Journal of Natural Products
Article
HRESIMS m/z [M + Na]+ calcd for C13H12NaO2 223.073 50, found
223.073 12.
(51 mg, 95%) as a white solid: {[α]21D +95 (c 0.4, CHCl3), lit.9 [α]20
D
+101.3 (c 0.4, CHCl3), lit.3 [α]20D −280 (c 0.18, CH2Cl2)}; 1H NMR
(400 MHz, CDCl3) δ 7.44−7.34 (5H, m), 4.96 (1H, m), 4.49 (1H,
m), 4.43 (1H, d, J = 9.6 Hz), 3.63 (1H, m), 3.01 (1H, dd, J = 19.3, 1.5
Hz), 2.89 (1H, dd, J = 19.3, 5.1 Hz), 2.25 (2H, m); 13C NMR (100
MHz, CDCl3) δ 168.7, 137.7, 128.7, 128.6 (2C), 127.3 (2C), 76.6,
74.4, 72.6, 65.8, 36.6, 29.9; ESIMS m/z 235 [M + H]+, 257 [M +
Na]+; HRESIMS m/z [M + Na]+ calcd for C13H14NaO4 257.078 43,
found 257.077 66.
(S)-6-((2R,3R)-3-Phenyloxiran-2-yl)-5,6-dihydro-2H-pyran-2-
one (9a). A buffer solution of 50 mM Na2B4O7·10H2O in 0.4 mM
aqueous Na2EDTA (11 mL) was added to a solution of (S)-
goniothalamin (8) (0.30 g, 1.5 mmol), (R,R)-(+)-N,N′-bis(3,5-di-tert-
butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride
(Jacobsen’s (R,R)-salen−Mn(III) catalyst, 0.040 g, 0.063 mmol) and
n-Bu4NHSO4 (0.018 g, 0.053 mmol) in CH3CN (16 mL), and the
reaction mixture was cooled to 0 °C. 1,1,1-Trifluoroacetone (0.2 mL)
was added, followed by portionwise addition of two solutions of
Oxone (3.40 g, 5.5 mmol) in 0.4 mM aqueous Na2EDTA (17 mL) and
aqueous NaHCO3 (1.1 g in 17 mL of H2O, 13 mmol) with stirring
over a period of 1.5 h. The mixture was treated with H2O (1 mL) and
extracted with Et2O (2 × 5 mL). The combined organic layers were
dried over MgSO4, filtered, and concentrated in vacuo. The residue
was purified by flash chromatography (n-hexane/EtOAc, 1:2) to give
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
1D and 2D NMR spectra of all new compounds (PDF)
epoxide lactone 9a (289 mg, 89%, dr 98:2) as a white solid: {[α]25
D
−97 (c 0.7, CHCl3), for ent-9a [α]25D +95 (c 0.7, CHCl3)}; 1H NMR
(500 MHz, CDCl3) δ 7.38−7.28 (5H, m), 6.93 (1H, ddd, J = 9.7, 5.4,
2.8 Hz), 6.07 (1H, ddd, J = 9.7, 2.4, 1.0 Hz), 4.68 (1H, ddd, J = 10.6,
4.5, 3.6 Hz), 4.08 (1H, d, J = 1.8 Hz), 3.24 (1H, dd, J = 3.6, 2.1 Hz),
2.69−2.63 (1H, m), 2.58−2.52 (1H, m); 13C NMR (125 MHz,
CDCl3) δ 162.8, 144.0, 135.9, 128.6 (3C), 125.7 (2C), 121.6, 75.1,
62.1, 55.0, 26.2; ESIMS m/z 239 [M + Na]+; HRESIMS m/z [M +
Na]+ calcd for C13H12NaO3 239.067 87, found 239.066 81.
AUTHOR INFORMATION
Corresponding Author
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
(6S,7S,8S)-Goniodiol (2). A suspension of compound 9a (0.050 g,
0.23 mmol) in distilled H2O (6 mL) was stirred at 60 °C for 24 h. The
mixture was extracted with EtOAc (2 × 5 mL), and the organic phase
was washed with brine (1 mL), dried over MgSO4, concentrated, and
purified by silica gel flash column chromatography (n-hexane/EtOAc,
4:6) to afford (6S,7S,8S)-goniodiol (2) (52 mg, 96%, dr 97:3) as a
■
The authors thank Council of Scientific and Industrial
Research, Ministry of Science and Technology, New Delhi,
for funding the project ORIGIN (CSC-0108).
