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d, J¼10.7 Hz), 4.83 (1H, d, J¼10.7 Hz), 4.97 (1H,
d, J¼11.0 Hz), 6.11 (1H, dd, J¼1.5, 15.6 Hz), 7.02 (1H,
dd, J¼4.9, 15.9 Hz), 7.26–7.37 (15H, m); 13C NMR
(68 MHz, CDCl3) d 14.2, 55.3, 60.4, 69.2, 73.4, 75.4,
75.9, 79.7, 81.6, 81.8, 98.1, 122.0, 127.7, 127.9, 128.0,
128.1, 128.1, 128.4, 128.4, 128.5, 137.6, 138.0, 138.5,
143.8, 166.2.
5.3.9. 5a-Lanosta-8,24-dien-3-one (12j). Mp 87–898C.
(lit.36 87–898C).
5.3.10. N-Triphenylmethyl-4-piperidone (12k). Colorless
1
solid; mp .2008C; IR (KBr, cm21) 1705, 1219; H NMR
(270 MHz, CDCl3) d 2.43–2.71 (8H, m), 7.15–7.53 (15H,
m); 13C NMR (68 MHz, CDCl3) d 42.1, 47.7, 77.3, 126.3,
127.7, 128.8, 142.4, 209.1.
5.3.4. (4R,5R)-Ethyl 4,5-epoxy-5-phenylpent-2-enoate.
After alcohol (7l)33 was oxidized according to the general
5.3.11. Methyl N a-Boc-4-keto-prolinate (12l).37 1H NMR
(270 MHz, CDCl3) d 1.42–1.47 (9H, m), 2.54–2.62 (1H,
m), 2.88–3.02 (1H, m), 3.77 (3H, s), 3.83–3.90 (2H, m),
4.70–4.82 (1H, m); 13C NMR (68 MHz, CDCl3) d 28.1,
40.7, 41.1, 52.4, 52.7, 55.5, 56.2, 81.2, 153.4, 154.3, 172.2,
207.5, 208.3.
procedure,
(carbethoxymethylene)triphenylphosphorane
(241 mg, 0.69 mmol) was added to the solution of the
crude product in benzene. The reaction mixture was stirred
at room temperature for 2 h, and the solvent was evaporated.
The residue was purified by column chromatography (silica
gel, hexane/AcOEt¼3/1) to give (4R,5R)-ethyl 4,5-epoxy-
5-phenylpent-2-enoate (E/Z¼76/24, 87 mg, 80%) as a
5.3.12. (3R)-4-Benzyloxy-2,2-dimethyl-3-hydroxy-1-
butanal (14a). Colorless oil; TLC Rf 0.71 (hexane/
AcOEt¼1/1); [a]1D7¼21.29 (c 0.5, EtOH); IR (neat,
1
colorless oil; TLC Rf 0.71 (hexane/AcOEt¼2/1); H NMR
(270 MHz, CDCl3) d 1.23 (0.72H, t, J¼7.3 Hz), 1.30
(2.28H, t, J¼7.3 Hz), 3.46 (0.76H, ddd, J¼0.66, 1.8,
6.9 Hz), 3.82–3.83 (1H, m), 4.16 (0.48H, q, J¼7.3 Hz),
4.22 (1.52 Hz, q, J¼7.3 Hz), 4.63 (0.24H, ddd, J¼0.66, 1.8,
7.9 Hz), 5.91 (0.24H, dd, J¼7.9, 11.5 Hz), 6.04 (0.24H, dd,
J¼0.66, 11.5 Hz), 6.18 (0.76H, dd, J¼0.66, 15.8 Hz), 6.81
(0.76H, dd, J¼6.9, 15.8 Hz) 7.26–7.40 (5H, m); 13C NMR
(68 MHz, CDCl3) d 14.0, 14.2, 58.2, 59.7, 60.4, 60.5, 60.6,
61.0, 124.0, 124.2, 125.5, 125.8, 128.4, 128.5, 128.6, 136.1,
136.2, 143.5, 145.5, 165.5, 165.7.
1
cm21) 3417, 1720, 1095; H NMR (270 MHz, CDCl3) d
1.08 (3H, s), 1.09 (3H, s), 2.75 (1H, brs), 3.46 (1H, dd,
J¼7.4, 9.6 Hz), 3.57 (1H, dd, J¼3.1, 9.6 Hz), 3.92 (1H, dd,
J¼3.1, 7.4 Hz), 4.53 (2H, s), 7.26–7.39 (5H, m), 9.59 (1H,
s); 13C NMR (68 MHz, CDCl3) d 17.6, 18.9, 48.6, 70.5,
73.4, 74.2, 127.7, 127.8, 128.4, 137.5, 205.3; HRMS calcd
for C13H18O3 (Mþ): 222.1256, found m/z 222.1257.
5.3.13. 9-Hydroxy-1-tridecanal (14b). Colorless oil; TLC
Rf 0.70 (hexane/AcOEt¼1/1); IR (neat, cm21) 3340, 1720;
1H NMR (270 MHz, CDCl3) d 0.91 (3H, t, J¼6.8 Hz),
1.32–1.66 (19H, m), 2.43 (2H, td, J¼1.8, 7.3 Hz),
3.57–3.60 (1H, m), 9.77 (1H, t, J¼1.8 Hz); 13C NMR
(68 MHz, CDCl3) d 14.1, 22.0, 22.7, 25.5, 27.8, 29.1, 29.3,
29.4, 37.2, 37.4, 43.9, 71.9, 202.9; MS (EI) m/z 213 (Mþ);
HRMS calcd for C13H26O2 (M2H)þ: 213.1855, found m/z
213.1857.
