1.7.2 EXPERIMENTAL PROCEDURES AND SPECTROSCOPIC DATA
1.7.2.5 Spectroscopic Data for the Iridium-Catalyzed Allylic Alkylation Products Products
2951, 1734, 1686, 1601, 1453, 1438, 1289, 1240, 1219, 1000, 917, 808, 746 cm-1. HRMS (MM: ESI-APCI+) m/z calc’d for C16H19O3 [M+H]+: 259.1329, found 259.1332. Please note that the provided spectra for epi-54 reflect the inseparable mixture of epi-54 and 54, while the tabulated NMR data is for only epi-54.
Linear isomer 55 was isolated as a colorless oil: 23% ee; [α]D25 –5.2 (c 0.7, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.14 – 8.06 (m, 1H), 7.60 – 7.47 (m, 1H), 7.36 (tdd, J = 7.8, 1.3, 0.6 Hz, 1H), 7.29 – 7.23 (m, 1H), 5.68 – 5.56 (m, 1H), 5.56 – 5.40 (m, 1H), 3.73 (s, 3H), 3.19 – 3.08 (m, 1H), 2.97 (dt, J = 17.3, 4.9 Hz, 1H), 2.71 (ddt, J = 7.2, 2.5, 1.2 Hz, 2H), 2.57 (dt, J = 13.8, 4.9 Hz, 1H), 2.26 – 2.13 (m, 1H), 1.71 (dq, J = 6.4, 1.2 Hz, 3H);
13C NMR (101 MHz, CDCl3) δ 195.3, 172.3, 143.5, 133.6, 132.1, 129.8, 128.9, 128.2, 126.9, 125.7, 57.8, 52.6, 37.7, 30.5, 26.0, 18.2; IR (Neat Film, NaCl) 2918, 2850, 1732, 1689, 1601, 1434, 1263, 1236, 1086, 973, 944, 802, 743 cm-1. HRMS (MM: ESI-APCI+) m/z calc’d for C16H19O3 [M+H]+: 259.1329, found 259.1324; HPLC conditions: 1% IPA, 1 mL/min, Chiralpak IC column, λ = 254 nm, tR (min): major = 19.785, minor = 24.041.
1.7.2.5 Spectroscopic Data for the Iridium-Catalyzed Allylic Alkylation
preparatory TLC (10% Et2O/hexanes) to give the isolated yield of the branched and linear products (30.3 mg, 56% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (2% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 96% ee; [α]D25 –44.3 (c 0.1, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 7.5, 1.5 Hz, 1H), 7.44 (td, J = 7.5, 1.5 Hz, 1H), 7.31 – 7.26 (m, 1H), 7.19 (d, J = 7.5 Hz, 1H), 5.84 (ddd, J = 17.0, 10.2, 8.8 Hz, 1H), 5.20 – 4.96 (m, 2H), 4.24 – 3.95 (m, 2H), 3.26 – 3.08 (m, 2H), 2.89 (ddd, J = 17.4, 4.7, 3.0 Hz, 1H), 2.41 (ddd, J = 13.7, 4.7, 3.0 Hz, 1H), 2.21 (ddd, J = 13.7, 12.3, 4.7 Hz, 1H), 1.19 – 1.09 (m, 6H); 13C NMR (101 MHz, CDCl3) δ 194.4, 170.7, 143.2, 139.1, 133.5, 132.9, 128.8, 128.1, 126.7, 116.5, 61.4, 60.8, 43.4, 28.1, 26.3, 16.6, 14.2; IR (Neat Film, NaCl) 3073, 2978, 2938, 1729, 1693, 1639, 1600, 1454, 1290, 1237, 1220, 1019, 909, 746, 652 cm-1; HRMS (MM: ESI-APCI+) m/z calc’d for C17H21O3 [M+H]+: 273.1485, found 273.1493; SFC conditions: 3% MeOH, 3.5 mL/min, Chiralpak AD-H column, λ = 254 nm, tR (min): major = 4.539, minor = 5.113.
