 31.0, 31.8, 49.7, 53.1, 80.9, 87.2,
123.0, 127.6, 127.9, 128.2, 129.7, 131.5, 132.9, 143.7; HRMS (EI) Calcd. for C23H25NO2S
379.1606, Found 379.1593.
Ts
N
H
Ph
Pr trans-2c
3-Aza-1-phenylethynyl-6-propyl-3-tosylbicyclo[3.1.0]hexane (trans–2c). Isolated as a yellow
oil; Rf (SiO2, Hexane:EtOAc = 5:1) = 0.35; 1H NMR (CDCl3, 270.05 MHz) δ 0.92 (3H, t, J = 7.1
Hz), 1.37–1.45 (5H, m), 1.91 (1H, dd, J = 7.7, 3.9 Hz), 2.43 (3H, s), 3.42 (1H, d, J = 9.6 Hz), 3.42–
3.43 (2H, m), 3.63 (1H, d, J = 9.6 Hz), 7.15–7.36 (7H, m), 7.71 (2H, d, J = 8.2 Hz); 13C NMR
(CDCl3, 67.80 MHz) δ 13.7, 21.5, 21.7, 22.7, 23.4, 29.9, 30.7, 47.0, 50.5, 78.7, 90.4, 122.9, 127.4,
127.9, 128.2, 129.7, 131.5, 133.3, 143.6; HRMS (EI) Calcd. for C23H25NO2S 379.1606, Found
379.1615.
Ts
N
H
2d
4-ClC6H4
3-Aza-1-[(4-chlorophenyl)ethnyl]-3-tosylbicyclo[3.1.0]hexane (2d). Isolated as a white solid
(Mp.: 170.0–171.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.25; 1H NMR (CDCl3, 270.05 MHz) δ
1.10 (1H, dd, J = 5.1, 5.0 Hz), 1.26 (1H, dd, J = 7.9, 5.1 Hz), 1.80 (1H, ddd, J = 7.9, 5.0, 3.0), 2.45
(3H, s), 3.11 (1H, d, J = 8.9 Hz), 3.15 (1H, dd, J = 9.4 Hz), 3.57 (1H, d, J =9.4, 3.9 Hz), 3.72 (1H,
d, J = 8.9 Hz), 7.21–7.31 (4H, m), 7.37 (2H, d, J = 8.2 Hz), 7.71 (2H, d, J = 7.9 Hz); 13C NMR
(CDCl3, 67.8 MHz) δ 16.6, 17.8, 21.5, 26.0, 49.3, 52.3, 78.3, 89.9, 121.3, 127.6, 128.6, 129.8,
132.8, 133.0, 134.1, 143.8; HRMS (EI) Calcd. for C20H18ClNO2S 371.0747, Found 371.0748.
Ts
N
H
Me 2e
4-ClC6H4
3-Aza-1-[(4-chlorophenyl)ethynyl]-6-methyl-3-tosylbicyclo[3.1.0]hexane (2e). Isolated as a
white solid (Mp.: 125.5–126.5 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.39; 1H NMR (CDCl3,
270.05 MHz) δ 1.21 (3H, t, J = 5.9 Hz), 1.26–1.38 (1H, m), 1.45 (1H, t, J = 3.9 Hz), 2.44 (3H, s),
3.12 (1H, dd, J = 8.9, 3.9 Hz), 3.13 (1H, d, J = 8.9 Hz), 3.59 (1H, d, J = 9.1 Hz), 3.70 (1H, d, J =
2
9.1 Hz), 7.12–7.36 (6H, m), 7.69 (2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.6, 21.3,
21.5, 23.8, 32.9, 49.6, 52.8, 80.1, 88.1, 121.5, 127.6, 128.6, 129.7, 132.8, 132.9, 133.9, 143.7;
HRMS (EI) Calcd. for C21H20ClNO2S 385.0903, Found 385.0903.
