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11a Compound 2: ¹H NMR (500 MHz,
CDCl3): δ = 6.83 (td, J = 7.0,
15.5 Hz, 1 H), 6.16 (td, J = 1.3,
15.5 Hz, 1 H), 3.41 (t, J = 6.6
Hz, 2 H), 2.95 (q, J = 7.5 Hz,
2 H), 2.38 (ddt, J = 1.3, 7.0,
7.0 Hz, 2 H), 2.03 (tt, J = 6.6,
7.0 Hz, 2 H), 1.28 (t, J = 7.1
Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 189.6, 142.4,
129.5, 32.4, 30.6, 30.2, 23.0, 14.6. HRMS (FAB+): m/z [M + Na] calcd
for C8H13BrOSNa: 259.9766; found: 258.9768.
FTIR (neat): 2965, 2960, 2872, 1667, 1633, 1436, 1265, 1026, 970
cm-¹. Anal. Calcd for C8H13OBrS:
C, 40.52; H, 5.53. Found: C, 40.13; H, 5.53.
11b Compound 3: ¹H NMR (500 MHz,
CDCl3): δ = 6.83 (td, J = 7.1,
15.4 Hz, 1 H), 6.16 (td, J = 1.3,
5.4 Hz, 1 H), 3.41 (t, J = 6.7
Hz, 2 H), 2.95 (t, J = 7.3 Hz,
2 H), 2.37 (ddt, J = 1.3, 7.1,
7.1 Hz, 2 H), 2.03 (tt, J = 6.7,
7.1 Hz, 2 H), 1.59 (tt, J = 7.3,
7.3 Hz, 2 H), 1.41 (qt, J = 7.3,
7.3 Hz, 2 H), 0.92 (t, J = 7.3
Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 189.4,
142.2, 129.5, 32.3, 31.4, 30.6, 30.1, 28.2, 21.7, 13.4. HRMS (FAB+): m/z [M + Na] calcd
for C10H17OBrNa: 287.00813; found: 287.00812. FTIR
(neat): 2959, 2930, 2872, 1671, 1632 cm-¹.
Anal. Calcd for C10H17OBr: C, 45.29; H, 6.46.
Found: C, 45.57; H, 6.57.
11c Compound 4: ¹H NMR (500 MHz,
CDCl3): δ = 6.75 (td, J = 7.1,
15.5 Hz, 1 H), 6.06 (td, J = 1.3,
15.5 Hz, 1 H), 3.41 (t, J = 6.6
Hz, 2 H), 2.34 (tdd, J = 1.3,
7.1, 7.1 Hz, 2 H), 2.01 (tt, J = 6.6,
7.1 Hz, 2 H), 1.50 (s, 9 H). ¹³C NMR (75
MHz, CDCl3): δ = 190.4, 141.4, 130.3,
47.9, 32.5, 30.7, 30.2, 29.8. HRMS (FAB+): m/z [M + Na] calcd
for C10H17OBrSNa: 287.00825; found: 287.00812.
FTIR (neat): 2962, 1667, 1630, 1454, 1363, 968 cm-¹.
Anal. Calcd for C10H17OBrS: C, 45.29; H, 6.46.
Found: C, 45.54; H, 6.50.
11d Compound 5: Treatment of bromide 2 (237
mg, 1 mmol), with tributylphosphine (0.23 mL, 1 mmol) in t-BuOH (2 mL) followed by addition of
KOH (56 mg, 1 mmol) and BnEt3NCl (23 mg, 0.1 mmol) in
CH2Cl2-H2O (10 mL, 1:1) yielded
enone 5 in 99% yield (155 mg). ¹H
NMR (500 MHz, CDCl3): δ = 6.79 (tt, J = 2.2, 2.4 Hz, 1 H), 2.93
(q, J = 7.4 Hz, 2 H), 2.62 (dtt, J = 2.2, 2.3, 7.6 Hz, 2 H),
2.51 (tdt, J = 2.3, 2.4, 7.6
Hz, 2 H), 1.96 (tt, J = 7.6,
7.6 Hz, 2 H), 1.27 (t, J = 7.4
Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 188.9, 144.0,
141.4, 33.2, 31.0, 22.8, 22.7, 13.4. HRMS (CI+): m/z [M + H] calcd
for C8H13OS: 157.06899; found: 157.06872. FTIR
(neat): 2957, 2871, 1655, 1459, 1154 cm-¹.
Anal. Calcd for C8H12OS: C, 61.50; H, 7.74.