Isopropyl (S)-2-((S)-but-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-
carboxylate (58b). Product 58b was prepared according to the general procedure and isolated by preparatory TLC (8% EtOAc/hexanes) to give the isolated yield of the branched and linear products (31.3 mg, 55% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (2% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 96% ee;
O
CO2i-Pr
[α]D25 –61.5 (c 0.6, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.9, 1.4 Hz, 1H), 7.43 (td, J = 7.5, 1.5 Hz, 1H), 7.37 – 7.22 (m, 1H), 7.18 (d, J = 7.7 Hz, 1H), 5.86 (ddd, J
= 17.1, 10.2, 8.8 Hz, 1H), 5.12 – 4.92 (m, 3H), 3.23 – 3.11 (m, 1H), 3.11 – 2.98 (m, 1H), 2.89 (ddd, J = 17.5, 5.1, 2.9 Hz, 1H), 2.39 (ddd, J = 13.7, 4.8, 2.9 Hz, 1H), 2.20 (ddd, J = 13.7, 12.2, 5.0 Hz, 1H), 1.18 (dd, J = 6.6, 5.3 Hz, 6H), 1.02 (d, J = 6.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 194.6, 170.4, 143.0, 139.2, 133.3, 133.2, 128.7, 128.0, 126.7, 116.5, 69.0, 60.6, 43.4, 28.5, 26.3, 21.8, 21.6, 16.7; IR (Neat Film, NaCl) 3073, 2979, 2936, 1724, 1694, 16001, 1456, 1374, 1288, 1244, 1220, 1179, 1144, 1105, 915, 744 cm-1; HRMS (MM: ESI-APCI+) m/z calc’d for C18H23O3 [M+H]+: 287.1642, found 287.1650;
HPLC conditions: 1% EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min): major = 10.378, minor = 11.179.
2-(Trimethylsilyl)ethyl (S)-2-((S)-but-3-en-2-yl)-1-oxo-1,2,3,4-
tetrahydronaphthalene-2-carboxylate (58c). Product 58c was prepared according to the general procedure and isolated by preparatory TLC (5% Et2O/hexanes) to give the isolated yield of the branched and linear products (18.3 mg, 27% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (1%
EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 89% ee; [α]D25 –46.0 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 8.0, 1.5 Hz, 1H), 7.44 (td, J = 8.0, 1.5 Hz, 1H), 7.29 (t, J = 8.0, 1H), 7.19 (d, J = 8.0, 1H), 5.84 (ddd, J = 17.0, 10.2, 8.8 Hz, 1H), 5.15 – 5.00 (m, 2H), 4.23 – 4.03
O
CO2CH2CH2TMS
(m, 2H), 3.26 – 3.02 (m, 2H), 2.88 (ddd, J = 17.4, 4.9, 2.9 Hz, 1H), 2.40 (ddd, J = 13.7, 4.7, 2.9 Hz, 1H), 2.21 (ddd, J = 13.6, 12.3, 4.9 Hz, 1H), 1.16 (d, J = 6.8 Hz, 3H), 0.89 (dd, J = 9.3, 8.1 Hz, 2H), –0.03 (s, 9H); 13C NMR (101 MHz, CDCl3) δ 194.4, 171.0, 143.3, 139.2, 133.5, 133.0, 128.8, 128.2, 126.7, 116.5, 63.9, 60.8, 43.5, 28.2, 26.3, 17.4, 16.6, –1.5 (3C); IR (Neat Film, NaCl) 3074, 2955, 2899, 1727, 1693, 1601, 1454, 1289, 1251, 1220, 1141, 1041, 918, 860, 837, 746, 695 cm-1; HRMS (FAB+) m/z calc’d for C20H28O3SiNa [M+Na]+: 367.1706, found 367.1720; HPLC conditions: 1%
EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min):
major = 9.018, minor = 9.737.
Ethyl (S)-2-((S)-but-3-en-2-yl)-6-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate (58d). Product 58d was prepared according to the general procedure and isolated by preparatory TLC (8% Et2O/hexanes) to give the isolated yield of the branched and linear products (33.0 mg, 55% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (7% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 84% ee; [α]D25 –12.3 (c 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.8 Hz, 1H), 6.81 (ddd, J = 8.8, 2.6, 0.7 Hz, 1H), 6.63 (d, J = 2.6 Hz, 1H), 5.82 (ddd, J = 17.1, 10.2, 8.8 Hz, 1H), 5.12 – 4.97 (m, 2H), 4.20 – 3.99 (m, 2H), 3.84 (s, 3H), 3.26 – 3.08 (m, 2H), 2.84 (ddd, J = 17.4, 4.9, 3.0 Hz, 1H), 2.39 (ddd, J = 13.6, 4.7, 2.9 Hz, 1H), 2.17 (ddd, J = 13.7, 12.4, 4.9 Hz, 1H), 1.16 (t, J = 7.1 Hz, 3H), 1.12 (d, J = 6.9 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 193.0,
O
CO2Et MeO
170.8, 163.7, 145.9, 139.2, 130.7, 126.5, 116.4, 113.5, 112.3, 61.4, 60.6, 55.6, 43.3, 27.7, 26.7, 16.5, 14.3; IR (Neat Film, NaCl) 3075, 2964, 2935, 2849, 1727, 1681, 1600, 1494, 1446, 1354, 1253, 1217, 1094, 1022, 917, 854, 824 cm-1; HRMS (MM: ESI-APCI+) m/z calc’d for C18H23O4 [M+H]+: 303.1591, found 303.1583; HPLC conditions: 1%
EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min):
major = 23.903, minor = 29.498.