Ts
N
H
Pr 2f
4-ClC6H4
3–Aza–1–[(4–chlorophenyl)ethynyl]–6–propyl–3–tosylbicyclo[3.1.0] hexane (2f). Isolated as a
yellow oil; Rf (SiO2, Hexane:EtOAc = 5:1) = 0.30; 1H NMR (CDCl3, 270.05 MHz) δ 0.92 (3H, t, J
= 6.8 Hz), 1.23–1.25 (1H, m), 1.40–1.50 (5H, m), 2.44 (3H, s), 3.12 (1H, dd, J = 9.7, 4.8 Hz), 3.16
(1H, d, J = 9.7 Hz), 3.59 (1H, d, J = 9.7 Hz), 3.71 (1H, d, J = 9.7 Hz), 7.20–7.24 (4H, m), 7.35 (2H,
d, J = 7.8 Hz), 7.69 (2H, d, J = 8.7 Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.9, 21.5, 22.0, 23.3,
26.8, 31.0, 31.9, 49.6, 53.0, 79.9, 88.3, 121.5, 127.6, 128.6, 129.7, 132.8, 132.9, 133.9, 143.7;
HRMS (EI) Calcd. for C23H24ClNO2S 413.1216, Found 413.1216.
Ts
N
H
2g
4-BrC6H4
3-Aza-1-[(4-bromophenyl)ethnyl]-3-tosylbicyclo[3.1.0]hexane (2d). Isolated as a white solid
(Mp.: 173.0–174.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.25; 1H NMR (CDCl3, 270.05 MHz) δ
1.11 (1H, dd, J = 8.2, 5.3 Hz), 1.12 (1H, t, J = 5.3, Hz), 1.79–1.86 (1H, m), 2.45 (3H, s), 3.10 (1H,
d, J = 9.2 Hz), 3.14 (1H, dd, J = 9.2, 3.6 Hz), 3.58 (1H, d, J =8.9 Hz), 3.73 (1H, d, J = 8.9 Hz), 7.16
(2H, d, J = 8.6 Hz), 7.36 (2H, d, J = 8.2 Hz), 7.40 (2H, d, J = 8.6 Hz), 7.70 (2H, d, J = 8.2 Hz); 13C
NMR (CDCl3, 67.8 MHz) δ 16.6, 17.8, 21.5, 25.9, 49.3, 52.3, 78.3, 90.1, 121.7, 122.2, 127.6,
128.9, 129.8, 131.5, 133.0, 143.8; HRMS (EI) Calcd. for C20H18BrNO2S 415.0242, Found
415.0241.
Ts
N
H
Me 2h
4-BrC6H4
3-Aza-1-[(4-bromophenyl)ethynyl]-6-methyl-3-tosylbicyclo[3.1.0]hexane (2h). Isolated as a
white solid (Mp.: 132.0–132.5 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.29; 1H NMR (CDCl3,
270.05 MHz) δ 1.20 (3H, d, J = 5.9 Hz), 1.30–1.38 (1H, m), 1.45 (1H, t, J = 34.0 Hz), 2.44 (3H, s),
3.11 (1H, dd, J = 8.9, 4.0 Hz), 3.13 (1H, d, J = 8.9 Hz), 3.59 (1H, d, J = 9.1 Hz), 3.70 (1H, d, J =
9.1 Hz), 7.20 (2H, d, J = 8.6 Hz), 7.34 (2H, d, J = 8.2 Hz), 7.39 (2H, d, J = 8.6 Hz), 7.69 (2H, d, J =
8.2 Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.6, 21.3, 21.5, 23.8, 32.9, 49.6, 52.8, 80.2, 88.3, 122.0,
122.1, 127.6, 129.7, 131.5, 132.9, 133.0, 143.7; HRMS (EI) Calcd. for C20H18BrNO2S 429.0398,
Found 429.0386.