Found: C, 61.03; H, 7.65.
11e Compound 6: ¹H NMR (500 MHz,
CDCl3): δ = 6.80 (tt, J = 2.1,
2.3 Hz, 1 H), 2.93 (t, J = 7.4
Hz, 2 H), 2.62 (dtt, J = 2.1,
2.2, 7.6 Hz, 2 H) 2.51 (tdt, J = 2.2,
2.3, 7.6 Hz, 2 H), 1.96 (tt, J = 7.6,
7.6 Hz, 2 H), 1.58 (m, 2 H), 1.41 (tq, J = 7.4,
7.4 Hz, 2 H), 0.94 (t, J = 7.4
Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 189.1,
144.1, 141.5, 33.4, 31.7, 31.2, 28.1, 22.9, 22.0, 13.6. HRMS (CI+): m/z [M+] calcd
for C10H16OS: 185.0999; found: 185.1000. FTIR
(neat): 2958, 2930, 1655, 1613, 1156 cm-¹.
Anal. Calcd for C10H16OS: C, 65.17; H, 8.75.
Found: C, 64.82; H, 8.87.
11f Compound 7: Kishimoto N.
Fujimoto T.
Yamamoto I.
J. Org. Chem.
1999,
64:
5988
11g Compound 8: ¹H NMR (500 MHz, CDCl3): δ = 6.86
(td, J = 6.9, 15.4 Hz, 1 H),
6.12 (td, J = 1.5, 15.4 Hz,
1 H), 3.41 (t, J = 6.6 Hz, 2
H), 2.95 (q, J = 7.3 Hz, 2 H),
2.23 (dtd, J = 1.5, 7.1, 7.1
Hz, 2 H), 1.89 (tt, J = 6.6, 7.1
Hz, 2 H), 1.64 (tt, J = 7.1,
7.1 Hz, 2 H), 1.28 (t, J = 7.3 Hz,
3 H). ¹³C NMR (75 MHz, CDCl3): δ = 189.7,
143.9, 129.0, 33.0, 31.9, 31.0, 26.3, 22.9, 14.7. HRMS (FAB+):
m/z [M + Na] calcd
for C9H15OBrSNa: 272.9927; found: 272.9925.
FTIR (neat): 2930, 1670, 1632, 1451, 1265, 969 cm-¹.
Anal. Calcd for C9H15OBrS: C, 43.03; H, 6.02.
Found: C, 43.36; H, 5.98.
11h Compound 9: Schaumann E.
Mergardt B.
J.
Chem. Soc., Perkin Trans. 1: Organic and Bioorganic Chem.
1989,
1361
11i Compound 10: ¹H NMR (500 MHz,
CDCl3): δ = 6.70 (td, J = 7.8,
15.4 Hz, 1 H), 6.15 (td, J = 1.2,
15.4 Hz, 1 H), 4.23 (ABq, J = 7.1,
7.1 Hz, 2 H), 4.22 (ABq, J = 7.1,
7.1 Hz, 2 H), 3.36 (t, J = 8.2
Hz, 2 H), 2.94 (q, J = 7.4 Hz,
2 H) 2.77 (dd, J = 1.2, 7.8
Hz, 2 H), 2.45 (t, J = 8.2 Hz,
2 H), 1.28 (t, J = 7.4 Hz, 3
H), 1.27 (t, J = 7.1 Hz, 6 H). ¹³C
NMR (75 MHz, CDCl3): δ = 189.3, 169.5, 137.5,
132.2, 61.9, 57.2, 36.7, 36.2, 26.6, 23.1, 14.6, 13.9. HRMS (FAB+): m/z [M + Na] calcd
for C15H23O5BrSNa: 417.0340; found:
417.0347. FTIR (neat): 2980, 2934, 1730, 1671, 1633, 1443, 1261
cm-¹. Anal. Calcd for C15H23O5BrS: C,
45.57; H, 5.86. Found: C, 45.47; H, 5.95.
11j Compound 11: ¹H NMR (500 MHz,
CDCl3): δ = 6.89 (tt, J = 1.8,
4.0 Hz, 1 H), 4.19 (ABq, J = 7.1,
7.1 Hz, 2 H), 4.19 (ABq, J = 7.1, 7.1
Hz, 2 H), 2.91 (q, J = 7.4 Hz,
2 H), 2.76 (td, J = 2.4, 4.0 Hz,
2 H), 2.39 (dtt, J = 1.8, 2.4,
6.4 Hz, 2 H), 2.18 (t, J = 6.4 Hz,
2 H), 1.26 (t, J = 7.4 Hz, 3
H), 1.25 (t, J = 7.1 Hz, 6 H). ¹³C
NMR (75 MHz, CDCl3): δ = 192.0, 170.7,
137.0, 134.2, 61.5, 52.4, 30.9, 27.0, 22.9, 21.2, 14.7, 13.9. HRMS
(CI+): m/z [M + H] calcd
for C15H23O5S: 315.1262; found: 315.1266.
