Y. Ishii et al. / Tetrahedron 62 (2006) 716–725
723
3.1.18. (2R,3R,6R,8R,8(1R),9S)-2-Hydroxymethyl-8-
(2-hydroxy-1-methylethyl)-3,9-dimethyl-1,7-dioxaspiro[5.5]-
undecane (21). To a solution of 20 (334 mg, 0.903 mmol)
in methanol (3 ml) was added CSA (20 mg, 0.0862 mmol)
at room temperature. The mixture was stirred for 1 h, then
quenched with saturated aqueous NaHCO3 and extracted
with Et2O. The extract was dried over MgSO4 and
concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel eluted with
hexane–AcOEt (1/1) to give 21 (244 mg, 0.897 mmol, 99%)
as a colorless oil: [a]D19 K66.1 (c 1.03, CHCl3); IR (neat)
3379 cmK1; 1H NMR (400 MHz, CDCl3) d 3.74 (1H, d, JZ
10.6 Hz), 3.64 (1H, dd, JZ10.9, 4.3 Hz), 3.58–3.43 (3H,
m), 3.35 (1H, ddd, JZ9.9, 6.9, 3.0 Hz), 2.20–1.97 (2H, m),
1.88–1.73 (2H, m), 1.72–1.37 (9H, m), 1.09 (3H, d, JZ
6.8 Hz), 0.96 (3H, d, JZ7.3 Hz), 0.85 (3H, d, JZ6.4 Hz);
13C NMR (100 MHz, CDCl3) d 95.9, 75.1, 72.4, 64.7, 64.0,
37.5, 36.0, 30.9, 29.9, 28.1, 27.7, 26.7, 17.4, 14.3, 11.4;
SIMS m/z 273 (MCC1); HR-MS m/z 273.2082 (Calcd for
C15H29O4: 273.2064). Anal. Calcd for C15H28O4: C, 66.14;
H, 10.36. Found: C, 65.76; H, 11.02.
4.25 (1H, dd, JZ11.2, 2.4 Hz), 4.09 (1H, dd, JZ11.2,
6.8 Hz), 3.64 (1H, dd, JZ10.7, 3.9 Hz), 3.57–3.44 (3H, m),
2.13–2.00 (1H, m), 2.08 (3H, s), 1.87–1.20 (11H, m), 1.08
(3H, d, JZ6.3 Hz), 0.95 (3H, d, JZ6.8 Hz), 0.88 (3H, d,
JZ6.3 Hz); 13C NMR (100 MHz, CDCl3) d 171.2 (s), 96.0
(s), 72.8 (d), 72.4 (d), 65.6 (t), 64.9 (t), 37.4 (d), 35.6 (t),
31.4 (d), 29.8 (t), 28.1 (d), 28.0 (t), 26.7 (t), 20.9 (q), 17.5
(q), 14.3 (q), 11.3 (q); SIMS m/z 315 (MCC1); HR-MS m/z
315.2167 (Calcd for C17H31O5: 315.2170).
3.1.20. (2R,2(1R),3S,6R,8R,9R)-2-(2-Acetoxy-1-methyl-
ethyl)-8-formyl-3,9-dimethyl-1,7-dioxaspiro
[5.5]-
undecane (25). To solution of 23 (95.0 mg,
a
0.303 mmol) in CH2Cl2 (2 ml) was added Dess–Martin
periodinane (193 mg, 0.455 mmol) at 0 8C under an argon
atmosphere. The mixture was stirred at 0 8C for 1 h, then
quenched with saturated aqueous NaHCO3 and extracted
with Et2O. The extract was dried over MgSO4 and
concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel eluted with
hexane–AcOEt (9/1) to give 25 (80.0 mg, 0.256 mmol,
84%) as a colorless oil: [a]2D2 K45.6 (c 1.22, CHCl3); IR
(neat) 1742 cmK1; 1H NMR (400 MHz, CDCl3) d 9.58 (1H,
d, JZ2.4 Hz), 4.05 (1H, dd, JZ11.2, 4.4 Hz), 3.85 (1H, dd,
JZ11.2, 6.3 Hz), 3.59 (1H, d, JZ10.0 Hz), 3.42 (1H, d, JZ
10.0 Hz), 2.06 (3H, s), 2.02–1.37 (11H, m), 1.07 (3H, d, JZ
6.8 Hz), 0.95 (6H, d, JZ6.8 Hz); 13C NMR (100 MHz,
CDCl3) d 201.3, 171.2, 95.8, 79.4, 73.1, 66.0, 35.3, 34.7,
30.1, 29.5, 28.0, 27.3, 26.3, 20.9, 16.6, 14.8, 11.0; SIMS m/z
313 (MCC1); HR-MS m/z 313.2013 (Calcd for C17H29O5:
312.2013).