5.3.5. (2R,3R)-2,3-Epoxyundecanal (8k). Colorless oil;
TLC Rf 0.50 (hexane/ethyl acetate¼6/1); [a]1D7¼221.4 (c
1.0, EtOH); IR (neat, cm21) 1728, 1450; 1H NMR
(270 MHz, CDCl3) d 0.88 (3H, t, J¼6.4 Hz), 1.20–1.60
(12H, m), 1.62–1.71 (2H, m), 3.13 (1H, dd, J¼2.0, 6.3 Hz),
3.23 (1H, td, J¼5.3, 2.0 Hz), 9.01 (1H, d, J¼6.3 Hz); 13C
NMR (68 MHz, CDCl3) d 14.0, 22.6, 25.7, 29.1, 29.2, 29.3,
31.2, 31.8, 56.7, 59.1, 198.4; MS (EI) m/z 184 (Mþ).
5.3.14. 9-Hydroxy-1-decanal (14c).38 1H NMR (270 MHz,
CDCl3) d 1.18 (3H, d, J¼6.1 Hz), 1.21–1.80 (13H, m), 2.43
(2H, td, J¼7.3, 1.5 Hz), 3.75–3.82 (1H, m), 9.76 (1H, t,
J¼1.5 Hz); 13C NMR (68 MHz, CDCl3) d 22.0, 23.4, 25.6,
29.0, 29.2, 29.3, 39.2, 43.8, 68.0, 202.9.
5.3.6. (5S,6R,8R,9S,10S)-6-(tert-Butyldimethylsiloxy)-
5,9-dibenzyloxy-7,7-dimethyl-10-(4-formylbut-1-en-2-
yl)-8-(4-methoxybenzyloxy)-1-oxa-4-oxospiro[2.7]-
decane (8l). Colorless oil; TLC Rf 0.51 (30% EtOAc in
hexanes); [a]1D5.7¼–33.0 (c 1.0, EtOH); IR (neat, cm21
)
1
3424, 3070, 2954, 2892, 1720, 1087; H NMR (270 MHz,
C6D6) d 20.03 (3H, s), 0.00 (3H, s), 0.79 (9H, s), 0.99 (6H,
s), 1.74–1.83 (2H, m), 1.90–2.01 (1H, m), 2.14 (1H, d,
J¼4.8 Hz), 2.29–2.40 (1H, m), 2.47 (1H, d, J¼4.8 Hz),
2.82 (1H, d, J¼11.1 Hz), 3.05 (3H, s), 3.31 (1H, s), 3.79
(1H, d, J¼10.9 Hz), 3.90 (1H, d, J¼11.2 Hz), 4.16–4.29
(4H, m), 4.41 (1H, d, J¼10.9 Hz), 4.50 (1H, s), 4.76 (1H, d,
J¼11.4 Hz), 4.84 (1H, brs), 5.07 (1H, s), 6.59 (1H, d, J¼
8.7 Hz), 6.79–7.27 (12H, m), 9.04 (1H, t, J¼1.3 Hz); 13C
NMR (75 MHz, C6D6) d 24.6, 23.8, 18.5, 26.4, 28.8, 41.4,
44.5, 51.0, 52.0, 54.7, 62.7, 72.7, 74.1, 75.4, 80.8, 89.1, 113.3,
114.1 127.7, 127.8, 127.8, 128.1, 128.3, 128.6, 129.8, 130.9,
138.6, 138.7, 147.9, 159.7, 200.4, 206.1; HRMS calcd for
C44H58NaO8Si (MþNaþ): 765.3799, found m/z 765.3834.
5.4. Large-scale catalytic oxidation of 1-decanol (15c)
(Table 8, entry 3)
To a mechanically stirred suspension of potassium carbonate
˚
(138.2 g, 1.0 mol), molecular sieves 4 A (10 g), and NCS
(14.7 g, 110 mmol) in dichloromethane (400 mL) was added a
solution of 1-decanol (15c) (15.8 g, 100 mmol) in dichloro-
methane (70 mL) at room temperature. After 1 h at room
temperature, the reaction mixture was filtered through Celite
pad, and the filtrate was concentrated by a rotary evaporator.
Ether (200 mL) was added to the residue, and the ether layer
was washed with 20% KOH solution (50 mL£2), 1 M HCl
solution (50 mL£2), H2O (50 mL£2), and brine (50 mL£2),
dried over anhydrous Na2SO4, filtered, and concentrated. The
crude product was purified by distillation (658C, 2 mm Hg) to
give 1-decanal (16c) (14.2 g, 91%) as a colorless oil.
5.3.7. 5-Cholesten-3-one (12h). Mp 125–1268C. (lit.34
124–1298C).
5.5. Synthesis of N-Fmoc phenylglycinal (10) (Eq. (2))25
N-Fmoc-(S)-phenylglycinol (9)39 (.99% ee, 108 mg,
5.3.8. 5a-Androstane-3,17-dione (12i). Mp 129–1308C.
(lit.35 1308C).