FTIR (neat): 2957, 2930, 2871, 1655, 1156 cm-¹. Anal.
Calcd for C15H22O5S: C, 57.30;
H, 7.05. Found: C, 57.34; H, 7.07.
11k Compound 12: ¹H NMR (500 MHz, CDCl3): δ = 6.67
(td, J = 7.6, 15.3 Hz, 1 H),
6.15 (br d, J = 15.3 Hz, 1 H),
3.76 (s, 6 H), 3.35 (t, J = 8.2
Hz, 2 H), 2.94 (t, J = 7.3 Hz,
2 H), 2.78 (dd, J = 1.1, 7.6
Hz, 2 H), 2.46 (t, J = 8.2 Hz,
2 H), 1.58 (tt, J = 7.3, 7.3
Hz, 2 H), 1.40 (qt, J = 7.3, 7.3
Hz, 2 H), 0.92 (t, J = 7.3 Hz,
3 H). ¹³C NMR (75 MHz, CDCl3): δ = 189.2,
169.9, 137.0, 132.2, 57.3, 52.8, 36.6, 36.2, 31.4, 28.4, 26.5, 21.8,
13.5. HRMS (FAB+): m/z [M + Na] calcd
for C15H23O5BrSNa: 417.03409; found: 417.03472.
FTIR (neat): 2956, 1734, 1670, 1437, 1264 cm-¹. Anal.
Calcd for C15H23O5BrS: C, 45.57;
H, 5.86. Found: C, 45.57; H, 6.17.
11l Compound 13: ¹H NMR (500 MHz, CDCl3): δ = 6.91
(tt, J = 1.5, 4.0 Hz, 1 H),
3.73 (s, 6 H), 2.90 (t, J = 7.3
Hz, 2 H), 2.78 (td, J = 2.2,
4.0 Hz, 2 H), 2.38 (dtt, J = 1.5,
2.2, 6.4 Hz, 2 H), 2.19 (t, J = 6.4
Hz, 2 H), 1.56 (tt, J = 7.3,
7.4 Hz, 2 H), 1.39 (tq, J = 7.4,
7.4 Hz, 2 H), 0.92 (t, J = 7.4
Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 192.1, 171.2,
137.2, 134.0, 52.8, 52.5, 31.6, 31.1, 28.3, 27.2, 22.0, 21.3, 13.6.
HRMS (CI+): m/z [M + H] calcd
for C15H23O5S: 315.12677; found:
315.12662. FTIR (neat): 2955, 2872, 1736, 1651, 1257 cm-¹.
Anal. Calcd for C15H22O5S: C, 57.30;
H, 7.05. Found: C, 57.16; H, 7.20.
11m Compound 14: ¹H NMR (500 MHz,
CDCl3): δ = 6.59 (td, J = 7.6,
15.3 Hz, 1 H), 6.06 (td, J = 1.2,
15.3 Hz, 1 H), 3.76 (s, 6 H), 3.35 (t, J = 8.1
Hz, 2 H), 2.76 (dd, J = 1.2,
7.6 Hz, 2 H), 2.45 (t,
J = 8.1
Hz, 2 H), 1.49 (s, 9 H). ¹³C NMR (75
MHz, CDCl3): δ = 189.7, 170.0, 136.0,
133.0, 57.3, 52.9, 48.2, 36.6, 36.1, 29.7, 26.6. HRMS (FAB+): m/z [M + Na] calcd
for C15H23O5BrSNa: 417.03471; found:
417.02472. FTIR (neat): 2956, 1734, 1667, 1631, 1435, 1264 cm-¹.
Anal. Calcd for C15H23O5BrS: C,
45.57; H, 5.86. Found: C, 45.47; H, 5.95.