3
Ts
N
H
2i
4-MeC6H4
3-Aza-1-[4-anisylethynyl]-3-tosylbicyclo[3.1.0]hexane (2g). Isolated as a yellow solid (Mp.:
165.0–167.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.28; 1H NMR (CDCl3, 270.05 MHz)δ 1.09
(1H, t, J = 5.1 Hz), 1.12 (1H, dd, J = 5.1, 8.1 Hz), 1.80 (1H, ddd, J = 8.1, 5.1, 4.0 Hz), 2.32 (3H, s),
2.45 (3H, s), 3.10 (1H, d, J = 9.2 Hz, NCHHCH), 3.14 (1H, dd, J = 9.2, 4.0 Hz, NCHHCH), 3.56
(1H, d, J = 9.1 Hz, NCHHCC), 3.72 (1H, d, J = 9.1 Hz, NCHHCC), 7.07 (2H, d, J = 8.2 Hz, Ar),
7.23 (2H, d, J = 8.2 Hz, Ar), 7.35 (2H, d, J = 8.2 Hz, Ar), 7.69 (2H, d, J = 8.2 Hz. Ar), 21H; 13C
NMR (CDCl3, 67.8 MHz) δ 16.6, 17.8, 21.4, 21.5, 25.8, 49.4, 52.5, 79.3 , 88.0, 119.6, 127.6, 129.0,
131.4, 132.8, 138.2, 143.7, 16C; HRMS (EI) Calcd. for C21H21BrNO2S 351.1293, Found 351.1285.
Ts
N
H
Me 2j
4-MeC6H4
3-Aza-6-methyl-1-(4-tolylethynyl)-3-tosylbicyclo[3.1.0] hexane (2j). Isolated as a white solid
(Mp.: 109.5–110.5 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.26; 1H NMR (CDCl3, 270.05 MHz) δ
1.21 (3H, d, J = 5.9 Hz), 1.26–1.34 (1H, m), 1.44 (1H, t, J = 3.9 Hz), 2.32 (3H, s,), 2.45 (3H, s),
3.15 (1H, dd, J = 8.9, 3.9 Hz), 3.15 (1H, d, J = 8.9 Hz), 3.59 (1H, d, J = 9.1 Hz), 3.71 (1H, d, J =
9.1 Hz), 7.07 (2H, d, J = 7.9 Hz), 7.25 (2H, d, J = 8.2 Hz), 7.35 (2H, d, J = 7.9 Hz), 7.69 (2H, d, J =
7.9 Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.6, 21.2, 21.4, 21.5, 23.9, 32.7, 49.6, 53.0, 81.2, 86.2,
119.9, 127; HRMS (EI) Calcd. for C22H23NO2S 365.1449, Found 365.1446.
Ts
N
H
Pr 2k
4-MeC6H4
3-Aza-1-(4-tolylethynylethynyl)-6-propyl-3-tosylbicyclo[3.1.0] hexane (2k). Isolated as a yellow
oil; Rf (SiO2, Hexane:EtOAc = 5:1) = 0.38; 1H NMR (CDCl3, 270.05 MHz) δ 0.92 (3H, t, J = 7.1
Hz), 1.22–1.23 (1H, m), 1.41–1.51 (5H, m), 2.32 (3H, s), 2.45 (3H, s), 3.12 (1H, dd, J = 9.2, 4.0
Hz), 3.13 (1H, d, J = 9.2 Hz), 3.58 (1H, d, J = 9.1 Hz), 3.70 (1H, d, J = 9.1 Hz), 7.07 (2H, d, J = 7.9
Hz), 7.22 (2H, d, J = 7.9 Hz), 7.35 (2H, d, J = 7.9 Hz), 7.69 (2H, d, J = 7.9 Hz), 27 H; 13C NMR
(CDCl3, 67.80 MHz) δ 13.9, 21.4, 21.5, 22.0, 23.4, 26.7, 31.0, 31.8, 49.7, 53.1, 81.0, 86.4, 119.9,
127.6, 129.0, 129.7, 131.4, 132.9, 138.1, 143.7; HRMS (EI) Calcd. for C24H27NO2S 393.1762,
Found 393.1764.
