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DOI: 10.1055/s-2002-35582
Synthesis of the C1-C11 Segment of Tedanolide via Vinylogous Mukaiyama Aldol Reaction
Publication History
Publication Date:
20 November 2002 (online)
Abstract
The successful construction of complex natural products depends to a large extent on how efficiently key intermediates can be generated. Here we report our efforts towards the first total synthesis of tedanolide (1), employing Evans’ aldol methodology in combination with a vinylogous Mukaiyama aldol reaction (VMAR) and Sharpless’ asymmetric dihydroxylation. This protocol allows for rapid access to its numerous chiral centers.
Key words
aldol reactions - Mukaiyama - natural products - dihydroxylations - stereoselective synthesis
- 1 Tedanolide was isolated from Tedanis ignis:
Schmitz FJ.Gunasekera SP.Yalamanchili G.Hossain MB.van der Helm D. J. Am. Chem. Soc. 1984, 106: 7251 - 2 13-Deoxytedanolide was isolated from Mycale adhaerens:
Fusetani N.Sugawara T.Matsunaga S.Hirota H. J. Org. Chem. 1991, 56: 4971 -
3a
Matsushima T.Horita K.Nakajima N.Yonemitsu O. Tetrahedron Lett. 1996, 37: 385 -
3b
Matsushima T.Mori M.Nakajima N.Maeda H.Uenishi J.Yonemitsu O. Chem. Pharm. Bull. 1998, 46: 1335 -
3c
Liu J.-F.Abiko A.Pei Z.Buske DC.Masamune S. Tetrahedron Lett. 1998, 39: 1873 -
3d
Taylor RE.Ciavarri JP.Hearn BR. Tetrahedron Lett. 1998, 39: 9361 -
3e
Roush WR.Lane GC. Org. Lett. 1999, 1: 95 -
3f
Matsushima T.Mori M.Zheng B.-Z.Maeda H.Nakajima N.Uenishi J.Yonemitsu O. Chem. Pharm. Bull. 1999, 47: 308 -
3g
Jung ME.Karama U.Marquez R. J. Org. Chem. 1999, 64: 663 -
3h
Matsushima T.Zheng B.-Z.Maeda H.Nakajima N.Uenishi J.Yonemitsu O. Synlett 1999, 780 -
3i
Smith AB.Lodise SA. Org. Lett. 1999, 1: 1249 -
3j
Zheng B.-Z.Maeda H.Mori M.Kusaka S.-I.Yonemitsu O.Matsushima T.Nakajima N.Uenishi J. Chem. Pharm. Bull. 1999, 47: 1288 -
3k
Jung ME.Marquez R. Tetrahedron Lett. 1999, 40: 3129 -
3l
Matsushima T.Nakajima N.Zheng B.-Z.Yonemitsu O. Chem. Pharm. Bull. 2000, 48: 855 -
3m
Zheng B.-Z.Yamauchi M.Dei H.Kusaka S.-I.Matsui K.Yonemitsu O. Tetrahedron Lett. 2000, 41: 6441 -
3n
Zheng B.-Z.Yamauchi H.Dei H.Yonemitsu O. Chem. Pharm. Bull. 2000, 48: 1761 -
3o
Jung ME.Marquez R. Org. Lett. 2000, 2: 1669 -
3p
Jung ME.Lee CP. Org. Lett. 2001, 3: 333 -
3q
Loh T.-P.Feng L.-C. Tetrahedron Lett. 2001, 42: 6001 -
3r
Loh T.-P.Feng L.-C. Tetrahedron Lett. 2001, 42: 3223 -
3s
Matsui K.Zheng B.-Z.Kusaka S.-I.Kuroda M.Yoshimoto K.Yamada H.Yonemitsu O. Eur. J. Org. Chem. 2001, 3615 -
3t
Hearn BR.Ciavarri JP.Taylor RE. Org. Lett. 2002, 4: 2953 - 4
Roush WR.Bannister TD.Wendt MD.Jablonowski JA.Scheidt KA. J. Org. Chem. 2002, 67: 4275 -
5a
Christmann M.Bhatt U.Quitschalle M.Claus E.Kalesse M. Angew. Chem. Int. Ed. 2000, 39: 4364 ; Angew. Chem. 2000, 112, 4535 -
5b
Christmann M.Bhatt U.Quitschalle M.Claus E.Kalesse M. J. Org. Chem. 2001, 66: 1885 -
6a
Christmann M.Kalesse M. Tetrahedron Lett. 2001, 42: 1269 -
6b
Hassfeld J.Christmann M.Kalesse M. Org. Lett. 2001, 3: 3561 -
6c
Hassfeld J.Kalesse M. Tetrahedron Lett. 2002, 43: 5093 - 7
Hoffmann RW.Weidmann U. Chem. Ber. 1985, 118: 3980
References
Aldehyde 11 (92
mg, 0.218 mmol) dissolved in diethyl ether (2 mL) was cooled to -78 °C
under an argon atmosphere. Tris(pentafluorophenyl)borane (110 mg,
0.217 mmol) was added and a mixture of ketene acetal 12 (100
mg, 0.438 mmol) and isopropyl alcohol (17 µL, 0.24 mmol)
dissolved in diethyl ether (1 mL) was added via syringe pump over
6 h. An additional equivalent of ketene acetal 12 (100
mg, 0.438 mmol) was added in diethyl ether (1 mL) over 4 h. After
complete addition, the reaction was quenched by sat. aq NaHCO3 (2
mL), slowly warmed to r.t. and stirred overnight. Water (3 mL) was
added and the mixture was extracted with ether (2 × 15
mL). The organic layer was separated, dried with MgSO4 and
evaporated in vacuo. Flash column chromatography using petroleum
ether/ethyl acetate (4:1) as eluent afforded 13 (73 mg, 62%) as a colorless
oil. 1H NMR (400 MHz, CDCl3): δ = 7.21
(d, J = 8.78
Hz, 2 H), 6.85 (d, J = 8.78 Hz, 2 H), 6.70
(dd, J = 15.69,
9.29 Hz,
1 H), 5.80 (dd, J = 15.69, 0.75 Hz, 1
H), 5.16 (d, J = 9.54 Hz,
1 H), 4.38 (s, 2 H), 3.87 (d, J = 7.44 Hz, 1 H), 3.77
(s,
3 H), 3.70 (s, 3 H), 3.28 (dd, J = 8.90, 5.90 Hz, 1
H), 3.28-3.24 (m, 1 H), 3.18 (dd, J = 8.90, 8.03 Hz, 1
H), 2.77-2.66 (m, 1 H), 2.44-2.36 (m, 2 H), 1.59-1.51
(m, 1 H), 1.53 (d, J = 1.25 Hz, 3 H), 0.97
(d, J = 6.52
Hz, 3 H), 0.90 (d, J = 6.77 Hz, 3 H), 0.85
(d, J = 6.90
Hz, 3 H), 0.85 (s, 9 H), 0.02 (s, 3 H), -0.05 (s, 3 H); 13C
NMR (100 MHz, CDCl3):
δ = 166.9,
159.2, 151.0, 136.2, 130.8, 130.3, 129.2, 120.7, 113.8, 82.4, 75.1,
72.7, 55.2, 51.4, 40.8, 39.7, 32.5, 26.9, 25.9, 18.1, 17.1, 16.7,
11.9, 8.1, -4.4, -5.1; HRMS calcd for C30H50O6Si:
534.3377. Found: 534.3371.