Optically Active R,γ-Substituted γ-Butyrolactones
J . Org. Chem., Vol. 66, No. 11, 2001 3961
1
cm-1; H NMR (300 MHz, CDCl3) δ 1.36 (d, 7.2 Hz, C-2 CH3,
332 (M+, 1.28), 330 (M+, 1.23), 288 (18.24), 286 (18.84), 273
(21.97), 271 (23.56), 207 (100.00), 192 (70.96); HRMS calcd for
3H), 1.93-2.03 (m, H3, H2′, H3′, 3H), 2.18-2.26 (m, H2′, 1H),
2.69 (dd, J 1 ) 13.1 Hz, J 2 ) 9.9 Hz, H3, 1H), 2.82-2.88 (m,
H4′, 2H), 3.06 (m, H2, 1H), 7.11-7.26 (m, ArH, 4H); 13C NMR
(75 MHz, CDCl3) δ 16.98, 19.44, 28.78, 35.379, 38.22, 44.92,
83.62, 124.92, 126.55, 128.16, 129.50, 136.66, 139.12, 179.95;
EIMS (m/z, %) 216 (M+, 37.20), 147 (87.73), 146 (62.45), 129
(100.00), 128 (75.67), 118 (92.53), 115 (59.08), 90 (55.94);
HRMS calcd for C14H16O2 216.1151, found 216.1176; HPLC
(Chiralcel AD, hexane/i-PrOH ) 60:40 (v/v), flow rate ) 0.7
mL/min) tR ) 6.4 min (major), tR ) 7.7 min (minor).
C
17H15O2Br 330.0256, found 330.0277; HPLC (Chiralcel OD,
hexane/i-PrOH ) 80:20 (v/v), flow rate ) 0.7 mL/min) tR
)
16.8 min (major), tR ) 21.2 min (minor).
(-)-tr a n s-r-Eth yl-γ-m eth yl-γ-(2-n a p h th yl)-γ-bu tyr ola c-
ton e (tr a n s-36). [R]20 -12 (c 0.28, CHCl3) for 96% ee; FT-IR
D
(film) ν 2968, 1778, 1602, 1507, 1380, 1223, 1133, 1065, 953,
861, 821, 751 cm-1; 1H NMR (400 MHz, CDCl3) δ 0.95 (t, 3H,
J ) 7.5 Hz), 1.48-1.59 (m, 1H), 1.81 (s, 3H), 1.86-1.97 (m,
1H), 2.10 (t, 1H, J ) 12.2 Hz), 2.39-2.47 (m, 1H), 2.81 (dd,
1H, J 1 ) 12.4 Hz, J 2 ) 8.2 Hz), 7.41-7.51 (m, 3H), 7.82-7.87
(m, 4H); 13C NMR (100 MHz, CDCl3) δ 11.79, 23.23, 30.39,
41.62, 42.52, 84.88, 122.77, 122.94, 126.50, 127.79, 127.71,
128.36, 128.82, 132.75, 133.13, 141.44, 178.74; EIMS (m/z, %)
254 (M+, 55.39), 239 (78.50), 181 (22.57), 166 (15.30), 165
(21.67), 155 (100.00), 152 (14.38), 127 (33.19); HRMS calcd for
C17H18O2 254.1307, found 254.1315; HPLC (Chiralcel AD,
(-)-cis-Sp ir o[(d ih yd r o-3-m eth yl-2(3H)-fu r a n on e)-5,1′-
(1′,2′,3′,4′-tetr a h yd r on a p h th a len e)] (cis-31). [R]20 -17 (c
D
0.25, CHCl3) for 75% ee; FT-IR (KBr) ν 2949, 1760, 1494, 1454,
1322, 1227, 1168, 1091, 977, 933, 767 cm-1; 1H NMR (300 MHz,
CDCl3) δ 1.37 (d, 7.1 Hz, C-2 CH3, 3H), 1.80-1.89 (m, H2′, 1H),
1.98-2.09 (m, H3, H2′, H3′, 4H), 2.66 (dd, J 1 ) 13.1 Hz, J 2
)
8.9 Hz, H3, 1H), 2.80-2.87 (m, H4′, 2H), 2.90-2.96 (m, H2, 1H),
7.08-7.36 (m, ArH, 4H); 13C NMR (100 MHz, CDCl3) δ 15.68,
20.56, 29.25, 34.41, 35.28, 45.09, 83.81, 126.70, 126.79, 128.14,
128.96, 137.49, 138.548, 179.46; EIMS (m/z, %) 216 (M+, 35.01),
147 (80.01), 146 (62.13), 129 (100.00), 128 (80.32), 118 (83.17),
115 (55.35), 90 (52.00); HRMS calcd for C14H16O2 216.1151,
found 216.1155; HPLC (Chiralcel AD, hexane/i-PrOH ) 60:
hexane/i-PrOH ) 80:20 (v/v), flow rate ) 0.7 mL/min) tR
8.7 min (major), tR ) 12.6 min (minor).