Ts
N
H
Me 2l
4-MeOC6H4
3-Aza-6-methyl-1-(4-anisylethynyl)-3-tosylbicyclo[3.1.0]hexane (2l). Isolated as a white solid
(Mp.: 119.5–120.5 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.34; 1H NMR (CDCl3, 270.05 MHz) δ
1.20 (3H, d, J = 5.9 Hz), 1.26–1.32 (1H, m), 1.42 (1H, t, J = 4.0 Hz), 2.44 (3H, s), 3.11 (1H, dd, J =
9.1, 4.0 Hz), 3.14 (1H, d, J = 9.1 Hz), 3.58 (1H, d, J = 9.2 Hz), 3.69 (1H, d, J = 9.2 Hz), 3.78 (3H,
4
s), 6.79 (2H, d, J = 8.9 Hz), 7.28 (2H, d, J = 8.9 Hz), 7.34 (2H, d, J = 8.1 Hz), 7.69 (2H, d, J = 8.1
Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.6, 21.1, 21.5, 23.9, 32.6, 49.6, 53.0, 55.2, 80.9, 85.3,
113.8, 115.1, 127.6, 129.7, 132.9, 133.0, 142.6, 159.3; HRMS (EI) Calcd. for C22H23NO3S
381.1399, Found 381.1393.
Ts
N
H
2m
2-ClC6H4
3-Aza-1-(2-chlorophenylethynyl)-3-tosylbicyclo[3.1.0]-hexane (2m). Isolated as a white solid
(Mp.: 160.0–162.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.24; 1H NMR (CDCl3, 270.05 MHz) δ
1.13 (1H, t, J = 5.1 Hz), 1.26 (1H, dd, J = 7.8, 5.1 Hz), 1.85–1.90 (1H, m), 2.46 (3H, s), 3.16 (1H,
d, J = 8.9 Hz), 3.15 (1H, dd, J = 8.9, 4.6 Hz), 3.59 (1H, d, J =9.3 Hz), 3.76 (1H, d, J = 9.3 Hz),
7.14–7.37 (6H, m), 7.69 (2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.8 MHz)δ 16.9, 17.9, 21.6, 26.2,
49.3, 52.2, 76.1, 94.3, 122.7, 126.4, 127.6, 129.0, 129.2, 129.8, 133.0, 133.2, 135.8, 143.8; HRMS
(EI) Calcd. for C20H18ClNO2S 371.0747, Found 371.0751.
Ts
N
H
Me 2n
2-ClC6H4
3-Aza-1-(2–chlorophenylethynyl-6-methyl-3-tosylbicyclo[3.1.0]hexane (2n). Isolated as a white
solid (Mp.: 104.0−105.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.30; 1H NMR (CDCl3, 270.05
MHz) δ 1.25 (3H, d, J = 5.9 Hz), 1.32–1.38 (1H, m), 1.51 (1H, t, J = 4.0 Hz), 2.44 (3H, s), 3.14
(1H, dd, J = 9.2, 4.0 Hz), 3.19 (1H, d, J = 9.2 Hz), 3.60 (1H, d, J = 9.1 Hz), 3.74 (1H, d, J = 9.1
Hz), 7.16–7.20 (2H, m), 7.33–7.40 (4H, m), 7.69 (2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.80
MHz) δ 13.7, 21.5, 21.7, 24.1, 33.2, 49.6, 52.7, 77.9, 92.7, 122.9, 126.3, 127.6, 128.9, 129.1, 129.7,
133.0, 133.2, 135.6, 143.7; HRMS (EI) Calcd. for C21H20ClNO2S 385.0903, Found 385.0897.