3.1.19. (2R,3R,6R,8R,8(1R),9S)-2-Acetoxymethyl-8-2-
acetoxy-1-methylethyl)-3,9-dimethyl-1,7-dioxaspiro-
[5.5]undecane (22), (2R,3S,3(1R),6R,8R,9R)-2-(2-
acetoxy-1-methylethyl)-8-hydroxymethyl-3,9-dimethyl-
1,7-dioxaspiro[5.5]undecane (23) and (2R,3R,6R,8R,
8(1R),9S)-2-acetoxymethyl-8-(2-hydroxy-1-methylethyl)-
3,9-dimethyl-1,7-dioxaspiro[5.5]undecane (24). A mixture
of spirodiol 1 (94.6 mg, 0.348 mmol), lipase Amano PS
(100 mg) and vinylacetate (20 ml) was incubated at 33 8C
for 39 h. The reaction mixture was filtered and the filtrate
was concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel eluted with
hexane–AcOEt (9/1/1/1) to give 22 (6.0 mg, 0.017 mmol,
5%), 23 (98.0 mg, 0.312 mmol, 90%), 24 (2.0 mg,
0.0064 mmol, 2%) and 21 (3.0 mg, 0.011 mmol, 3%) as
colorless oils. 22: [a]D22 K54.3 (c 1.06, CHCl3); IR (neat)
3.1.21. (2R)-1-Benzyloxy-2-methyl-3-phenylsulfonyl-
propane (26). According to the preparation of 3, (S)-(K)-
3-benzyloxy-2-methylpropanol17 (231 mg, 1.28 mmol) was
converted into the thiophenylated compound (334 mg,
1.23 mmol, 96%) as a colorless oil: [a]2D2 C10.3 (c 1.07,
CHCl3); IR (neat) 2962 cmK1; 1H NMR (400 MHz, CDCl3)
d 7.37–7.22 (9H, m), 7.14 (1H, tt, JZ7.3, 2.0 Hz), 4.47 (2H,
s), 3.46–3.38 (2H, m), 3.15 (1H, dd, JZ13.2, 6.0 Hz), 2.79
(1H, dd, JZ13.2, 7.3 Hz), 2.07 (1H, octet, JZ6.8 Hz), 1.06
(3H, d, JZ6.8 Hz); 13C NMR (100 MHz, CDCl3) d 138.5,
137.2, 128.82, 128.80, 128.3, 127.5, 125.6, 74.0, 73.0, 37.5,
33.8, 16.8; EI-MS m/z 272 (MC); HR-MS m/z 272.1238
(Calcd for C17H20O1S1: 272.1234). According to the
preparation of 4, this thiophenylated compound (300 mg,
1.10 mmol) was converted into 26 (317 mg, 1.04 mmol,
95%) as a colorless oil: [a]2D2 K4.6 (c 1.09, CHCl3); IR
1
1742 cmK1; H NMR (400 MHz, CDCl3) d 4.22 (1H, dd,
JZ11.7, 2.4 Hz), 4.12 (1H, dd, JZ11.7, 6.8 Hz), 4.06 (1H,
dd, JZ11.2, 4.4 Hz), 3.85 (1H, dd, JZ11.2, 6.3 Hz),
