The Journal of Organic Chemistry
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H-6b′), 0.93 (dq, 1H, J = 13.2, 3.0 Hz, H-3b′), 0.88 (d, 3H, J = 6.6 Hz,
Me-10′), 0.82 (m, 1H, H-4b′), 0.61 (d, 3H, J = 7.0 Hz, Me-8′), 0.43
(d, 3H, J = 7.0 Hz, Me-9′). 13C NMR (125 MHz, CDCl3): δ 168.8
(C-1), 138.2 (C-i), 128.5 (C-p), 128.0 (C-m), 126.8 (C-o), 85.7 (C-3),
80.3 (C-4), 76.1 (C-1′), 74.4 (C-2), 52.9 (OMe), 46.8 (C-2′), 40.1 (C-
6′), 34.1 (C-4′), 31.3 (C-5′), 25.3 (C-7′), 22.9 (C-3′), 21.9 (C-10′),
20.5 (C-9′), 15.6 (C-8′), 3.8 (Me-5). IR (CH2Cl2) νmax: 2953.2,
1741.1, 1449.5, 1240−5, 1096.4, 1012.9 cm−1. MS (EI) m/z (%): 311
([M − OMe]+·, 2.4), 159 ([M − CO2C10H19]+·, 100), 128 (2.3), 115
(2.5), 105 (3.1). HRESIMS calcd for C22H30O3 + Na: 365.2092, found
365.2098.
Me-10′), 0.63 (dd, 1H, J = 13.9, 3.79 Hz, H-3b′). 13C NMR (75.4
MHz, CDCl3): δ 169.4 (C-1), 138.3 (C-i), 128.5 (C-p), 128.1 (C-m),
126.6 (C-o), 85.4 (C-3), 81.4 (C-2′), 80.3 (C-4), 74.6 (C-2), 53.0
(OMe), 49.0 (C-7′), 47.7 (C-1′), 44.7 (C-4′), 36.0 (C-3′), 27.7 (C-6′),
26.8 (C-5′), 19.5 (Me-9′), 18.8 (Me-8′), 13.3 (Me-10′), 3.7 (Me-5). IR
(CH2Cl2) νmax: 2953.8, 1741.9, 1450.8, 1241.2, 1097.8, 1021.4 cm−1.
MS (EI) m/z (%): 159 ([M − CO2C10H17]+·, 100), 128 (3.5), 115
(3.1), 105 (3.7), 81 (5.5), 67 (4.7). HRESIMS calcd for C22H28O3 +
Na: 363.1936, found 363.1940.
(1S,2R)-Bornyl (S)-2-Methoxy-2-phenylpent-3-ynoate 12b.
Obtained in 49% yield as colorless syrup (Rf 0.42, hexane/ethyl
1
(1S,2R,5S)-Menthyl (S)-2-Methoxy-2-phenylpent-3-ynoate
ether 4:1); dr 71:29. [α]24 = −28.8 (c 0.56, CHCl3). H NMR (300
D
10b. Obtained in 50% yield as colorless syrup (Rf 0.54, hexane/
MHz, CDCl3): δ 7.70 (m, 2H, H-o), 7.34 (m, 3H, H-m,p), 4.81 (ddd,
1H, J = 10.0, 3.0, 2.0 Hz, H-2′), 4.42 (s, 3H, OMe), 2.29 (m, 1H, H-
3a′), 2.03 (s, 3H, Me-5), 1.72 (m, 1H, H-6a′), 1.63 (m, 1H, H-5a′),
1.63 (m, 1H, H-4′), 1.14 (m, 1H, H-5b′), 1.14 (m, 1H, H-6b′), 0.91
(dd, 1H, J = 13.7, 3.8 Hz, H-3b′), 0.84 (s, 3H, Me-9′), 0.81 (s, 3H, Me-
8′), 0.58 (s, 3H, Me-10′). 13C NMR (75.4 MHz, CDCl3): δ 169.4 (C-
1), 138.4 (C-i), 128.5 (C-p), 128.1 (C-m), 126.1 (C-o), 85.5 (C-3),
81.5 (C-2′), 80.4 (C-4), 74.5 (C-2), 53.0 (OMe), 48.9 (C-7′), 47.7 (C-
1′), 44.7 (C-4′), 36.2 (C-3′), 27.8 (C-6′), 26.7 (C-5′), 19.5 (Me-9′),
18.8 (Me-8′), 13.1 (Me-10′), 3.7 (Me-5). IR (CH2Cl2) νmax: 2953.8,
1741.9, 1450.9, 1241.9, 1097.7, 1021.5 cm−1. MS (EI) m/z (%): 159
([M − CO2C10H17]+·, 100) 128 (2.3), 105 (2.6), 81 (2.2), 67 (2.3).
