KOMINE ET AL.
5
905, 714 cm−1; MS (EI) m/z 91, 137 (100), 207, 322 (M+);
HRMS (EI) calcd for C19H30O4 (M+) 322.2144, found
322.2148.
(m, 1H), 5.84-5.80 (m, 1H), 5.53-5.50 (m, 1H), 4.51 (s,
2H), 3.64 (d, J = 9.0 Hz, 1H), 3.53 (s, 3H), 3.47 (d, J = 9.0
Hz, 1H), 2.81 (brd, J = 19.0 Hz, 1H), 2.30 (dd, J = 14.5,
5.0 Hz, 1H), 2.19 (dd, J = 14.5, 5.0 Hz, 1H), 2.13 (brd, J =
19.0 Hz, 1H); 13C-NMR (125 MHz, CDCl3) δ 174.9, 166.0,
137.9, 132.9, 130.8, 130.3, 129.6, 128.3, 128.2, 127.6, 127.4,
124.0, 75.2, 73.2, 67.1, 51.9, 45.3, 32.3, 30.0; FTIR (neat)
3033, 2950, 1717, 1602, 1452, 1274, 1207, 1111,
1025 cm−1; MS (ESI) m/z 270, 281, 403 [(M + Na)+];
HRMS (ESI) calcd for C23H24NaO5 [(M + Na)+] 403.1521,
found 403.1472.
2.2.3 | Methyl (1R,5R)-1-methyl-5-
(propionyloxy)cyclohex-3-ene-1-carboxylate
(20)
According to general procedure, 20 (66.8 mg, 0.295 mmol,
27
97%) was obtained as a yellow oil. [α]D + 48.1 (c 1.00,
1
CHCl3); H-NMR (400 MHz, CDCl3) δ 5.91 (dt, J = 10.0,
4.0 Hz, 1H), 5.67 (d, J = 10.0 Hz, 1H), 5.34 (brs, 1H), 3.68
(s, 3H), 2.61 (d, J = 18.0 Hz, 1H), 2.28 (q, J = 7.6 Hz, 2H),
2.09 (dd, J = 14.0, 6.0 Hz, 1H), 1.98 (dd, J = 14.0, 5.6 Hz,
1H), 1.93 (d, J = 18.0 Hz, 1H), 1.26 (s, 3H), 1.12 (t, J = 7.6
Hz, 3H); 13C-NMR (100 MHz, CDCl3) δ 177.1, 174.0,
129.9, 124.5, 67.1, 51.8, 40.3, 36.4, 33.7, 27.6, 24.1, 8.9;
FTIR (neat) 2946, 1736, 1459, 1195, 1125, 1079,
1013 cm−1; MS (EI) m/z 93 (100), 111, 152, 170, 226 (M+);
HRMS (EI) calcd for C12H18O4 (M+) 226.1205, found
226.1202.
2.2.6 | Methyl (1R,5R)-1-((benzyloxy)
methyl)-5-((pyridin-2-yloxy)carbonyl)
cyclohex-3-ene-1-carboxylate (25)
According to general procedure, 25 (67.0 mg, 0.176 mmol,
28
59%) was obtained as a yellow oil. [α]D + 105.2 (c 1.32,
1
CHCl3); H-NMR (500 MHz, CDCl3) δ 8.76 (brd, J = 5.0
Hz, 1H), 8.07 (d, J = 7.5 Hz, 1H), 7.82 (t, J = 7.5 Hz, 1H),
7.45 (dd, J = 7.5, 4.5 Hz, 1H), 7.36-7.26 (m, 5H), 6.01 (dt,
J = 10.0, 4.0 Hz, 1H), 5.86-5.82 (m, 1H), 5.62-5.59 (m,
1H), 4.52 (s, 2H), 3.64 (d, J = 8.5 Hz, 1H), 3.58 (s, 3H),
3.51 (d, J = 8.5 Hz, 1H), 2.75 (brd, J = 18.5 Hz, 1H), 2.31
(dd, J = 14.0, 5.5 Hz, 1H), 2.28 (dd, J = 14.0, 5.5 Hz, 1H),
2.15 (brd, J = 18.5 Hz, 1H); 13C-NMR (125 MHz, CDCl3)
δ 174.9, 164.4, 149.9, 148.1, 137.9, 136.8, 130.8, 128.3,
127.5, 127.4, 126.7, 125.1, 123.9, 74.5, 73.2, 68.2, 52.0,
45.5, 32.0, 29.9; FTIR (neat) 3033, 2949, 1739, 1582, 1438,
1336, 1305, 1244, 1133 cm−1; MS (ESI) m/z 281, 404
[(M + Na)+]; HRMS (ESI) calcd for C22H23NaO5 [(M +
Na)+] 404.1474, found 404.1431.
