(3H, d, J ) 6.6 Hz), 0.98 (3H, d, J ) 6.6 Hz); 13C NMR (75 MHz,
CDCl3) δ 152.8, 86.9, 82.9, 79.4, 67.8, 54.7, 34.3, 27.7, 18.0, 17.4.
ter t-Bu tyl (S)-4-Hyd r oxy-6-m eth ylh ep t-2-yn yl Ca r bon -
a te (5c). The general procedure was followed for Zn(OTf)2 (246
mg, 0.67 mmol), (-)-NME (120 mg, 0.67 mmol), toluene (1 mL),
and Et3N (112 µL, 0.73 mmol) at 50 °C for 2 h; alkyne 2 (116
mg, 0.74 mmol) for 1 h at rt; 3-methylbutanal (273 mg, 3.17
mmol) for 3 h. Direct purification by flash chromatography on
silica gel (EtOAc/hexane 1/9) gave 5c as a colorless oil (105 mg,
(S,S)-4-Isopr opyl-5-vin yl-1,3-dioxolan -2-on e (1b). The gen-
eral procedure was followed for alkenol 8b (34.7 mg, 0.15 mmol)
and Pd(PPh3)4 (8.0 mg, 0.007 mmol) in CH2Cl2 (1.8 mL) for 15
min. Purification by flash chromatography (CH2Cl2/hexane 1/1)
afforded 1b (20.6 mg, 87%, dr > 96:4) as a colorless oil: [R]25
D
-59.4 (c 1.05, CHCl3); IR (film) 2970, 1804, 1364, 1162, 1045
cm-1; 1H NMR (200 MHz, CDCl3) δ 5.88 (1H, ddd, J ) 17.0, 10.3,
7.0 Hz), 5.49 (1H, dt, J ) 17.0, 0.9 Hz), 5.42 (1H, dt, J ) 10.3,
0.9 Hz), 4.76 (1H, ddt, J ) 7.0, 6.6, 0.9 Hz), 4.09 (1H, t, J ) 6.7
Hz), 1.97 (1H, oct, J ) 6.8 Hz), 1.05 (3H, d, J ) 6.8 Hz), 0.99
(3H, d, J ) 6.8 Hz); 13C NMR (50 MHz, CDCl3) δ 154.2, 133.1,
120.7, 86.1, 80.3, 31.5, 17.4, 17.3; HRMS(EI) calcd for C8H12O3
(M+) 156.0786, found 156.0780.
58%): [R]25 -11.7 (c 0.73, CHCl3) for 89% ee;14 IR (film) 3445,
D
2959, 1748, 1369, 1279, 1153 cm-1; 1H NMR (400 MHz, CDCl3)
δ 4.70 (2H, d, J ) 1.8 Hz), 4.45 (1H, qt, J ) 6.6, 1.8 Hz), 1.89
(1H, bd, J ) 5.5 Hz), 1.84 (1H, hp, J ) 6.7 Hz), 1.67-1.52
(2H, m), 1.49 (9H, s), 0.94 (3H, d, J ) 6.6 Hz), 0.92 (3H, d, J )
6.6 Hz); 13C NMR (100 MHz, CDCl3) δ 152.8, 88.4, 82.9, 78.5,
60.9, 54.7, 46.5, 27.7, 24.6, 22.5, 22.4; HRMS(ESI) calcd for
C13H22NaO4 (M + Na+) 265.1416, found 265.1410.
(S,S)-4-Isobu tyl-5-vin yl-1,3-d ioxola n -2-on e (1c). The gen-
eral procedure was followed for alkenol 8c (26.0 mg, 0.11 mmol)
and Pd(PPh3)4 (6.2 mg, 0.005 mmol) in CH2Cl2 (1.8 mL) for 30
min. Purification by flash chromatography (CH2Cl2/hexane 1/1)
ter t-Bu tyl (S)-4-Hyd r oxy-4-p h en ylbu t-2-yn yl Ca r bon a te
(5d ). The general procedure was followed for Zn(OTf)2 (246 mg,
0.67 mmol), (-)-NME (120 mg, 0.67 mmol), toluene (1 mL), and
Et3N (112 µL, 0.73 mmol) at 50 °C for 2 h; Alkyne 2 (95 mg,
0.61 mmol) for 1 h at rt; benzaldehyde (63 µL, 0.91 mmol) for 3
h. Purification by flash chromatography on silica gel (Et2O/
afforded 1c (16.6 mg, 92%, dr 90:10) as a colorless oil: [R]25
D
-51.6 (c 0.94, CHCl3); IR (film) 2962, 1806, 1470, 1368, 1260
cm-1; 1H NMR (300 MHz, CDCl3) δ 5.87 (1H, ddd, J ) 17.1, 10.4,
7.2 Hz), 5.49 (1H, dt, J ) 17.1, 1.0 Hz), 5.43 (1H, dt, J ) 10.4,
0.9 Hz), 4.59 (1H, ddt, J ) 7.7, 7.2, 1.0 Hz), 4.36 (1H, ddd, J )
9.0, 7.7, 4.0 Hz), 1.90-1.69 (2H, m), 1.49 (1H, ddd, J ) 14.1,
7.9, 4.0 Hz), 0.98 (3H, d, J ) 6.6 Hz), 0.97 (3H, d, J ) 6.6 Hz);
13C NMR (75 MHz, CDCl3) δ 154.3, 131.9, 121.4, 83.1, 80.6, 41.9,
24.8, 22.8, 21.9.