HRESIMS calcd for C22H28O3 + Na: 363.1936, found 363.1935.
(1R,2S,4S)-2-Fenchyl (R)-2-Methoxy-2-phenylpent-3-ynoate
1
ethyl ether 4:1); dr 91:9. [α]26 = +63.0 (c 0.24, CHCl3). H NMR
D
(500 MHz, CDCl3): δ 7.65 (m, 2H, H-o), 7.33 (m, 3H, H-m,p), 4.67
(td, 1H, J = 10.9, 4.4 Hz, H-1′), 3.39 (s, 3H, OMe), 1.99 (s, 3H, Me-5),
1.79 (m, 1H, H-6a′), 1.76 (sept-d, 1H, J = 7.0, 2.8 Hz, H-7′), 1.62
(m, 1H, H-4a′), 1.60 (m, 1H, H-3a′), 1.43 (m, 1H, H-5′), 1.36 (tt, 1H,
J = 11.7, 3.1 Hz, H-2′), 1.00 (qd, 1H, J = 13.0, 3.3 Hz, H-3b′), 0.83 (d,
3H, J = 6.5 Hz, Me-10′), 0.82 (d, 3H, J = 7.0 Hz, Me-8′), 0.79 (m, 1H,
H-6b′), 0.79 (m, 1H, H-4b′), 0.67 (d, 3H, J = 7.0 Hz, Me-9′). 13C
NMR (125 MHz, CDCl3): δ 168.8 (C-1), 138.3 (C-i), 128.5 (C-p),
128.1 (C-m), 126.5 (C-o), 85.4 (C-3), 80.4 (C-4), 76.1 (C-1′), 74.8
(C-2), 52.9 (OMe), 47.0 (C-2′), 39.9 (C-6′), 34.1 (C-4′), 31.3 (C-5′),
25.9 (C-7′), 23.3 (C-3′), 21.9 (C-10′), 20.6 (C-9′), 16.1 (C-8′), 3.6
(Me-5). IR (CH2Cl2) νmax: 2954, 1739, 1450, 1240, 1095, cm−1.
HREIMS calcd for C22H30O3: 342.2195, found 342.2207.
13a. Obtained in 42% yield as colorless syrup (Rf 0.56 hexane/Et2O
1
(1R,2S,5R)-Menthyl (R)-2-Methoxy-2-phenylpent-3-ynoate
4:1); dr 88:12. [α]23 = +21.5 (c 0.28, CHCl3). H NMR (500 MHz,
D
11a. Obtained in 53% yield as colorless syrup (Rf 0.54, hexane/
CDCl3): δ 7.70 (m, 2H, H-o), 7.32 (m, 3H, H-m,p), 4.27 (d, 1H, J =
1.9 Hz, H-2′), 3.42 (s, 3H, OMe), 2.01 (s, 3H, Me-5), 1.67 (m, 1H, H-
4′), 1.62 (m, 1H, H-5a′), 1.51 (m, 1H, H-6a′), 1.49 (m, 1H, H-7a′),
1.38 (tdd, 1H, J = 12.4, 5.7, 4.0 Hz, H-5b′), 1.09 (dd, 1H, J = 10.4, 1.5
Hz, H-7b′), 1.06 (s, 3H, Me-9′), 0.90 (tdd, 1H, J = 12.4, 3.4, 2.0 Hz, H-
6b′), 0.71 (s, 3H, Me-10′), 0.69 (s, 3H, Me-8′). 13C NMR (125 MHz,
CDCl3): δ 169.6 (C-1), 138.6 (C-i), 128.5 (C-p), 128.1 (C-m), 126.7
(C-o), 87.6 (C-2′), 85.5 (C-3), 80.3 (C-4), 74.7 (C-2), 53.0 (OMe),
48.4 (C-1′), 48.3 (C-4′), 41.1 (C-7′), 39.7 (C-3′), 29.5 (Me-9′), 26.2
(C-6′), 25.7 (C-5′), 19.9 (Me-10′), 18.9 (Me-8′), 3.6 (Me-5). IR
(CH2Cl2) νmax: 2956, 1743, 1242, 1098 cm−1. MS (EI) m/z (%): 188
(4.3), 159 ([M − CO2C10H17]+·, 100), 128 (3.2), 105 (4.6), 81 (7.7),
67 (6.7). HRESIMS: calcd for C22H28O3 + Na: 363.1936, found
363.1946.