)
(-)-cis-r-E t h yl-γ-m et h yl-γ-(2-n a p h t h yl)-γ-b u t yr ola c-
ton e (cis-36). [R]20D -1 (c 0.22, CHCl3) for 14% ee; FT-IR (KBr)
ν 2938, 1754, 1600, 1358, 1293, 1222, 1111, 1065, 953, 859,
1
822, 745 cm-1; H NMR (400 MHz, CDCl3) δ 0.97 (t, 3H, J )
40 (v/v), flow rate ) 0.7 mL/min) tR ) 7.8 min (major), tR
7.3 min (minor).
)
7.4 Hz), 1.41-1.52 (m, 1H), 1.76 (s, 3H), 1.86-1.97 (m, 1H),
2.20 (dd, 1H, J 1 ) 12.4 Hz, J 2 ) 9.6 Hz), 2.72 (dd, 1H, J 1 )
(+)-tr a n s-r-Eth yl-γ-m eth yl-γ-(4-br om op h en yl)-γ-bu tyr -
12.5 Hz, J 2 ) 8.9 Hz), 2.81-2.89 (m, 1H), 7.44-7.53 (m, 3H),
7.81-7.88 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 11.89, 23.89,
29.14, 41.72, 42.12, 84.91, 122.54, 122.62, 126.42, 126.71,
127.79, 128.40, 128.75, 132.77, 133.27, 142.87, 178.32; EIMS
(m/z, %) 254 (M+, 47.40), 239 (86.97), 181 (17.40), 166 (12.99),
165 (18.85), 155 (100.00), 152 (12.63), 127 (31.30); HRMS calcd
for C17H18O2 254.1307, found 254.1313; HPLC (Chiralcel AD,
ola cton e (tr a n s-34). [R]20 +17.7 (c 0.39, CHCl3) for 92% ee;
D
FT-IR (film) ν 2967, 1775, 1593, 1487, 1380, 1221, 1139, 1085,
1009, 953, 828 cm-1; 1H NMR (400 MHz, CDCl3) δ 0.96 (t, 3H,
J ) 7.5 Hz), 1.48-1.56 (m, 1H), 1.71 (s, 3H), 1.87-1.94 (m,
1H), 2.05 (t, 1H, J ) 12.2 Hz), 2.34-2.43 (m, 1H), 2.67 (dd,
1H, J 1 ) 12.4 Hz, J 2 ) 8.3 Hz), 7.24-7.27 (m, 2H), 7.48-7.51
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 11.77, 23.21, 30.45,
41.56, 42.53, 84.31, 121.80, 126.28, 131.92, 143.41, 178.28;
EIMS (m/z, %) 285 (M+ + 3, 41.39), 283 (M+ + 1, 44.90), 269
(94.93), 267 (100.00), 185 (61.43), 183 (63.74), 130 (36.03), 115
(18.70); HRMS calcd for C13H15O2Br 282.0255, found 282.0222;
HPLC (Chiralcel AD, hexane/i-PrOH ) 90:10 (v/v), flow rate
) 0.7 mL/min) tR ) 8.2 min (major), tR ) 9.0 min (minor).
cis-r-E t h yl-γ-m et h yl-γ-(4-b r om op h en yl)-γ-b u t yr ola c-
ton e (cis-34). FT-IR (film) ν 2975, 1763, 1487, 1378, 1218,
hexane/i-PrOH ) 80:20 (v/v), flow rate ) 0.7 mL/min) tR
)
8.4 min (major), tR ) 7.8 min (minor).