Ethyl (S)-2-((S)-but-3-en-2-yl)-6-(dimethylamino)-1-oxo-1,2,3,4-
tetrahydronaphthalene-2-carboxylate (58e). Product 58e was prepared according to the general procedure and isolated by preparatory TLC (10% EtOAc/hexanes) to give the isolated yield of the branched and linear products (29.0 mg, 46% combined yield). The major diastereomer was isolated as a colorless solid by preparatory HPLC (10%
EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 86% ee; [α]D25 +8.5 (c 0.9, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.9 Hz, 1H), 6.59 (dd, J = 9.0, 2.6 Hz, 1H), 6.31 (d, J = 2.5 Hz, 1H), 5.82 (ddd, J = 17.1, 10.2, 8.7 Hz, 1H), 5.15 – 4.96 (m, 2H), 4.10 (ddq, J = 41.7, 10.8, 7.1 Hz, 2H), 3.31 – 3.12 (m, 2H), 3.04 (s, 6H), 2.78 (ddd, J = 17.1, 4.8, 3.0 Hz, 1H), 2.36 (ddd, J
= 13.4, 4.6, 3.0 Hz, 1H), 2.13 (ddd, J = 13.4, 12.5, 4.8 Hz, 1H), 1.18 (t, J = 7.1 Hz, 3H), 1.09 (d, J = 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 192.1, 171.2, 153.6, 145.5, 139.5, 130.5, 121.9, 116.1, 110.5, 109.2, 61.2, 60.5, 43.2, 40.2 (2C), 27.4, 26.9, 16.4, 14.3; IR (Neat Film, NaCl) 3078, 2935, 1725, 1666, 1595, 1520, 1446, 1370, 1293, 1221,
O
CO2Et Me2N
1196, 1125, 1025, 912, 813 cm-1; HRMS (MM: ESI-APCI+) m/z calc’d for C19H26NO3
[M+H]+: 316.1907, found 316.1912; HPLC conditions: 3% EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min): major = 24.809, minor = 33.026.
Ethyl (S)-2-((S)-but-3-en-2-yl)-7-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate (58f). Product 58f was prepared according to the general procedure and isolated by preparatory TLC (8% Et2O/hexanes) to give the isolated yield of the branched and linear products (41.0 mg, 68% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (2% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 94% ee; [α]D25 –76.8 (c 0.8, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 2.8 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 7.03 (dd, J = 8.4, 2.8 Hz, 1H), 5.84 (ddd, J = 17.0, 10.2, 8.9 Hz, 1H), 5.12 – 4.95 (m, 2H), 4.20 – 4.02 (m, 2H), 3.83 (s, 3H), 3.17 – 3.04 (m, 2H), 2.83 (ddd, J = 17.2, 5.0, 2.9 Hz, 1H), 2.39 (ddd, J = 13.6, 4.6, 2.9 Hz, 1H), 2.19 (ddd, J = 13.7, 12.2, 5.0 Hz, 1H), 1.22 – 1.09 (m, 6H); 13C NMR (101 MHz, CDCl3) δ 194.4, 170.7, 158.3, 139.0, 135.7, 133.6, 129.9, 122.0, 116.4, 109.6, 61.3, 60.5, 55.5, 43.4, 28.4, 25.4, 16.6, 14.1; IR (Neat Film, NaCl) 3075, 2963, 2936, 2838, 1728, 1688, 1609, 1497, 1463, 1419, 1329, 1279, 1232, 1175, 1143, 1034, 920, 881, 819 cm-1; HRMS (MM: ESI-APCI+) m/z calc’d for C18H23O4 [M+H]+: 303.1591, found 303.1583; HPLC conditions: 1% EtOH/hexanes, 1
O
CO2Et MeO
mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min): major = 17.216, minor
= 14.519.