hexane 3/7) gave 5d as a colorless oil (56 mg, 35%): [R]25 -1.5
D
(c 1.05, CHCl3) for >96% ee;15 IR (film) 3436, 3033, 2983, 2936,
1746, 1256, 1161 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.53-7.51
(2H, m), 7.37-7.33 (3H, m), 5.49 (1H, s), 4.74 (2H, d, J ) 1.8
Hz), 2.57 (1H, bs), 1.49 (9H, s); 13C NMR (100 MHz, CDCl3) δ
152.8, 140.0, 128.6, 128.4, 126.6, 86.8, 83.0, 80.3, 64.4, 54.7, 27.7;
HRMS(ESI) calcd for C15H18NaO4 (M + Na+) 285.1103, found
285.1118.
(S,S)-4-P h en yl-5-vin yl-1,3-d ioxola n -2-on e (1d ). The gen-
eral procedure was followed for alkenol 8d (33.0 mg, 0.13 mmol)
and Pd(PPh3)4 (8.5 mg, 0.007 mmol) in CH2Cl2 (1.8 mL) for 1 h.
Purification by flash chromatography (CH2Cl2/hexane 1/1) af-
forded 1d (19.6 mg, 83%, dr 90:10) as a colorless oil: [R]25D +3.74
ter t-Bu tyl (R,R)-4-(2,2-Dim eth yl-1,3-d ioxola n -4-yl)-4-h y-
d r oxybu t-2-yn yl Ca r bon a te (5f). The general procedure was
followed for Zn(OTf)2 (246 mg, 0.67 mmol), (+)-NME (120 mg,
0.67 mmol), toluene (1 mL), and Et3N (112 µL, 0.73 mmol) at
50 °C for 2 h; alkyne 2 (118 mg, 0.75 mmol) for 45 min at rt;
(+)-2,3-O-isopropylidene-D-glyceraldehyde (415 mg, 3.20 mmol)
for 30 min. Direct purification by flash chromatography on silica
gel (EtOAc/hexane 3/7) gave 5f as a colorless oil (170 mg, 78%)
(c 0.6, CHCl3); IR (film) 2923, 1802, 1654 cm-1 1H NMR (300
;
MHz, CDCl3) δ 7.46-7.35 (5H, m), 5.99 (1H, ddd, J ) 17.0, 10.5,
7.1 Hz), 5.48 (1H, dt, J ) 10.5, 0.9 Hz), 5.46 (1H, dt, J ) 17.0,
1.0 Hz), 5.28 (1H, d, J ) 8.1 Hz), 4.88 (1H, ddt, J ) 8.1, 7.1, 1.0
Hz); 13C NMR (75 MHz, CDCl3) δ 154.0, 134.7, 131.2, 129.7,
129.2, 125.8, 122.1, 84.7, 83.0; HRMS(ESI) calcd for C11H10NaO3
(M + Na+) 213.0528, found 213.0556.