Ts
N
H
Me 2o
2-MeC6H4
3-Aza-6-methyl-1-(2-tolylethynyl)-3-tosylbicyclo[3.1.0]hexane (2o). Isolated as a white solid
(Mp.: 125.0−126.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.38; 1H NMR (CDCl3, 270.05 MHz) δ
1.23 (3H, d, J = 5.9 Hz), 1.26–1.35 (1H, m), 1.45 (1H, t, J = 4.0 Hz), 2.35 (3H, s), 2.45 (3H, s), 3.14
(1H, dd, J = 9.0, 4.0 Hz), 3.18 (1H, d, J = 9.0 Hz), 3.60 (1H, d, J = 9.2 Hz), 3.73 (1H, d, J = 9.2
Hz), 7.05–7.15 (3H, m), 7.30–7.36 (3H, m), 7.70 (2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.80
MHz) δ 13.8, 20.7, 21.3, 21.5, 24.1, 33.0, 49.6, 53.0, 80.1, 90.9, 122.8, 125.5, 127.6, 127.9, 129.3,
129.7, 131.8, 133.1, 139.9, 143.7; HRMS (EI) Calcd. for C22H23NO2S 365.1449, Found 365.1447.
Ts
N
H
2p
1-naphtyl
3-Aza-1-(1-naphtylethnyl)-3-tosylbicyclo[3.1.0]hexane (2p). Isolated as a white solid (Mp.:
181.0–182.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.28; 1H NMR (CDCl3, 270.05 MHz) δ 1.17
5
(1H, t, J = 5.1 Hz), 1.25 (1H, dd, J = 7.8, 5.1 Hz), 1.93 (1H, ddd, J = 7.8, 4.9, 3.8 Hz), 2.45 (3H, s),
3.22 (1H, d, J = 9.1, Hz), 3.24 (1H, dd, J = 9.1, 3.8, Hz), 3.62 (1H, d, J = 9.2 Hz), 3.83 (1H, d, J =
9.2 Hz), 7.35–7.40 (3H, m), 7.47–7.58 (3H, m), 7.71–7.84 (4H, m), 8.17 (1H, d, J = 7.6 Hz); 13C
NMR (CDCl3 , 67.8 MHz) δ 16.9, 18.1, 21.5, 26.2, 49.4, 52.5, 77.4, 93.8, 107.6, 120.4, 125.1,
125.8, 126.4, 127.6, 128.3, 128.5, 129.8, 130.3, 133.1, 133.3, 143.8, one carbon was not observed;
HRMS (EI) Calcd. for C24H21NO2S 387.1293, Found 387.1287.
Ts
N
H
Me 2q
1-naphtyl
3-Aza-1-(1-naphthylethynyl)-6-methyl-3-tosylbicyclo[3.1.0]hexane (2q). Isolated as a white
solid (Mp.: 156.5–157.5 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.22; 1H NMR (CDCl3, 270.05
MHz) δ 1.32 (3H, d, J = 5.6 Hz), 1.37–1.43 (1H, m), 1.57 (1H, t, J = 4.0 Hz), 2.45 (3H, s), 3.20
(1H, dd, J = 9.1, 4.0 Hz), 3.28 (1H, d, J = 9.1 Hz), 3.65 (1H, d, J = 9.2 Hz), 3.82 (1H, d, J = 9.2
Hz), 7.34–7.41 (3H, m), 7.47–7.60 (3H, m), 7.72 (2H, d, J = 8.2 Hz), 7.77–7.85 (2H, m), 8.20 (1H,
d, J = 7.9 Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.9, 21.49, 21.53, 24.2, 33.1, 49.7, 53.1, 79.2,
91.9, 120.7, 125.1, 125.9, 126.3, 126.6, 127.6, 128.3, 128.4, 129.7, 130.4, 133.0, 133.1, 133.3,
143.7; HRMS (EI) Calcd. for C25H23NO2S 401.1449, Found 401.1446.