(-)-tr a n s-r-P h en yl-γ-m eth yl-γ-(2-n a p h th yl)-γ-bu tyr o-
la cton e (tr a n s-37). [R]20 -96.5 (c 0.195 CHCl3) for 89% ee;
D
FT-IR (KBr) ν 2985, 1771, 1602, 1501, 1381, 1263, 1223, 1133,
1102, 1068, 1020, 971, 946, 930, 900, 829, 759, 750, 703, 692
cm-1; 1H NMR (400 MHz, CDCl3) δ 1.90 (s, 3H), 2.63 (t, 1H, J
) 12.6 Hz), 3.14 (dd, 1H, J 1 ) 12.6 Hz, J 2 ) 8.3 Hz), 3.74 (dd,
1H, J 1 ) 12.6 Hz, J 2 ) 8.3 Hz), 7.25-7.36 (m, 5H), 7.50-7.55
(m, 3H), 7.87-7.95 (m, 4H); 13C NMR (100 MHz, CDCl3) δ
30.35, 45.74, 46.56, 84.91, 122.76, 123.14, 126.71, 126.98,
127.81, 127.89, 128.37, 128.47, 129.08 (2), 132.92, 133.22,
136.40, 140.90, 176.80; EIMS (m/z, %) 302 (M+, 50.27), 258
(86.78), 243 (100.00), 165 (43.65), 155 (57.67), 127 (40.25), 115
(29.91), 91 (23.55); HRMS calcd for C21H18O2 302.1306, found
302.1302; HPLC (Chiralcel AD, hexane/i-PrOH ) 80:20 (v/v),
flow rate ) 0.7 mL/min) tR ) 13.2 min (major), tR ) 19.4 min
(minor).
1206, 1155, 1115, 1079, 1009, 952, 823 cm-1 1H NMR (400
;
MHz, CDCl3) δ 0.97 (t, 3H, J ) 7.4 Hz), 1.40-1.51 (m, 1H),
1.65 (s, 3H), 1.85-1.95 (m, 1H), 2.05 (dd, 1H, J 1 ) 12.5 Hz, J 2
) 10.7 Hz), 2.63 (dd, 1H, J 1 ) 12.5 Hz, J 2 ) 8.9 Hz), 2.76-
2.83 (m, 1H), 7.25-7.28 (m, 2H), 7.49-7.51 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 11.83, 23.80, 29.08, 41.65, 41.99, 84.25,
121.69, 125.98, 131.90, 144.72, 177.92; EIMS (m/z, %) 284 (M+,
9.20), 282 (M+, 8.97), 269 (97.18), 267 (100.00), 185 (62.27),
183 (63.57), 130 (21.86), 129 (13.59); HRMS calcd for C13H15O2-
Br 282.0255, found 282.0276.
(+)-cis-r-P h en yl-γ-m eth yl-γ-(2-n a p h th yl)-γ-bu tyr ola c-
ton e (cis-37). [R]20D +32.5 (c 0.205, CHCl3) for 37% ee; FT-IR
(KBr) ν 3061, 3034, 1760, 1603, 1497, 1386, 1303, 1220, 1199,
1183, 1124, 1080, 1064, 943, 892, 857, 822, 758, 702, 695, 631
cm-1; 1H NMR (300 MHz, CDCl3) δ 1.88 (s, 3H), 2.69 (t, 1H, J
) 12.4 Hz), 3.07 (dd, 1H, J 1 ) 12.8 Hz, J 2 ) 9.1 Hz), 4.20 (dd,
1H, J 1 ) 11.7 Hz, J 2 ) 9.1 Hz), 7.25-7.34 (m, 5H), 7.49-7.54
(m, 3H), 7.83-7.94 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 28.84,
45.03, 46.98, 84.74, 122.46, 122.78, 126.54, 126.80, 127.84,
127.88, 128.36, 128.44, 128.89, 129.10, 132.88, 133.29, 136.70,
142.43, 176.30; EIMS (m/z, %) 302 (M+, 48.23), 258 (47.98),
243 (49.34), 168 (57.44), 155 (66.75), 115 (30.21), 91 (41.04),
43 (100.00); HRMS calcd for C21H18O2 302.1306, found 302.1293;
HPLC (Chiralcel OD, hexane/i-PrOH ) 80:20 (v/v), flow rate
) 0.7 mL/min) tR ) 18.1 min (major), tR ) 21.4 min (minor).