1
ethyl ether 4:1); dr 97:3. [α]24 = −51.4 (c 0.53, CHCl3). H NMR
D
(500 MHz, CDCl3): δ 7.65 (m, 2H, H-o), 7.33 (m, 3H, H-m,p), 4.67
(td, 1H, J = 11.3, 4.4 Hz, H-1′), 3.39 (s, 3H, OMe), 1.99 (s, 3H, Me-
5), 1.79 (m, 1H, H-6a′), 1.76 (sept-d, 1H, J = 7.0, 2.5 Hz, H-7′), 1.62
(m, 1H, H-4a′), 1.60 (m, 1H, H-3a′), 1.43 (m, 1H, H-5′), 1.36 (tt, 1H,
J = 11.3, 2.5 Hz, H-2′), 1.00 (qd, 1H, J = 13.0, 3.3 Hz, H-3b′), 0.83 (d,
3H, J = 6.5 Hz, Me-10′), 0.82 (d, 3H, J = 7.0 Hz, Me-8′), 0.79 (m, 1H,
H-6b′), 0.79 (m, 1H, H-4b′), 0.67 (d, 3H, J = 7.0 Hz, Me-9′). 13C
NMR (125 MHz, CDCl3): δ 168.8 (C-1), 138.3 (C-i), 128.5 (C-p),
128.1 (C-m), 126.5 (C-o), 85.4 (C-3), 80.4 (C-4), 76.1 (C-1′), 74.8
(C-2), 52.9 (OMe), 47.0 (C-2′), 39.9 (C-6′), 34.1 (C-4′), 31.3 (C-5′),
25.9 (C-7′), 23.3 (C-3′), 21.9 (C-10′), 20.6 (C-9′), 16.1 (C-8′), 3.6
(Me-5). IR (CH2Cl2) νmax: 29534.7 1740.4 1450.5, 1240.4, 1095.9,
999.0 cm−1. MS (EI) m/z (%): 311 ([M − OMe]+·, 2.3), 159 ([M −
CO2C10H19]+·, 100), 128 (2.8), 115 (2.3), 105 (2.6). HRESIMS calcd
for C22H30O3 + Na: 365.2092, found 365.2084.
(1R,2S,4S)-2-Fenchyl (S)-2-Methoxy-2-phenylpent-3-ynoate
13b. Obtained in 40% yield as colorless syrup (Rf 0.56 hexane/Et2O
1
4:1); dr 87:13. [α]22 = −8.1 (c 0.12, CHCl3). H NMR (500 MHz,
D
(1R,2S,5R)-Menthyl (S)-2-Methoxy-2-phenylpent-3-ynoate
CDCl3): δ 7.70 (m, 2H, H-o), 7.33 (m, 3H, H-m,p), 4.32 (d, 1H, J =
1.9 Hz, H-2′), 3.41 (s, 3H, OMe), 2.01 (s, 3H, Me-5), 1.63 (m, 1H, H-
6a′), 1.61 (m, 1H, H-4′), 1.51 (m, 1H, H-7a′), 1.48 (m, 1H, H-5a′),
1.35 (tdd, 1H, J = 12.4, 5.9, 4.0 Hz, H-5b′), 1.12 (dd, 1H, J = 10.3, 1.5
Hz, H-7b′), 1.003 (tdd, 1H, J = 12.4, 3.3, 2.1 Hz, H-6b′), 0.999 (s, 3H,
Me-8′), 0.98 (s, 3H, Me-9′), 0.25 (s, 3H, Me-10′). RMN 13C (125
MHz, CDCl3): δ 169.6 (C-1), 138.4 (C-i), 128.5 (C-p), 128.1 (C-m),
126.9 (C-o), 87.7 (C-2′), 85.5 (C-3), 80.3 (C-4), 74.8 (C-2), 53.0
(OMe), 48.6 (C-1′), 48.2 (C-4′), 41.1 (C-7′), 39.5 (C-3′), 29.5 (Me-
9′), 26.3 (C-6′), 25.6 (C-5′), 19.5 (Me-10′), 19.1(Me-8′), 3.6 (Me-5).
IR (CH2Cl2) νmax: 2956, 17343, 1242, 1098 cm−1. MS (EI) m/z (%):
188 (4.2), 159 ([M − CO2C10H17]+·, 100), 128 (3.0), 105 (4.9), 81
(7.5), 67 (6.5). HRESIMS: calcd for C22H28O3 + Na: 363.1936, found
363.1943.