3.49–3.43 (2H, m), 2.08 (3H, s), 2.06 (3H, s), 2.10–1.99
(1H, m), 1.98–1.86 (1H, m), 1.81–1.71 (1H, m), 1.70–1.36
(8H, m), 1.07 (3H, d, JZ6.3 Hz), 0.94 (3H, d, JZ6.8 Hz),
0.88 (3H, d, JZ6.3 Hz); 13C NMR (100 MHz, CDCl3) d
171.1, 171.0, 95.9, 73.0, 72.7, 66.3, 65.5, 35.7, 34.7, 31.2,
29.7, 28.1, 27.9, 26.5, 21.0, 20.9, 17.6, 14.9, 11.0; SIMS m/z
357 (MCC1); HR-MS m/z 357.2262 (Calcd for C19H33O6:
357.2275). 23: [a]2D2 K68.9 (c 0.99, CHCl3); IR (neat) 3480,
1
(neat) 1586, 1305 cmK1; H NMR (400 MHz, CDCl3) d
1
1741 cmK1; H NMR (400 MHz, CDCl3) d 4.06 (1H, dd,
7.94–7.89 (2H, m), 7.64 (1H, tt, JZ7.3, 1.5 Hz), 7.55 (2H, t,
JZ6.8 Hz), 7.36–7.23 (5H, m), 4.43 (1H, d, JZ12.2 Hz),
4.40 (1H, d, JZ12.2 Hz), 3.45–3.38 (2H, m), 3.31(1H, dd,
JZ9.3, 6.0 Hz), 2.93 (1H, dd, JZ14.2, 7.8 Hz), 2.46–2.33
(1H, m), 1.12 (3H, d, JZ6.8 Hz); 13C NMR (100 MHz,
CDCl3) d 140.1, 138.1, 133.5, 129.2, 128.4, 127.8, 127.6,
127.5, 73.5, 72.9, 59.3, 29.4, 17.2; EI-MS m/z 304 (MC);
HR-MS m/z 304.1105 (Calcd for C17H20O3S1: 304.1132).
JZ11.0, 4.2 Hz), 3.86 (1H, dd, JZ11.0, 6.2 Hz), 3.73 (1H,
br d, JZ10.7 Hz), 3.59–3.52 (1H, m), 3.45 (1H, dd, JZ
10.1, 2.4 Hz), 3.34 (1H, ddd, JZ10.1, 6.8, 2.9 Hz), 2.06
(3H, s), 2.06–1.89 (2H, m), 1.82–1.73 (1H, m), 1.70–1.39
(9H, m), 1.08 (3H, d, JZ6.6 Hz), 0.95 (3H, d, JZ7.0 Hz),
0.85 (3H, d, JZ6.4 Hz); 13C NMR (100 MHz, CDCl3) d
171.2, 95.9, 75.0, 72.7, 66.1, 64.0, 36.0, 34.8, 30.8, 29.8,
28.1, 27.6, 26.6, 20.9, 17.4, 14.8, 11.1; SIMS m/z 315
(MCC1); HR-MS m/z 315.2170 (Calcd for C17H31O5:
315.2170). Anal. Calcd for C17H30O5: C, 64.94; H, 9.62.
Found: C, 64.99; H, 10.15. 24: [a]2D2 K64.3 (c 1.36, CHCl3);
IR (neat) 3422, 1734 cmK1; 1H NMR (400 MHz, CDCl3) d
3.1.22. (2R,2(3S),3R,6R,8R,8(1R),9S)-2-(4-Benzyloxy-3-
methyl-1-butenyl)-8-(2-hydroxy-1-methylethyl)-3,
9-dimethyl-1,7-dioxaspiro[5.5]undecane (27). To a solution
of 26 (112 mg, 0.368 mmol) in THF (1.7 ml) was added