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or isomerization under the aldol conditions used or dur-
ing the subsequent purification.
In conclusion, we have developed convergent routes to
synthesize both diketoester 4 and aldehyde 5 and dem-
onstrated their synthetic viability for an aldol coupling.
The stereoselective assembly of the C1–C23 carbon
backbone of tedanolide was accomplished using a chiral
boron reagent with good selectivity. The desired diaste-
reomer 3 represents the carbon framework of tedanolide
with all the required chiral centers installed with the
exception of the epoxide functionality. Efforts directed
at further synthetic exploration to tedanolide are cur-
rently in progress.
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Acknowledgments
Grants from Nanyang Technological University,
National University of Singapore and the Ministry of
Education, Singapore provided the financial support
for this work. We also thank Dr. Li-Chun Feng for
his assistance in this work.
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16. Compound 3a (mixture of 85:15 with 3). Rf = 0.63 (n-
hexane/EtOAc, 4:1); 1H NMR (500 MHz, CDCl3) d
(ppm): 7.23 (d, J = 8.3 Hz, 2H, PhH), 6.86 (d,
J = 8.3 Hz, 2H, PhH), 5.32 (dq, J = 10.6, 6.9 Hz, 1H,
MeCH@CH), 5.26 (dd, J = 0.9, 9.7 Hz, 1H, C@CH), 5.20
(dd, J = 1.9, 8.8 Hz, 1H, CHCH@CMe), 5.19 (ddd,
J = 1.9, 9.3, 10.6 Hz, 1H, MeCH@CHCH), 4.52 (d,
J = 11.6 Hz, 1H, OCHaHbPhOMe), 4.42 (d, J = 11.1 Hz,
1H, OCHaHbPhOMe), 4.33 (d, J = 6.0 Hz, 1H, CHO),
4.19 (d, J = 9.2 Hz, 1H, TBSOCHMeC@), 4.09 (d,
J = 5.1 Hz, 1H, TBSOCHCO), 3.97 (dd, J = 2.8, 5.1 Hz,
1H, MeOCH), 3.95 (ddd, J = 4.2, 4.6, 6.0 Hz, 1H,
CHOH), 3.84 (dd, J = 4.2, 4.2 Hz, 1H, CHO), 3.80 (s,
3H, PhOMe), 3.49 (d, J = 6.9 Hz, 1H, CHcHdO), 3.42 (s,
3H, MeOCH), 3.39 (m, 3H, @CHCHMeCH@, CHcHdO,
MeCHC@O), 3.01 (dq, J = 9.3, 6.9 Hz, 1H, MeCHC@O),
2.72 (dq, J = 2.3, 6.9 Hz, 1H, MeCHC@O), 2.50 (d,
J = 6.0 Hz, 2H, CH2C@O), 2.17 (m, 1H, CH), 2.13 (m,