(4S,4′R,5S)-4-(2,2-Dim et h yl-1,3-d ioxola n yl)-5-vin yl-1,3-
d ioxola n -2-on e (1f). The general procedure was followed for
alkenol 8f (41.0 mg, 0.14 mmol) and, Pd(PPh3)4 (8.2 mg, 0.007
mmol) in CH2Cl2 (1.8 mL) for 1 h. Purification by flash chro-
matography on silica gel (CH2Cl2) afforded 1f (18.5 mg, 61%) as
a colorless oil: [R]25D +20.3 (c 0.65, CHCl3); IR (film) 2925, 1802,
1456, 1374 cm-1; 1H NMR (400 MHz, CDCl3) δ 5.91 (1H, ddd, J
) 17.1, 10.5, 6.4 Hz), 5.52 (1H, bd, J ) 17.1 Hz), 5.41 (1H, bd,
J ) 10.5 Hz), 5.04 (1H, ddt, J ) 6.4, 5.3, 1.2 Hz), 4.28-4.13
(3H, m), 3.94 (1H, dd, J ) 9.2, 3.7 Hz), 1.43 (3H, s), 1.36 (3H, s);
13C NMR (100 MHz, CDCl3) δ 153.7, 132.8, 120.0, 110.6, 80.6,
79.3, 74.9, 66.2, 26.7, 24.7; HRMS(ESI) calcd for C10H14NaO5
(M + Na+) 237.0739, found 237.0744.
as the anti isomer: [R]25 +17.7 (c 0.93, CHCl3); IR (film) 3440,
D
2987, 2939, 1748, 1480, 1457, 1374, 1279, 1256 cm-1; H NMR
1
(400 MHz, CDCl3) δ 4.70 (2H, d, J ) 1.8 Hz), 4.50 (1H, dt, J )
4.5, 1.8 Hz), 4.23 (1H, ddd, J ) 6.5, 6.1, 4.5 Hz), 4.08 (1H, dd, J
) 8.6, 6.5 Hz), 4.03 (1H, dd, J ) 8.6, 6.1 Hz), 1.49 (9H, s), 1.46
(3H, s), 1.37 (3H, s); 13C NMR (100 MHz, CDCl3) δ 152.4, 109.8,
84.0, 82.7, 79.8, 76.4, 65.0, 62.3, 54.2, 27.3, 26.0, 24.8; HRMS-
(ESI) calcd for C14H22NaO6 (M + Na+) 309.1314, found 309.1340.
Gen er a l P r oced u r e for Cycliza t ion s.
A solution of
Pd(PPh3)4 in CH2Cl2 was added to a flask (sealed with a septum)
that contained the alkenol under N2. The size of the flask should
be appropriated to the volume of solvent added, trying to
minimize the nitrogen atmosphere. The mixture was stirred at
rt until TLC showed complete disappearance of the starting
material. The solvent was removed in vacuo, and the crude
mixture was purified by flash chromatography on silica gel.
(S,S)-4-Cycloh exyl-5-vin yl-1,3-d ioxola n -2-on e (1a ). The
general procedure was followed for alkenol 8a (42.6 mg, 0.18
mmol) and Pd(PPh3)4 (10.4 mg, 0.009 mmol) in CH2Cl2 (1.8 mL)
for 15 min. Purification by flash chromatography (CH2Cl2/hexane
Ack n ow led gm en t. This work has been supported
by the Ministerio de Ciencia y Tecnologia (BQU2003-
01269) and Direccio´ General de Recerca, Generalitat de
Catalunya (2001SGR051). We also thank to the Inter-
national Graduate School of Catalonia for a doctorate
studentship to Y. G., and the Swiss National Science
Foundation for a postdoctoral fellowship to Y. A.
1/1) afforded 1a (28.2 mg, 91%, dr 96:4) as a colorless oil: [R]25
D
-44.8 (c 1.13, CHCl3); IR (film) 2931, 1804, 1451, 1362, 1275
cm-1; 1H NMR (400 MHz, CDCl3) δ 5.86 (1H, ddd, J ) 17.2, 10.3,
6.8 Hz), 5.48 (1H, bd, J ) 17.2 Hz), 5.40 (1H, bd, J ) 10.3 Hz),
4.79 (1H, t, J ) 6.8 Hz), 4.09 (1H, t, J ) 6.8 Hz), 1.92-1.63 (5H,
m), 1.35-1.00 (6H, m); 13C NMR (100 MHz, CDCl3) δ 154.4,
133.1, 120.6, 85.4, 80.3, 41.0, 27.7, 27.6, 25.9 25.4, 25.2; HRMS-
(ESI) calcd for C11H16NaO3 (M + Na+) 219.0997, found 219.1001.
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
cedures and characterization data of compounds 1e, 6a , 7a ,
1
E-8a , 8a -d , 8f, 9a , 10a , 12e, 13e, and 14f. H and 13C NMR
spectra for all compounds. This material is available free of
J O048985G
7390 J . Org. Chem., Vol. 69, No. 21, 2004