Ts
N
H
Me 2r
2-furyl
3-Aza-1-(2-furanylethynyl)-6-methyl-3-tosylbicyclo[3.1.0]hexane (2r). Isolated as a yellow oil;
Rf (SiO2, Hexane:EtOAc = 5:1) = 0.29; 1H NMR (CDCl3, 270.05 MHz) δ 1.20 (3H, d, J = 6.3 Hz),
1.35–1.43 (1H, m), 1.50 (1H, t, J = 4.2 Hz), 2.45 (3H, s), 3.08 (1H, dd, J = 9.2, 4.2 Hz), 3.11 (1H, d,
J = 9.2 Hz), 3.59 (1H, d, J = 9.2 Hz), 3.70 (1H, d, J = 9.2 Hz), 6.35 (1H, dd, J = 3.3, 2.0 Hz), 6.49
(1H, dd, J = 3.3, 0.6 H), 7.32–7.36 (3H, m), 7.67 (2H, d, J = 8.2 Hz); 13C NMR (CDCl3, 67.80
MHz) δ 13.5, 21.5, 21.7, 23.8, 33.2, 49.5, 52.6, 71.2, 91.7, 110.8, 115.0, 127.6, 129.7, 132.7, 136.8,
143.2, 143.8; HRMS (EI) Calcd. for C19H19NO3S 341.1086, Found 341.1084.
Ts
N
H
Me 2s
NTs
3-Aza-6-methyl-3-(4-tosyl)-1-[1-(4-tosyl)-1H-indol-3-yl]bicyclo[3.1.0hexane (2s). Isolated as a
white solid (Mp.: 77.0–78.0 ºC; Rf (SiO2, Hexane:EtAOc = 3:1) = 0.20; 1H NMR (CDCl3, 270.05
MHz) δ 1.25 (3H, d, J = 5.9 Hz), 1.33–1.39 (1H, m), 1.48 (1H, t, J = 4.0 Hz), 2.33 (3H, s), 2.45
(3H, s), 3.14 (1H, dd, J = 9.1, 4.0 Hz), 3.18 (1H, d, J = 9.1 Hz), 3.61 (1H, d, J = 9.2 Hz), 3.74 (1H,
d, J = 9.2 Hz), 7.21 (2H, d, J = 8.6 Hz), 7.25–7.31 (2H, m), 7.35 (2H, d, 8.1 Hz), 7.51 (1H, d, J =
6.9 Hz), 7.64 (1H, s), 7.70 (2H, d, J = 8.1 Hz), 7.75 (2H, d, J = 8.6 Hz), 7.94 (1H, d, J = 8.2 Hz);
13C NMR (CDCl3, 67.80 MHz) δ 13.7, 21.3, 21.5, 21.6, 24.1, 33.1, 49.6, 52.9, 72.0, 91.3, 104.9,
113.5, 120.3, 123.6, 125.4, 126.9, 127.6, 128.7, 129.7, 130.0, 130.8, 132.9, 134.0, 134.8, 143.7,
145.3; HRMS (EI) Calcd. for C30H28N2O4S2 544.1490; found 544.1484.
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Ts
N
H
Me 2t
2-styryl
(E)-3-Aza-6-methyl-1-(2-phenylvinyl)-3-(4-tosyl)bicyclo[3.1.0]hexane (2t). Isolated as a white
solid (Mp.: 121.0–122.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.29; 1H NMR (CDCl3, 270.05
MHz) δ 1.19 (3H, d, J = 5.9 Hz), 1.30–1.37 (1H, m), 1.41 (1H, t, J = 4.0 Hz), 2.45 (3H, s), 3.08
(1H, dd, J = 9.1, 4.0 Hz), 3.10 (1H, d, J = 9.1 Hz), 3.58 (1H, d, J = 9.1 Hz), 3.68 (1H, d, J = 9.1
Hz), 6.10 (1H, d, J = 16.3 Hz), 6.86 (1H, d, J = 16.3 Hz), 7.28–7.36 (7H, m), 7.68 (2H, d, J = 8.2
Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.6, 21.4, 21.5, 24.2, 33.0, 49.6, 52.9, 80.5, 89.5, 107.8,
126.0, 127.6, 128.5, 128.7, 129.7, 132.8, 136.1, 141.0, 143.7; HRMS (EI) Calcd. for C23H23NO2S
377.1449, Found 377.1458.