(+)-tr a n s-r-Eth yl-γ-m eth yl-γ-(2-m eth oxyp h en yl)-γ-bu -
(-)-tr a n s-r-P h en yl-γ-m eth yl-γ-(4-br om op h en yl)-γ-bu -
tyr ola cton e (tr a n s-35). [R]20 -35.9 (c 0.37, CHCl3) for 92%
D
ee; FT-IR (film) ν 2976, 1770, 1592, 1377, 1262, 1224, 1133,
1100, 1083, 1072, 1009, 973, 950, 931, 836, 820, 765, 755, 698
cm-1; 1H NMR (300 MHz, CDCl3) δ 1.79 (s, 3H), 2.56 (t, 1H, J
) 12.6 Hz), 2.98 (dd, 1H, J 1 ) 12.7 Hz, J 2 ) 8.3 Hz), 3.68 (dd,
1H, J 1 ) 12.6 Hz, J 2 ) 8.3 Hz), 7.24-7.56 (m, 9H); 13C NMR
(100 MHz, CDCl3) δ 30.38, 45.66, 46.41, 84.32, 122.13, 126.35,
127.95, 128.28, 129.09, 132.13, 136.13, 142.86, 176.32; EIMS
(m/z, %) 333 (M+ + 1, 0.45), 331 (M+ + 1, 0.50), 273 (21.28),
271 (22.55), 207 (100.00), 193 (24.56), 192 (71.92), 191 (29.53);
HRMS calcd for C17H15O2Br 330.0256, found 330.0266; HPLC
(Chiralcel AD, hexane/i-PrOH ) 80:20 (v/v), flow rate ) 0.7
mL/min) tR ) 10.6 min (major), tR ) 15.9 min (minor).
(-)-cis-r-P h en yl-γ-m eth yl-γ-(4-br om op h en yl)-γ-bu tyr o-
la cton e (cis-35). [R]20 -2 (c 0.15, CHCl3) for 22% ee; FT-IR
tyr ola cton e (tr a n s-38). [R]20 +75.0 (c 0.39, CHCl3) for 92%
D
D
(film) ν 2978, 1769, 1604, 1487, 1382, 1315, 1307, 1212, 1201,
1130, 1071, 1010, 955, 944, 824, 755, 705, 697 cm-1; 1H NMR
(300 MHz, CDCl3) δ 1.77 (s, 3H), 2.59 (t, 1H, J ) 12.8 Hz),
ee; FT-IR (film) ν 2959, 1766, 1602, 1489, 1373, 1380, 1230,
1073, 1024, 962, 947, 715 cm-1; 1H NMR (400 MHz, CDCl3) δ
0.95 (t, 3H, 7.5 Hz), 1.45-1.56 (m, 1H), 1.78 (s, 3H), 1.83-
1.92 (m, 1H), 1.94 (dd, 1H, J 1 ) 12.7 Hz, J 2 ) 11.7 Hz), 2.31-
2.39 (m, 1H), 2.98 (dd, 1H, J 1 ) 12.8 Hz, J 2 ) 8.7 Hz), 3.88 (s,
2.97 (dd, 1H, J 1 ) 12.8 Hz, J 2 ) 9.0 Hz), 4.14 (dd, 1H, J 1
)
11.8 Hz, J 2 ) 9.0 Hz), 7.21-7.54 (m, 9H); 13C NMR (75 MHz,
CDCl3) δ 28.84, 44.88, 46.83, 84.10, 121.94, 126.01, 127.97,
128.28, 129.14, 132.04, 136.44, 144.28, 175.94; EIMS (m/z, %)
3H), 6.92-6.95 (m, 2H), 7.26-7.29 (m, 1H), 7.42 (dd, 1H, J 1
)
8.6 Hz, J 2 ) 1.6 Hz); 13C NMR (100 MHz, CDCl3) δ 11.79,