36
B. Schmidt
Table 2
Summary of total syntheses of seimatopolide A
Entry
Target structure
Source of chirality (stereocenter)
Specific rotation/°cm 2
(10 g) −1
Conclusion for structure assignment Ref.
1
114
Ti-BINOL-mediated allylation (C-9);
asymmetric dihydroxylation (C-6, C-7);
Sharpless epoxidation (C-3)
−143.5, CH
3 OH
Fully confirmed
[126]
2
114
(S)-4-Pentene-1,2-diol; diastereoselective
Prins reaction (C-9, C-7);
d-proline cat.
aminooxylation (C-6); Sharpless
epoxidation (C-3)
−59.3, CH
3 OH
Fully confirmed
[127]
3
114
l-Aspartic acid (C-9, C-3); asymmetric
dihydroxylation (C-6, C-7)
+30.0, CH
3 OH
Absolute configuration revised to
(3S,6S,7S,9R)
[128]
4
114
d-Mannitol (C-6, C-7);
(+)-l-DET-mediated Sharpless epoxidation
(C-9); lipase-mediated resolution (C-3)
+30.9, CH
3 OH
Absolute configuration revised to
(3S,6S,7S,9R)
[129]
5
ent-114
l-(+)-Tartrate (C-6, C-7);
(−)-d-DET-mediated Sharpless
epoxidation (C-9); lipase-mediated
resolution (C-3)
−27.1, CH
3 OH
6
ent-114
Two asymmetric dihydroxylations (C-9;
C-7, C-6); Ru-BINAP-diamine cat.
carbonyl reduction (C-3)
−28.9, CH
3 OH
Revised (3S,6S,7S,9R)
configuration confirmed
[130]
7
114
Sharpless kinetic resolution (C-7);
diastereoselective ketone reduction (C-9,
C-6); aldol addition with thiaoxazolidinone
auxiliary (C-3)
+21.7, CH
3 OH
Revised (3S,6S,7S,9R)
configuration confirmed
[131]
8
ent-114
l-Tartrate (C-6, C-7); oxazoborolidine
catalyzed ketone reduction (C-9);
lipase-Ru-cat. dynamic resolution (C-3)
−27.4, CH
3 OH
Revised (3S,6S,7S,9R)
configuration confirmed
[132]