9610
J. Maury et al. / Tetrahedron 68 (2012) 9606e9611
m/z: calcd for [Mþ] C10H16Nþ: 150.1277; found: 150.1278. MS (ESI):
m/e: 427.2 [(MI)Cþ] and 704.2 [(MI)2Cþ].
mixture was washed with saturated Na2CO3, organic layer was
dried over anhydrous Na2SO4 and concentrated under reduced
pressure to afford the crude product. Purification by FC (pentane/
Et2O 19:1) gave the major diastereomer of ethyl 3-(1-iodo-4-
phenylcyclohexyl) propanoate 3 (917 mg, 2.3 mmol) in 46% yield.
4.3.7. N-tert-Butyl-4-methoxyanilinium iodide (12). To a solution of
1-azido-4-methoxybenzene 11 (100 mg, 0.67 mmol, 1 equiv) 0.2 M
in dichloromethane were added at 30 ꢁC 4 equiv of tert-BuI (319
mL,
Light yellow oil. 1H NMR (300 MHz, CDCl3)
d: 1.07e1.20 (2H, m),
2.68 mmol) under an argon atmosphere. After stirring for 18 h at
room temperature, the reaction mixture was treated with solid
Na2S2O4, the mixture was filtered, and concentrated in vacuo to
give 13 (165 mg, 80%). Mp: 165e167 ꢁC. 1H NMR (400 MHz, CDCl3)
1.29 (3H, t, J¼7.2), 1.85e1.91 (2H, m), 1.99e2.15 (2H, m), 2.19e2.27
(4H, m), 2.53 (1H, tt, J¼12.2 and 3.8), 2.68e2.75 (2H, m), 4.17 (2H, q,
J¼7.2), 7.18e7.35 (5H, m). 13C NMR (75 MHz, CDCl3)
d: 14.3 (CH3),
32.2 (CH2), 32.9 (CH2), 43.6 (CH2), 43.7 (CH2), 44.4 (CH), 60.7 (CH2),
64.3 (C), 126.3 (]CH), 127.0 (]CH), 128.5 (]CH), 146.4 (]C), 173.2
(C]O). ESI-HRMS for [MHþ] C17H24IO2: calcd 387.0815; found
387.0830.
d
: 1.47 (9H, s), 3.80 (3H, s), 6.85 (2H, d, J¼9.0), 7.60 (2H, d, J¼9.0),
9.93 (2H, br s). 13C NMR (100 MHz, CDCl3)
d
: 26.3 (CH3), 55.6 (CH3),
63.6 (C), 114.5 (]CH), 122.9 (]C), 127.8 (]CH), 160.4 (]C). HRMS
(ESI): m/z: calcd for [Mþ] C11H18NOþ: 180.1383; found: 180.1383.
MS (ESI): m/e: 487.1 [(MI)Cþ].
4.4.2. Ethyl 3-(4-phenylcyclohex-1-enyl)propanoate (4 and 5).
Benzyl azide 1c (77 mg, 0.6 mmol) was added to a stirred solution
4.3.8. 3-Iodo-1,2,3,4-tetrahydriquinoline (8) and 1-iodo-2-(prop-2-
en-1-yl)benzene (9).23 To a solution of 1-azido-2-(prop-2-en-1-yl)
benzene 7 (100 mg, 0.63 mmol, 1 equiv) 0.2 M in dichloromethane
of g-iodoester 3 (226 mg, 0.6 mmol) in DMF (2 mL) and the reaction
mixture was stirred for 7 h at room temperature. The mixture was
diluted with H2O and extracted with Et2O, combined organic layers
were dried over anhydrous Na2SO4 and concentrated under re-
duced pressure. The residue was purified under pressure by flash
chromatography (pentane/ether 40:1), affording a mixture of the
two regioisomers 4 and 5 (110 mg, 72%, ratio 25:1) as a colorless
were added at room temperature 4 equiv of tert-BuI (300 mL,
2.51 mmol) under an argon atmosphere. After stirring for 18 h at
room temperature, the reaction mixture was washed with Na2S2O4
and the layers were separated. The organic phase was dried
(MgSO4), filtered, and concentrated in vacuo. Flash column chro-
matography on silica gel (pentane/ethyl acetate from 100/0 to 80/
20) afforded to 7 in 60% (60 mg), 9 in 17% (26 mg)24 and 8 in 16%
(25 mg).