11n Compound 15: ¹H NMR (500 MHz,
CDCl3): δ = 6.86 (tt, J = 2.0,
4.4 Hz, 1 H), 3.73 (s, 6 H), 2.73 (td, J = 2.2,
4.0 Hz, 2 H), 2.32 (dtt, J = 2.2,
2.2, 6.4 Hz, 2 H), 2.16 (t, J = 6.4
Hz, 2 H), 1.47 (s, 9 H). ¹³C NMR (75
MHz, CDCl3): δ = 193.0, 171.3, 138.0,
133.2, 52.9, 52.5, 47.6, 31.1, 29.9, 28.3, 27.3, 21.6. HRMS (CI+): m/z [M+] calcd
for C15H22O5S: 315.12718; found:
315.12662. FTIR (neat): 2954, 1735, 1645, 1257 cm-¹.
Anal. Calcd for C15H22O5S: C, 57.30;
H, 7.05. Found: C, 57.66; H, 7.21.
11o Compound 16: ¹H NMR (500 MHz,
CDCl3): δ = 6.70 (dd, J = 8.2,
15.7 Hz, 1 H), 6.13 (dd, J = 1.0,
15.7 Hz, 1 H), 3.40 (ABt, J = 9.7, 6.5
Hz, 1 H), 3.33 (ABt, J = 9.7,
6.5 Hz, 1 H), 2.95 (q, J = 7.4
Hz, 2 H), 2.57 (m, 1 H), 1.94 (ABdt, J = 14.0,
7.0, 7.0 Hz, 1 H), 1.91 (ABdt, J = 14.0,
7.0, 7.0 Hz, 1 H), 1.28 (t, J = 7.4
Hz, 3 H), 1.10 (d, J = 6.8 Hz,
3 H). ¹³C NMR (75 MHz, CDCl3): δ = 189.6,
147.5, 127.9, 43.9, 38.2, 34.7, 30.9, 26.6, 25.8, 23.2, 22.9, 18.8,
14.6, 14.5, 14.4. HRMS (FAB+): m/z [M + Na] calcd
for C9H15OBrNaS: 272.99276; found: 272.99247.
FTIR (neat): 2965, 1670, 1631, 1453 cm-¹.
Anal. Calcd for C9H15OBrS: C, 43.03; H, 6.02.
Found: C, 43.29; H, 6.23.
11p Compound 18: ¹H NMR (500 MHz,
CDCl3): δ = 6.98 (dd, J = 9.2,
15.5 Hz, 1 H), 6.23 (dd, J = 0.7,
15.5 Hz, 1 H), 3.25 (dd, J = 7.1,
10.0 Hz, 1 H), 3.14 (dd, J = 8.2,
10.0 Hz, 1 H), 2.96 (ABq, J = 15.0,
7.5 Hz, 1 H), 2.96 (ABq, J = 15.0,
7.5 Hz, 1 H), 2.78 (dddd, J = 4.0,
4.0, 8.0, 9.1 Hz, 1 H), 1.98 (ddddd, J = 4.0,
4.0, 7.1, 8.2, 10.8 Hz, 1 H), 1.3-1.75 (m, 7 H), 1.29 (t, J = 7.5 Hz, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 189.7, 143.1,
130.0, 42.6, 40.1, 36.6, 30.2, 27.2, 24.8, 23.1, 21.6, 14.7. HRMS
(FAB+): m/z [M + Na] calcd for
C12H19OBrSNa: 313.02361; found: 313.02377.
FTIR (neat): 2930, 2856, 1670, 1628, 1449 cm-¹.
Anal. Calcd for C12H19OBrS: C, 49.49; H, 6.58.
Found: C, 49.70; H, 6.53.
11q Compound 19: HRMS (CI+): m/z [M + Na] calcd
for C12H18OS: 211.1152; found: 211.1157. Anal.
Calcd for C12H18OS: C, 68.52; H, 8.63. Found:
C, 68.27; H, 8.67.
11r
Catalysis
of Reactions of α,β-Unsaturated Thioesters in
the MBH Reaction: General Procedure of the Catalytic MBH Alkylation
Reaction of Thioesters: A solution of thioester 2 (237
mg, 1 mmol) in CH2Cl2-t-BuOH (1:1; 2 mL, 0.5 M), and H2O
(10 mL, 0.1 M) with BnEt3NCl (23 mg, 0.1 mmol) and KOH
(56 mg, 1 mmol) was treated with tributylphosphine (0.45 mL, 0.2
mmol). The reaction was stirred in a resealable tube until complete
consumption of starting material as indicated by TLC. The organic
layer was then extracted with CH2Cl2, dried
over anhyd Na2SO4 and concentrated in vacuo.
Purification via column chroma-tography gave the desired product 5 (152 mg, 97%).