REFERENCES
white solid: {[α]25D −64 (c 0.7, CHCl3), for (+)-goniodiol (1) [α]25
■
D
1
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+76 (c 1, CHCl3)}; H NMR (500 MHz, CDCl3) δ 7.43−7.32 (5H,
m), 6.93 (1H, ddd, J = 9.7, 6.4, 2.1 Hz), 6.01 (1H, ddd, J = 9.7, 2.8, 0.7
Hz), 4.95 (1H, d, J = 7.3 Hz), 4.80 (1H, ddd, J = 12.8, 3.8, 2.2 Hz),
3.73 (1H, br t, J = 5.6 Hz), 2.80 (1H, ddt, J = 18.4, 10.9, 2.4 Hz), 2.58
(1H, br s), 2.28 (1H, br d, J = 7.6 Hz), 2.22−2.16 (1H, m); 13C NMR
(100 MHz, CDCl3) δ 163.5, 146.0, 140.6, 128.8 (2C), 128.3, 126.5
(2C), 120.6, 76.7, 75.0, 63.7, 26.0; ESIMS m/z 257 [M + Na]+;
HRESIMS m/z [M + Na]+ calcd for C13H14O4Na 257.078 43, found
257.078 58.
(S)-6-((2S,3S)-3-Phenyloxiran-2-yl)-5,6-dihydro-2H-pyran-2-
one (9b). A buffer solution of 50 mM Na2B4O7·10H2O in 0.4 mM
aqueous Na2EDTA (11 mL) was added to a solution of (S)-
goniothalamin (8) (0.30 g, 1.5 mmol), (S,S)-(+)-N,N′-bis(3,5-di-tert-
butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride
(0.040 g, 0.063 mmol), and n-Bu4NHSO4 (0.018 g, 0.053 mmol) in
CH3CN (16 mL), and the reaction mixture was cooled to 0 °C. 1,1,1-
Trifluoroacetone (0.2 mL) was added, followed by portionwise
addition of two portions of Oxone (3.4 g, 5.5 mmol) in 0.4 mM
aqueous Na2EDTA (17 mL) and aqueous NaHCO3 (1.1 g in 17 mL of
H2O, 13 mmol) with stirring for 2 h. The mixture was treated with
H2O (1 mL) and extracted with Et2O (2 × 5 mL). The combined
organic layers were dried over MgSO4, filtered, and concentrated in
vacuo. The residue was purified by flash chromatography (n-hexane/
EtOAc, 1:2) to give lactone epoxide 9b (291 mg, 90%) as a white
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1
solid: H NMR (400 MHz, CDCl3) δ 7.39−7.26 (5H, m), 6.95 (1H,
ddd, J = 9.7, 5.1, 3.4 Hz), 6.08 (1H, dt, J = 9.7, 2.0 Hz), 4.45 (1H, dt, J
= 9.7, 5.5 Hz), 3.90 (1H, d, J = 1.9 Hz), 3.28 (1H, dd, J = 5.5, 1.9 Hz),
2.62−2.57 (2H, m); 13C NMR (100 MHz, CDCl3) δ 162.8, 144.3,
135.6, 128.7, 128.6 (2C), 125.7 (2C), 121.5, 77.1, 61.5, 57.2, 25.9;
ESIMS m/z 239 [M + Na]+; HRESIMS m/z [M + Na]+ calcd for
C13H12NaO3 239.067 87, found 239.066 81.
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Parvistone E (Leiocarpin A) (6). A suspension of compound 9b
(0.050 g, 0.23 mmol) in distilled H2O (6 mL) was stirred at 60 °C for
24 h. The mixture was subsequently extracted with EtOAc (2 × 5 mL),
and the organic phase was washed with brine (1 mL), dried over
MgSO4, concentrated, and purified by silica gel flash column
chromatography (n-hexane/EtOAc, 4:6), providing parvistone E (6)
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