J. Cassayre, S.Z. Zard / Journal of Organometallic Chemistry 624 (2001) 316–326
323
1H), 3.17 (dd, J=15.4, 3.6 Hz, 1H), 3.25 (s, 3H), 3.91
5.13. (4i,8i,11i)-3-Benzyl-11-methyl-3-azatricyc1o-
[6.2.1.04,11]undec-1(10)-en-9-one (26) and
(1i,2i,6i)-2-benzylamino-1,9-dimethyl-8-bicyc1o-
[4.3.0]nonen-7-one (27)
(dd, J=15.4, 7.7 Hz, 1H), 4.28 (dd, J=7.7, 3.2 Hz,
1H), 7.05–7.28 (m, 3H). 13C-NMR (CDCl3, 50 MHz)
major rotamer l 17.4, 23.9, 24.0, 33.7, 37.1, 48.8, 58.5,
96.0, 126.2, 127.6, 132.0, 133.4, 140.5, 148.5, 167.6;
minor rotamer l 17.4, 23.5, 24.2, 33.6, 37.1, 49.7, 58.4,
96.0, 126.7, 127.5, 131.5, 133.4, 140.5, 148.5, 167.6. MS
(IC) m/z 389 (MNH+4 ), 372 (MH+), 356, 336, 300, 253,
190.
To a solution of propargylic amine 25 (239 mg, 1
mmol) in CH2Cl2 (5 ml) was added dicobalt octacar-
bonyl complex (376 mg, 1.1 mmol), and the resulting
mixture was stirred for 30 min at r.t. After concentra-
tion, the black residue was dissolved in 20 ml of the
given solvent (see Scheme 7), and N-methylmorpholine
oxide (1.3 g, 10 mmol) was added in one portion. The
mixture was stirred at r.t. (1–20 h), then filtered
through silica, and concentrated. Column chromatogra-
phy (silica gel, heptane–AcOEt, 9:1) afforded 26 and 27
in the proportions indicated in Scheme 7. Data for 26:
1H-NMR (300 MHz, CDCl3) 60.91–1.15 (m, 3H), 1.36
(s, 3H), 1.56–1.72 (m, 2H), 1.96 (m, 1H), 2.41 (t,
J=8.8 Hz, 1H), 2.94 (dd, J=9.8, 6.2 Hz, 1H), 3.41 (d,
J=17.4 Hz, 1H), 3.80 (d, J=13.4 Hz, 1H), 3.83 (d,
J=17.4 Hz, 1H), 3.93 (d, J=13.4 Hz, 1H), 5.69 (s,
1H), 7.22–7.37 (m, 5H). 13C-NMR (CDCl3, 75 MHz) l
21.4, 25.4, 26.8, 30.4, 50.5, 52.2, 55.0, 55.9, 64.9, 120.2,
127.1, 128.3, 128.4, 139.4, 188.1, 213.7. IR (neat) 1704,
5.11. (5R,6S)-2,4,4,4-Tetrachloro-N-(5-isopropyl-6-
tert-butyldimethylsiloxy-2-methyl-1,3-cyclohexadienyl)-
N-methyl-butyramide (20)
According to the general procedure, 19 (373 mg, 0.69
mmol) afforded diene 20 (173 mg, 54%) as a 85:15
mixture of diastereoisomers. Data for the major isomer:
1H-NMR (300 MHz, CDCl3) 0.08 (s, 3H), 0.10 (s, 3H),
0.86 (s, 9H), 0.93 (d, J=6.7 Hz, 1H), 1.10 (d, J=6.7
Hz, 1H), 1.72 (m, 1H), 1.74 (s, 3H), 2.27 (ddd, J=7.3,
5.0, 1.6 Hz, 1H), 3.19 (s, 3H), 3.28 (dd, J=15.6, 4.7
Hz, 1H), 3.72 (dd, J=15.6, 6.2 Hz, 1H), 4.49 (m, 1H),
4.77 (dd, J=6.2, 4.7 Hz, 1H); 5.88 (d, J=9.8 Hz, 1H),
5.92 (dd, J=9.8, 4.7 Hz, 1H). 13C-NMR (CDCl3, 75
MHz) l −4.1, −3.8, 17.9, 18.0, 20.2, 22.1, 26.0, 31.6,
39.0, 49.9, 52.5, 58.9, 72.1, 95.9, 125.5, 130.2, 131.9,
1
1641 cm−1. Data for 27: H-NMR (300 MHz, CDCl3)
l 0.91 (m, 1H), 1.29 (s, 3H), 1.33–1.69 (m, 6H), 2.00 (s,
3H), 2.02–2.15 (m, 1H), 2.71 (m, 1H), 3.49 (d, J=13.4
Hz, 1H), 3.78 (d, J=13.4 Hz, 1H), 6.00 (s, 1H),
7.21–7.33 (m, SH). 13C-NMR (CDCl3, 75 MHz) l 15.7,
16.4, 20.2, 23.0, 23.1, 49.9, 51.6, 53.5, 57.7, 126.9, 127.9,
128.4, 130.9, 140.6, 179.4, 208.2. IR (neat) 3350, 1704,
133.5, 167.7. IR (neat) 1670 cm−1
.