liquid. 1H NMR (300 MHz, CDCl3)
d
: 1.30 (3H, t, J¼7.2), 1.72e1.87
(1H, m), 1.19e2.38 (7H, m), 2.25 (2H, m), 2.73e2.82 (1H, m), 4.17
(2H, q, J¼7.2), 5.54e5.56 (1H, m), 7.19e7.35 (5H, m). 13C NMR
(75 MHz, CDCl3) d: 14.4 (CH3), 29.0 (CH2), 30.1 (CH2), 32.7 (CH2),
33.0 (CH2), 33.5 (CH2), 40.1 (CH), 60.3 (CH2), 121.3 (]CH), 126.1 (]
CH), 126.9 (]CH), 128.4 (]CH), 136.2 (]C), 147.1 (]C), 173.5 (C]
O). ESI-HRMS for [MHþ] C17H23O2: calcd 259.1693; found 259.1688.
4.3.8.1. 3-Iodo-1,2,3,4-tetrahydriquinoline
(400 MHz, CDCl3)
(8). 1H
NMR
d
: 1.55 (1H, s), 2.91 (1H, dd, J¼14.3 and 10.0), 3.49
(1H, dd, J¼14.3 and 4.3), 3.73 (1H, t, J¼10.0), 4.05 (1H, dd, J¼10.0
and 3.9), 4.57 (1H, tt, J¼10.0 and 4.0), 7.07e7.40 (4H, m). 13C NMR
4.4.3. 8-Phenyl-1-oxaspiro[4.5]decan-2-one (6). Benzyl azide 1c
(25 mg, 0.2 mmol) was added to a stirred solution of g-iodoester 3
(100 MHz, CDCl3)
d
: 14.4 (CH2), 31.7 (CH), 42.1 (CH2), 118.4 (]CH),
124.8 (]CH), 128.8 (]CH), 130.4 (]C), 131.7 (]CH), 138.5 (]C).
HRMS (ESI): m/z: calcd for [MHþ] C9H11IN: 259.9931; found:
259.9932.
(145 mg, 0.4 mmol) in DCM (2 mL) and the mixture was stirred for
12 h at room temperature. The mixture was diluted with DCM and
washed with H2O, combined organic layers were dried over an-
hydrous Na2SO4 and concentrated under reduced pressure. The
residue was purified by flash chromatography (pentane/ether
40:1), affording a mixture of two diastereomers of compound 6
(27 mg, 31%) as colorless crystalline solid. 1H NMR (300 MHz,
4.3.8.2. 1-Iodo-2-(prop-2-en-1-yl)benzene
(400 MHz, CDCl3)
(9).23 1H
NMR
d
: 3.49 (2H, d, J¼6.5), 5.08 (1H, dq, J¼17.1 and 1.8),
5.14 (1H, dq, J¼10.0 and 1.5), 5.96 (1H, ddt, J¼17.1, 10.0 and 6.5),
6.85e6.96 (1H, m), 7.18e7.24 (1H, m), 7.27e67.33 (1H, m),
CDCl3)
2.54e2.66 (3H, m), 7.53e7.19 (5H, m). Major diastereomer 13C NMR
(75 MHz, CDCl3) : 28.7 (CH2), 30.6 (CH2), 30.7 (CH2), 36.8 (CH2),
d: 1.50e1.70 (2H, m), 1.78e2.07 (6H, m), 2.18 (2H, t, J¼8.3),
7.79e7.88 (1H, m). 13C NMR (100 MHz, CDCl3)
d: 45.2 (CH2), 101.0
(]C), 116.9 (]CH2), 128.2 (]CH), 128.6 (]CH), 129.9 (]CH), 135.9
(]CH), 139.7 (]CH), 142.9 (]C).