Ts
N
H
Me 2u
3-Aza-6-methyl-3-(4-tosyl)-1-vinylbicyclo[3.1.0]hexane (2u). Isolated as a yellow solid (Mp.:
108.0–109.0 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.22; 1H NMR (CDCl3, 395.75 MHz) δ 1.14
(3H, d, J = 5.8 Hz), 1.25–1.30 (1H, m), 1.37 (1H, t, J = 3.9 Hz), 2.44 (3H, s), 3.05 (2H, d, J = 8.7
Hz), 3.55 (1H, d, J = 9.2 Hz), 3.64 (1H, d, J = 9.1 Hz), 5.40 (1H, dd, J = 11.6, 1.9 Hz), 5.54 (1H,
dd, J = 17.1, 1.9 Hz), 5.73 (1H, dd, J = 17.1, 11.6 Hz), 7.33 (2H, d, J = 8.7 Hz), 7.66 (2H, d, J = 8.7
Hz); 13C NMR (CDCl3, 67.80 MHz) δ 13.5, 21.2, 21.5, 23.8, 32.7, 49.6, 52.8, 79.9, 87.8, 116.8,
126.6, 127.6, 129.7, 132.8, 143.7; MS m/z 301 (M+, 11), 145 (50), 118 (100), 91 (90); HRMS (EI)
Calcd. for C17H19NO2S 301.1136, Found 301.1131.
Ts
N
H
Me 2v
Ph
3-Aza-6-methyl-1-(4-phenylbut-1,3-diynyl)-3-(4-tosyl)bicyclo[3.1.0]hexane (2w). Isolated as a
yellow solid (Mp.: 123.5–124.5 ºC); Rf (SiO2, Hexane:EtOAc = 5:1) = 0.33; 1H NMR (CDCl3,
270.05 MHz) δ 1.21 (3H, d, J = 6.3 Hz), 1.35–1.43 (1H, m), 1.51 (1H, t, J = 4.1 Hz), 2.45 (3H, s),
3.06 (1H, dd, J = 9.1, 4.1 Hz), 3.09 (1H, d, J = 9.1 Hz), 3.58 (1H, d, J = 9.2 Hz), 3.68 (1H, d, J =
9.1 Hz), 7.27–7.36 (5H, m), 7.43–7.47 (2H, m), 7.67 (2H, d, J = 8.3 Hz); 13C NMR (CDCl3, 67.80
MHz) δ 13.6, 21.5, 22.2, 24.0, 33.8, 49.5, 52.4, 65.7, 73.8, 75.8, 81.3, 121.5, 127.6, 128.4, 129.1,
129.7, 132.5, 132.6, 143.9; HRMS (EI) Calcd. for C23H21NO2S 375.1293, Found 375.1288.
Ts
N
Ph
H
nBu
2w
3-Aza-7-buthyl-1-phenylethynyl-3-tosylbicyclo[4.1.0]heptane (2w). Isolated as a colorless oil;
Rf (SiO2, Hexane:EtAOc = 3:1) = 0.43; 1H NMR (CDCl3, 270.05 MHz) δ 0.89 (3H, t, J = 6.4 Hz),
1.21–1.49 (10H, m), 2.45 (3H, s), 3.13 (1H, dd, J = 9.1, 4.0 Hz), 3.15 (1H, d, J = 9.1 Hz), 3.59 (1H,
d, J = 9.2 Hz), 3.72 (1H, d, J = 9.2 Hz), 7.25–7.36 (7H, m), 7.74 (2H, d, J = 8.2 Hz); 13C NMR
7
(CDCl3, 67.80 MHz) δ 14.0, 21.5, 22.6, 23.4, 27.0, 28.5, 28.9, 31.5, 31.9, 49.7, 53.1, 80.9, 87.2,
123.0, 127.6, 127.9, 128.2, 128.4, 129.7, 131.6, 143.7; HRMS (EI) Calcd. for C25H29NO2S
407.1919; Found 407.1914.
References
[1] S. Ichikawa, I. Tomita, A. Hosaka, T. Sato, Bull. Chem. Soc. Jpn. 1988, 61, 513.
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