Ethyl (S)-2-((S)-but-3-en-2-yl)-7-nitro-1-oxo-1,2,3,4-tetrahydronaphthalene-2-
carboxylate (58g). Product 58g was prepared according to the general procedure and isolated by preparatory TLC (20% EtOAc/hexanes) to give the isolated yield of inseparable branched and linear products (52.0 mg, 82% combined yield): 93% ee; [α]D25
–53.5 (c 1.4, CHCl3); 1H NMR (400 MHz, CDCl3, major diastereomer) δ 8.86 (d, J = 2.5 Hz, 1H), 8.27 (dd, J = 8.4, 2.5 Hz, 1H), 7.39 (dt, J = 8.7, 0.9 Hz, 1H), 5.81 (ddd, J = 17.1, 10.2, 8.9 Hz, 1H), 5.23 – 4.99 (m, 2H), 4.25 – 3.97 (m, 2H), 3.24 (dddd, J = 18.1, 12.3, 4.8, 1.1 Hz, 1H), 3.13 – 2.96 (m, 2H), 2.46 (ddd, J = 13.9, 4.8, 2.7 Hz, 1H), 2.24 (ddd, J
= 13.9, 12.4, 4.9 Hz, 1H), 1.21 – 1.12 (m, 6H); 13C NMR (101 MHz, CDCl3, major diastereomer) δ 192.4, 170.2, 149.7, 147.2, 138.5, 133.8, 130.3, 127.2, 123.4, 117.2, 61.8, 60.8, 43.6, 27.9, 26.7, 16.6, 14.2; IR (Neat Film, NaCl) 3079, 2979, 2938, 1727, 1698, 1612, 1526, 1421, 1347, 1218, 1181, 1018, 931, 740 cm-1; HRMS (FAB+) m/z calc’d for C17H20NO5 [M+H]+: 318.1341, found 318.1333; HPLC conditions: 5% EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min): major = 14.901, minor
= 13.808.
O
CO2Et O2N
Ethyl (S)-6-bromo-2-((S)-but-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate (58h). Product 58h was prepared according to the general procedure and isolated by silica gel flash column chromatography (5% Et2O/hexanes) to give the isolated yield of the branched and linear products (44.0 mg, 63% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (0.8%
EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 98% ee; [α]D25 –32.7 (c 2.3, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.4 Hz, 1H), 7.42 (ddd, J = 8.4, 2.0, 0.8 Hz, 1H), 7.40 – 7.35 (m, 1H), 5.81 (ddd, J = 17.1, 10.2, 8.9 Hz, 1H), 5.11 – 4.98 (m, 2H), 4.20 – 3.99 (m, 2H), 3.25 – 3.02 (m, 2H), 2.85 (ddd, J = 17.6, 4.9, 2.8 Hz, 1H), 2.40 (ddd, J = 13.7, 4.8, 2.9 Hz, 1H), 2.19 (ddd, J = 13.8, 12.3, 4.9 Hz, 1H), 1.20 – 1.12 (m, 6H); 13C NMR (101 MHz, CDCl3) δ 193.6, 170.5, 144.9, 138.9, 131.8, 131.7, 130.2, 129.8, 128.7, 116.8, 61.6, 60.7, 43.5, 28.0, 26.1, 16.6, 14.3; IR (Neat Film, NaCl) 3074, 2977, 2936, 1728, 1690, 1587, 1444, 1353, 1279, 1235, 1218, 1182, 1144, 1018, 910, 838, 670 cm-1; HRMS (EI+) m/z calc’d for C17H19O3Br [M]+: 350.0518, found 350.0491; SFC conditions: 3% MeOH/hexanes, 3.5 mL/min, Chiralpak AD-H column, λ = 254 nm, tR (min): major = 9.330, minor = 8.616.
O
CO2Et Br
Ethyl (S)-2-((S)-but-3-en-2-yl)-6,8-dimethyl-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate (58i). Product 58i was prepared according to the general procedure and isolated by preparatory TLC (9% EtOAc/hexanes) to give the isolated yield of the branched and linear products (31.0 mg, 52% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (1.5% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 96% ee;
[α]D25 –35.1 (c 0.3, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.72 (d, J = 2.0 Hz, 1H), 7.22 – 7.08 (m, 1H), 5.85 (ddd, J = 17.0, 10.2, 8.9 Hz, 1H), 5.18 – 4.94 (m, 2H), 4.20 – 3.86 (m, 2H), 3.18 – 3.08 (m, 1H), 2.92 (ddd, J = 16.9, 11.6, 5.0 Hz, 1H), 2.81 (ddd, J = 17.7, 5.6, 3.0 Hz, 1H), 2.45 (ddd, J = 13.8, 4.9, 3.0 Hz, 1H), 2.32 (s, 3H), 2.23 (s, 3H), 2.15 (ddd, J = 13.8, 11.5, 5.5 Hz, 1H), 1.17 – 1.10 (m, 6H); 13C NMR (101 MHz, CDCl3) δ 194.9, 170.7, 139.2, 138.7, 136.4, 136.0, 135.8, 132.9, 126.0, 116.4, 61.3, 60.2, 42.9, 27.1, 23.3, 21.0, 19.3, 16.5, 14.2; IR (Neat Film, NaCl) 3075, 2976, 2935, 1730, 1688, 1611, 1477, 1445, 1375, 1286, 1236, 1222, 1163, 1139, 1020, 919, 884 cm-1; HRMS (MM: ESI-APCI+) m/z calc’d for C19H25O3 [M+H]+: 301.1798, found 301.1801; HPLC conditions: 1% IPA/hexanes, 1 mL/min, Chiralpak IC column, λ = 254 nm, tR (min):
major = 9.599, minor = 10.926.