d
42.7 (CH), 86.6 (C), 126.5 (]CH), 126.8 (]CH), 128.6 (]CH), 145.6
(]C), 176.5 (C]O). Minor diastereomer, characteristic signals, 13C
4.4. Synthesis and reactivity of 3
NMR (75 MHz, CDCl3) d: 29.9 (CH2), 34.3 (CH2), 37.4 (CH2), 43.5
(CH), 85.1 (C), 126.3 (]CH), 127.0 (]CH), 128.5 (]CH), 146.5 (]C),
176.8 (C]O). ESI-HRMS for [MNaþ] C15H18NaO2: calcd 253.1189;
found 253.1198.
4.4.1. Ethyl 3-(1-iodo-4-phenylcyclohexyl) propanoate (3).7a Potass-
ium tert-butoxide (13.5 g, 120 mmol) and Ph3PCH3Br (43.0 g,
120 mmol) were refluxed in Et2O during 30 min. A solution of the
4-phenyl-cyclohexanone (14.0 g, 80 mmol) in Et2O (400 mL) was
cautiously added via syringe and the reaction mixture was refluxed
for another 60 min. The yellow suspension was cooled down and
washed with H2O, dried with MgSO4. Purification by FC (cyclo-
hexane/tBuOMe 30:1) provided 4-methylene-1-phenyl-cyclohex-
ane S1 (13.7 g, 79 mmol, 99%) as a colorless oil.25 1H NMR
Supplementary data
Electronic Supplementary data (ESI) available: 1H and 13C
NMR spectrum for all new compounds. Supplementary data
(300 MHz, CDCl3)
2.17e2.27 (2H, m), 2.42e2.48 (2H, m), 2.65e2.75 (1H, m), 4.71 (2H,
s), 7.18e7.35 (5H, m). 13C NMR (75 MHz, CDCl3)
: 35.1 (CH2), 35.5
(CH2), 44.1 (CH), 107.4 (]CH2), 126.0 (]CH), 126.8 (]CH), 128.3 (]
CH), 146.8 (]C), 148.7 (]C).
To a stirred solution of olefin S1 (861 mg, 5 mmol) and ethyl
iodoacetate (1.1 g, 5 mmol) in benzene (20 mL), triethylborane
(500 mL, 0.5 mmol, 1 M in hexane) was added (syringe has to be
d: 1.51e1.65 (2H, m), 1.99e2.04 (2H, m),
References and notes
d
ꢁ
1. For review, see: (a) L’abbe, G. Chem. Rev. 1969, 69, 345; (b) Scriven, E. F. V.;
Turnbull, K. Chem. Rev. 1988, 88, 297; (c) Grashey, R. In Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: 1991; Vol. 6, p 225; (d) Brase,
S.; Gil, C.; Knepper, K.; Zimmermann, V. Angew. Chem., Int. Ed. 2005, 44, 5188;
(e) Binder, W. H.; Kluger, C. Curr. Org. Chem. 2006, 10, 1791; (f) Palacios, F.;
Aparicio, D.; Rubiales, G.; Alonso, C.; De los Santos, J. M. Curr. Org. Chem. 2006,
10, 2371; (g) Pinho e Melo, T. M. V. D. In Organic Azides: Syntheses and Appli-
cations; Brase, S., Banert, K., Eds.; Wiley: Chichester, UK, 2010; pp 53e94.
2. Doyle, M. P.; Whitefleet, J. L.; Bosch, R. J. J. Org. Chem. 1979, 44, 2923.
€
immersed to the reaction mixture). Reaction mixture was stirred
under aerobic condition at room temperature for 6 h. Reaction