11b. Obtained in 48% yield as colorless syrup (Rf 0.54, hexane/
1
ethyl ether 4:1); dr 93:7. [α]23 = −65.2 (c 0.18, CHCl3). H NMR
D
(500 MHz, CDCl3): δ 7.65 (m, 2H, H-o), 7.32 (m, 3H, H-m,p), 4.60
(td, 1H, J = 11.6, 4.2 Hz, H-1′), 3.38 (s, 3H, OMe), 2.03 (s, 3H, Me-5),
1.96 (dtd, 1H, J = 11.6, 4.2, 1.9 Hz, H-6a′), 1.63 (m, 1H, H-4a′),
1.56 (dq, 1H, J = 13.2, 3.3 Hz, H-3a′), 1.45 (m, 1H, H-5′), 1.26 (tt, 1H,
J = 11.6, 3.2 Hz, H-2′), 1.09 (sept-d, 1H, J = 7.0, 2.8 Hz, H-7′), 0.98 (q,
1H, J = 11.6 Hz, H-6b′), 0.93 (qd, 1H, J = 13.1, 3.0 Hz, H-3b′), 0.88
(d, 3H, J = 6.6 Hz, Me-10′), 0.82 (m, 1H, H-4b′), 0.61 (d, 3H, J = 7.0
Hz, Me- 8′), 0.43 (d, 3H, J = 7.0 Hz, Me-9′). 13C NMR (125 MHz,
CDCl3): δ 186.8 (C-1), 138.2 (C-i), 128.5 (C-p), 128.1 (C-m), 126.8
(C-o), 85.7 (C-3), 80.3 (C-4), 76.1 (C-1′), 74.4 (C-2), 52.9 (OMe),
46.8 (C-2′), 40.1 (C-6′), 34.1 (C-4′), 31.3 (C-5′), 25.3 (C-7′), 23.0 (C-
3′), 22.0 (C-10′), 20.5 (C-9′), 15.6 (C-8′), 3.8 (Me-5). IR (CH2Cl2)
νmax: 1254, 1740, 1450, 1240, 1096 cm−1. HREIMS calcd for
C22H30O3: 342.2195, found 342.2184.
(3R)-3-Tetrahydrofuranyl (R)-2-Methoxy-2-phenylpent-3-
ynoate 14a. Obtained in 21% yield as colorless syrup (Rf 0.16
hexane/AcOEt/CH2Cl2 8:1:1); dr 95:5. [α]23 = +17.0 (c 0.08,
D
(1S,2R)-Bornyl (R)-2-Methoxy-2-phenylpent-3-ynoate 12a.
CHCl3). 1H NMR (500 MHz, CDCl3): δ 7.66 (m, 2H, H-o), 7.35 (m,
3H, H-m,p), 5.30 (ddt, 1H, J = 6.3, 4.7, 1.7 Hz, H-3′), 3.90 (dd, 1H, J =
10.6, 4.7 Hz, H-2a′), 3.77 (dd, 1H, J = 10.6, 1.7 Hz, H-2b′), 3.76 (td,
1H, J = 8.4, 3.8 Hz, H-5a′), 3.64 (td, 1H, J = 8.4, 6.5 Hz, H-5b′), 3.38
(s, 3H, OMe), 2.03 (m, 1H, H-4a′), 2.02 (s, 3H, Me-5), 1.74 (m, 1H,
H-4b′). 13C NMR (125 MHz, CDCl3): δ 169.1 (C-1), 137.9 (C-i),
128.7 (C-p), 128.3 (C-m), 126.7 (C-o), 86.0 (C-3), 80.3 (C-4), 76.4
(C-3′), 74.1 (C-2), 72.6 (C-2′), 66.9 (C-5′), 53.0 (OMe), 32.6 (C-4′),
Obtained in 41% yield as colorless syrup (Rf 0.42, hexane/ethyl
1
ether 4:1); dr 87:13. [α]24 = −7.4 (c 0.53, CHCl3). H NMR (300
D
MHz, CDCl3): δ 7.69 (m, 2H, H-o), 7.34 (m, 3H, H-m,p), 4.85 (ddd,
1H, J = 10.1, 3.1, 1.9 Hz, H-2′), 3.42 (s, 3H, OMe), 2.20 (m, 1H, H-
3a′), 2.02 (s, 3H, Me-5), 1.81 (ddd, 1H, J = 13.1, 9.3, 3.9 Hz, H-6a′),
1.63 (m, 1H, H-5a′), 1.57 (m, 1H, H-4′), 1.20 (m, 1H, H-6b′), 0.92
(m, 1H, H-5b′), 0.84 (s, 3H, Me-9′), 0.82 (s, 3H, Me-8′), 0.79 (s, 3H,
1648
dx.doi.org/10.1021/jo2016554 | J. Org. Chem. 2012, 77, 1640−1652