5.12. N-Benzyl-2,2-dichloro-N-(2-methyl-3-
phenylseleno-cyclohex-1-enyl)-acetamide (22)
To a solution of 21 (693 mg, 2 mmol) in 2-propanol
(20 mmol) were added diphenyldiselenide (1.8 g, 6
mmol), AcOH (2.2 ml, 40 mmol) and nickel powder
(3.4 g, 60 mmol). The resulting mixture was stirred
under reflux in an inert atmosphere for 3 h, then cooled
to r.t., diluted with ether and filtered through Celite.
Water was added to the filtrate, which was subse-
quently neutralised with saturated NaHCO3, washed
with water, brine, dried over magnesium sulphate and
concentrated. The residue was purified by column chro-
matography (silica gel, heptane–AcOEt, 4:1) to afford
22 (757 mg, 81%) as an inseparable mixture of two
isomers (ratio 55:45). 1H-NMR (300 MHz, CDCl3)
major isomer l 1.49 (s, 3H), 1.73–2.06 (m, 6H), 3.69
(m, 1H), 4.49 (d, J=13.8 Hz, 1H), 4.77 (d, J=13.8 Hz,
1H), 6.20 (s, 1H), 7.25–7.59 (m, 10H); minor isomer l
1.52 (s, 3H), 1.73–2.06 (m, 6H), 3.74 (m, 1H), 4.65 (s,
2H), 6.22 (s, 1H), 7.25–7.59 (m, 10H). 13C-NMR
(CDCl3, 75 MHz) major isomer l 18.0, 19.0, 28.5, 29.2,
47.9, 50.3, 64.1, 127.8, 128.0, 128.5, 129.3, 129.8, 130.5,
133.2, 134.6, 135.5, 136.4, 163.5; minor isomer l 18.1,
19.4, 29.2, 29.5, 48.1, 50.4, 63.6, 128.0, 128.1, 128.7,
129.3, 129.4, 130.1, 132.7, 134.4, 135.9, 136.5, 163.9. IR
(neat) 1682 cm−1. MS (IC) m/z 485 (MNH+4 ), 468
(MH+), 391, 310, 293, 276.
1609 cm−1
.
5.14. (+)-(1S,5R,6S)-N-(6-acetoxy-5-isopropyl-2-
methyl-cyclohex-2-enyl)-N-methyl-N-(prop-2-ynyl)-
amine (28)
To a solution of amino-alcohol 2 (1.06 g, 5.8 mmol)
and potassium carbonate (1.6 g, 11.6 mmol) in MeCN
(60 ml) at 0°C, was added propargyl bromide (80% in
toluene, 1.14 ml, 8.7 mmol) and the reaction mixture
was stirred at r.t. for 18 h. Water was added and the
mixture was extracted with EtOAc (3×50 ml). The
combined organic layer was washed with brine, dried
over magnesium sulphate, filtered, and concentrated.
To a solution of the residue in CH2Cl2 (25 ml) at 0°C
was added pyridine (1.17 ml, 14.5 mmol), Ac2O (5 ml,
53 mmol) and a catalytic amount of DMAP. The
reaction mixture was stirred at r.t. for 3 h, and satd. aq.
NaHCO3 was added. The mixture was extracted with
CH2Cl2 (3×50 ml). The combined organic layer was
washed with brine, dried over magnesium sulphate and
concentrated. The residue was purified by column chro-
matography (silica gel, heptane–AcOEt, 95:5) to give
28 (1.34 g, 88%) as a colourless oil. [h]2D5 +137.0° (c
1
0.98, CHCl3). H-NMR (300 MHz, CDCl3) 60.74 (d,