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DOI: 10.1055/s-0028-1087296
A Stereoselective Approach for the Total Synthesis of Clonostachydiol
Publikationsverlauf
Publikationsdatum:
21. Oktober 2008 (online)
Abstract
A stereoselective synthesis of clonostachydiol is accomplished using readily available (±)-epichlorohydrin as a precursor. The synthesis involves direct and straightforward reactions such as Sharpless asymmetric epoxidation, iodination, stereoselective opening of epoxide with allylmagnesium chloride and Sharpless asymmetric dihydroxylation.
Key words
Sharpless asymmetric epoxidation - allylmagnesium chloride - Sharpless asymmetric dihydroxylation
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References and Notes
Compound 15: [α]D +7.5
(c = 1, CDCl3). ¹H
NMR (300 MHz, CDCl3): δ = 6.95 (dd, J = 15.8, 4.5 Hz, 1 H), 6.00
(d, J = 15.8 Hz, 1 H), 4.25
(dd, J = 6.7, 4.5 Hz, 1 H),
3.75-3.85 (m, 1 H), 3.72 (s, 3 H), 1.15 (d, J = 6.7 Hz, 3 H), 0.95 (s,
9
H), 0.10 (s, 3 H), 0.06 (s, 3 H). ¹³C
NMR (50 MHz, CDCl3): δ = 166.4, 147.4,
121.6, 75.6, 70.2, 51.3, 25.6, 18.0, -4.6. IR (Neat): 3452,
2928, 2885, 1714, 1642, 1412, 1225, 915 cm-¹.
MS (ESI): m/z = 297 [M + Na+].
HRMS: m/z calcd for
C13H26O4SiNa: 297.1498; found:
297.1491.
Compound 21: [α]D +7.5
(c = 0.6, CDCl3). ¹H
NMR (300 MHz, CDCl3): δ = 7.22-7.35
(m, 5 H), 6.90 (dd, J = 15.6,
6.2 Hz, 1 H), 5.95 (d, J = 15.6
Hz, 1 H), 4.50-4.62 (m, 2 H), 4.45 (d, J = 6.6
Hz, 2 H), 4.06-4.15 (m, 1 H), 3.45-3.55 (m, 1
H), 3.35 (s, 3 H), 1.50-1.75 (m, 4 H), 1.20 (d, J = 6.0 Hz, 3 H). ¹³C
NMR (50 MHz, CDCl3): δ = 173.4, 152.2,
130.0, 129.6, 129.4, 123.5, 97.2, 77.0, 76.1, 72.5, 55.0, 34.5,
32.2, 23.6. MS (ESI): m/z = 309 [M+ + 1],
331 [M+ + Na]. HRMS: m/z calcd
for C17H24O5Na: 331.1521; found:
331.1519.
Compound 1: [α]D +101
(c = 1, MeOH). ¹H
NMR (300 MHz, CDCl3): δ = 6.85 (dd, J = 14.3, 4.3 Hz, 1 H), 6.78
(dd, J = 15.1, 6.1 Hz, 1 H),
6.08 (d, J = 14.3 Hz, 1 H),
5.95 (d,
J = 15.1
Hz, 1 H), 4.90-4.98 (m, 1 H), 4.15-4.25 (m, 2
H), 3.85-3.95 (m, 1 H), 1.55-1.68 (m, 4 H), 1.25
(d, J = 6.0 Hz, 3 H, Me), 1.25
(d, J = 6.0 Hz, 3 H, Me). IR
(Neat): 3350, 2984, 2918, 1709, 1643, 1252, 1175 cm-¹.
LCMS: m/z = 307 [M+ + Na].