2.2.4 | Methyl (1S,5R)-1-((benzyloxy)
methyl)-5-(propionyl-oxy)cyclohex-3-ene-1-
carboxylate (23)
According to general procedure, 23 (98.4 mg, 0.296 mmol,
28
100%) was obtained as a yellow oil. [α]D + 12.0 (c 1.00,
1
CHCl3); H-NMR (400 MHz, CDCl3) δ 7.35-7.26 (m, 5H),
5.86 (brd, J = 10.0 Hz, 1H), 5.65 (brd, J = 10.0 Hz, 1H),
5.40 (brs, 1H), 4.49 (s, 2H), 3.70 (s, 3H), 3.55 (s, 2H), 2.58
(d, J = 18.4 Hz, 1H), 2.36 (dd, J = 13.6, 6.0 Hz, 1H), 2.29
(q, J = 7.6 Hz, 2H), 2.19 (d, J = 18.4 Hz, 1H), 1.80 (dd,
J = 13.6, 7.2 Hz, 1H), 1.11 (t, J = 7.6 Hz, 3H); 13C-NMR
(100 MHz, CDCl3) δ 175.0, 173.9, 138.1, 129.0, 128.3,
127.6, 127.3, 125.5, 75.1, 73.1, 67.1, 52.1, 46.7, 32.6, 29.7,
27.7, 8.9; FTIR (neat) 3036, 2944, 2869, 1729, 1447, 1359,
1181, 1088, 1009, 736, 695 cm−1; MS (ESI) m/z 165 (100),
166, 208, 355 [(M + Na)+]; HRMS (ESI) calcd for
C19H24NaO5 [(M + Na)+] 355.1521, found 355.1475.
2.2.7 | Methyl (1R,5R)-5-(acryloyloxy)-1-
((benzyloxy)methyl)-cyclohex-3-ene-1-
carboxylate (26)
According to general procedure, 26 (48.2 mg, 0.146 mmol,
28
49%) was obtained as a colorless oil. [α]D + 116.6
1
(c 0.97, CHCl3); H-NMR (500 MHz, CDCl3) δ 7.36-7.26
(m, 5H), 6.39 (dd, J = 17.0, 1.5 Hz, 1H), 6.06 (dd, J =
17.0, 10.0 Hz, 1H), 6.00-5.97 (m, 1H), 5.81 (dd, J = 10.0,
1.5 Hz, 1H), 5.73-5.70 (m, 1H), 5.37-5.34 (m, 1H), 4.50 (s,
2H), 3.65 (s, 3H), 3.61 (d, J = 8.5 Hz, 1H), 3.45 (d, J = 8.5
Hz, 1H), 2.75 (brd, J = 18.5 Hz, 1H), 2.18-2.07 (m, 3H);
13C-NMR (125 MHz, CDCl3) δ 174.8, 165.6, 137.9, 130.8,
130.7, 128.5, 128.3, 127.6, 127.4, 123.9, 74.9, 73.2, 66.7,
52.0, 45.3, 32.2, 30.0; FTIR (neat) 3033, 2949, 1713, 1633,
1452, 1402, 1265, 1181, 1091 cm−1; MS (ESI) m/z
270, 281, 286, 353 [(M + Na)+]; HRMS (ESI) calcd for
C19H22NaO5 [(M + Na)+] 353.1365, found 353.1330.
2.2.5 | Methyl (1R,5R)-1-((benzyloxy)
methyl)-5-(phenoxy-carbonyl)cyclohex-3-
ene-1-carboxylate (24)
According to general procedure, 24 (99.5 mg, 0.262 mmol,
28
87%) was obtained as a colorless oil. [α]D + 161.8
1
(c 1.26, CHCl3); H-NMR (500 MHz, CDCl3) δ 8.01 (d,
J = 8.5 Hz, 2H), 7.54 (t, J = 7.5 Hz, 1H), 7.42 (t, J = 7.5
Hz, 2H), 7.35-7.32 (m, 2H), 7.30-7.26 (m, 3H), 6.05-6.01