O
CO2Et
(R)-2-((S)-but-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carbonitrile (58j).
Product 58j was prepared according to the general procedure and isolated by preparatory TLC (17% EtOAc/hexanes) to give the isolated yield of the branched and linear products (43.0 mg, 95% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (4% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 52% ee; [α]D25 +11.4 (c 0.4, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.03 (dd, J = 8.0, 1.4 Hz, 1H), 7.54 (td, J = 7.5, 1.5 Hz, 1H), 7.45 – 7.32 (m, 1H), 7.29 – 7.25 (m, 1H), 5.91 (ddd, J = 17.0, 10.3, 8.0 Hz, 1H), 5.17 (dt, J = 10.3, 1.1 Hz, 1H), 5.05 (dt, J = 17.1, 1.2 Hz, 1H), 3.27 – 2.89 (m, 3H), 2.43 (ddd, J = 7.1, 5.3, 3.4 Hz, 2H), 1.22 (d, J = 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 190.3, 142.4, 137.1, 134.6, 130.7, 129.0, 128.9, 127.6, 118.5, 118.1, 53.0, 39.8, 28.5, 25.2, 15.3;
IR (Neat Film, NaCl) 2975, 2930, 1693, 1600, 1454, 1292, 1223, 1158, 1096, 992, 927, 904, 788, 741 cm-1; HRMS (FAB+) m/z calc’d for C15H16ON [M+H]+: 226.1232, found 226.1240; HPLC conditions: 2% EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min): major = 24.027, minor = 26.658.
(R)-2-acetyl-2-((S)-but-3-en-2-yl)-3,4-dihydronaphthalen-1(2H)-one (58k). Product 10k was prepared according to the general procedure and isolated by preparatory TLC (9% EtOAc/hexanes) to give the isolated yield of the branched and linear products (11.0
O
CN
O
C(O)Me
mg, 23% combined yield). The major diastereomer was isolated as a colorless oil by preparatory HPLC (4% EtOAc/hexanes, two Agilent Zorbax RX-sil silica columns in series; flow rate = 15 mL/min; λ = 254 nm): 65% ee; [α]D25 –43.3 (c 0.2, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.05 (dt, J = 8.0, 0.9 Hz, 1H), 7.47 (td, J = 7.5, 1.5 Hz, 1H), 7.33 – 7.27 (m, 1H), 7.19 (dtt, J = 7.7, 1.2, 0.6 Hz, 1H), 5.64 (ddd, J = 17.0, 10.2, 8.8 Hz, 1H), 5.27 – 4.94 (m, 2H), 3.46 – 3.32 (m, 1H), 3.16 (dddt, J = 17.4, 12.6, 4.7, 1.1 Hz, 1H), 2.84 (ddd, J = 17.4, 5.0, 2.7 Hz, 1H), 2.47 (ddd, J = 13.5, 4.7, 2.7 Hz, 1H), 2.12 – 2.06 (m, 1H), 2.09 (s, 3H), 1.06 (d, J = 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 204.7, 196.8, 144.2, 138.3, 134.1, 132.8, 129.0, 128.0, 126.7, 116.5, 68.4, 42.6, 26.9, 25.9, 24.7, 16.3; IR (Neat Film, NaCl) 3076, 2971, 2937, 1708, 1674, 1599, 1446, 1359, 1295, 1231, 1208, 1120, 995, 912, 781, 754, 737 cm-1; HRMS (FAB+) m/z calc’d for C16H19O2 [M+H]+: 243.1385, found 243.1381; HPLC conditions: 1% EtOH/hexanes, 1 mL/min, Chiralpak AD then AD-H column, λ = 254 nm, tR (min): major = 11.271, minor
= 11.944.
1.7.2.6 Experimental Procedures and Spectroscopic Data for the