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DOI: 10.1055/s-2005-872236
Synthesis of the C19-C26 Segment of Amphidinolide H2
Publication History
Publication Date:
20 July 2005 (online)
Abstract
The synthesis of the C19-C26 methyl ketone of amphidinolide H2 is described employing a stereoselective catalytic vinylogous Mukaiyama aldol reaction. Selective dihydroxylation and deoxygenation completes the synthesis of the C19-C26 segment.
Key words
aldol reactions - vinylogous - natural products - deoxygenation - dihydroxylation
- 1
Kobayashi J.Shimbo K.Sato M.Tsuda M. J. Org. Chem. 2002, 67: 6585 - 2
Kobayashi J.Shimbo K.Sato M.Shiro M.Tsuda M. Org. Lett. 2000, 2: 2805 - 3
Usui T.Kazami S.Dohmae N.Mashimo Y.Kondo H.Tsuda M.Terasaki AG.Ohashi K.Kobayashi J.Osada H. Chem. Biol. 2004, 11: 1269 - 4
Saito S.-Y.Feng J.Kira A.Kobayashi J.Ohizumi Y. Biochem. Biophys. Res. Commun. 2004, 320: 961 - Amphidinolide H:
-
5a
Chakraborty TK.Suresh VR. Tetrahedron Lett. 1998, 39: 7775 -
5b
Chakraborty TK.Suresh VR. Tetrahedron Lett. 1998, 39: 9109 - Amphidinolide B:
-
6a
Zhang W.Carter RG.Yokochi AFT. J. Org. Chem. 2004, 69: 2569 -
6b
Cid MB.Pattenden G. Tetrahedron Lett. 2000, 41: 7373 -
6c
Lee D.-H.Rho M.-D. Tetrahedron Lett. 2000, 41: 2573 -
6d
Chakraborty TK.Thippeswamy D. Synlett 1999, 150 -
6e
Eng HM.Myles DC. Tetrahedron Lett. 1999, 40: 2275 -
6f
Eng HM.Myles DC. Tetrahedron Lett. 1999, 40: 2279 -
6g
Ishiyama H.Takemura T.Tsuda M.Kobayashi J. J. Chem. Soc., Perkin Trans. 1 1999, 1163 -
6h
Ishiyama H.Takemura T.Tsuda M.Kobayashi J. Tetrahedron 1999, 55: 4583 -
6i
Ohi K.Nishiyama S. Synlett 1999, 573 -
6j
Ohi K.Nishiyama S. Synlett 1999, 571 -
6k
Cid MB.Pattenden G. Synlett 1998, 540 -
6l
Lee D.-H.Rho M.-D. Bull. Korean Chem. Soc. 1998, 19: 386 -
6m
Ohi K.Shima K.Hamada K.Saito Y.Yamada N.Ohba S.Nishiyama S. Bull. Chem. Soc. Jpn. 1998, 71: 2433 -
6n
Chakraborty TK.Thippeswamy D.Jayaprakash S. J. Indian Chem. Soc. 1998, 75: 741 -
6o
Chakraborty TK.Thippeswamy D.Suresh VR.Jayaprakash S. Chem. Lett. 1997, 563 -
6p
Chakraborty TK.Suresh VR. Chem. Lett. 1997, 565 -
6q
Lee D.-H.Lee S.-W. Tetrahedron Lett. 1997, 38: 7909 - Amphidinolide L:
-
7a
Kobayashi J.Hatakeyama A.Tsuda M. Tetrahedron 1998, 54: 697 -
7b
Tsuda M.Hatakeyama A.Kobayashi J. J. Chem. Soc., Perkin Trans. 1 1998, 149 - 8
Trost BM.Chisholm JD.Wrobleski ST.Jung M. J. Am. Chem. Soc. 2002, 124: 12420 - 9
Trost BM.Papillon JPN. J. Am. Chem. Soc. 2004, 126: 13618 - 10
Trost BM.Harrington PE. J. Am. Chem. Soc. 2004, 126: 5028 -
11a
Hassfeld J.Christmann M.Kalesse M. Org. Lett. 2001, 3: 3561 -
11b
Hassfeld J.Kalesse M. Tetrahedron Lett. 2002, 43: 5093 -
11c
Hassfeld J.Kalesse M. Synlett 2002, 2007 -
11d
Hassfeld J.Eggert U.Kalesse M. Synthesis 2005, 1183 -
11e For a review on the recent achievements in vinylogous Mukaiyama aldol reactions, see:
Kalesse M. In Topics in Current Chemistry Vol. 244:Mulzer JH. Springer Verlag; Berlin: 2004. p.43-76 - Aldehyde 10 is readily available from l-ascorbic acid:
-
12a
Andrews GC.Crawford TC.Bacon BE. J. Org. Chem. 1981, 46: 2976 -
12b
Vekemans JAJM.Boerekamp J.Godefroi EF.Chittenden GJF. Recl. Trav. Chim. Pays-Bas 1985, 104: 266 -
12c
Hubschwerlen C. Synthesis 1986, 962 - 13
Bergquist C.Bridgewater BM.Harlan CJ.Norton JR.Friesner RA.Parkin G. J. Am. Chem. Soc. 2000, 122: 10581 - 15
Ohtani I.Kusumi T.Kashman Y.Kakisawa H. J. Am. Chem. Soc. 1991, 113: 4092 - 16
Hermitage SA.Murphy A.Nielsen P.Roberts SM. Tetrahedron 1998, 54: 13185 - 18
Boydell AJ.Jeffrey MJ.Bürkstümmer E.Linclau B. J. Org. Chem. 2003, 68: 8252
References
Typical Procedure for the Synthesis of 11. Freshly distilled aldehyde 10 (3.13 g, 24.0 mmol) dissolved in Et2O (75 mL) was cooled to -50 °C under argon atmosphere. Tris(pentafluorophenyl)borane monohydrate [13] (318 mg, 600 µmol) was added, and a mixture of ketene acetal 9 [11a] (6.59 g, 28.8 mmol) and i-PrOH (1.27 mL, 16.6 mmol) dissolved in Et2O (30 mL) was added via syringe pump over 40 min. After 1 h, the reaction mixture was warmed to r.t. The solvent was evaporated and flash chromatography using n-hexane-EtOAc (3:1 to 1:1) as eluent afforded 3.51 g (14.4 mmol, 60%, dr 14:1:1:0) of product 11 as a colorless oil: R f = 0.24 (n-hexane-EtOAc, 2:1); [α]D 23 -51.5 (c 0.94, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 6.92 (dd, J = 15.7, 8.2 Hz, 1 H), 5.85 (dd, J = 15.7, 1.0 Hz, 1 H), 4.02 (q-like, J = 5.7 Hz, 1 H), 3.96 (dd, J = 8.0, 6.3 Hz, 1 H), 3.89 (dd, J = 7.9, 6.5 Hz, 1 H), 3.72 (s, 3 H), 3.71-3.68 (m, 1 H), 2.51-2.43 (m, 1 H), 2.24 (br s, 1 H), 1.40 (s, 3 H), 1.33 (s, 3 H), 1.14 (d, J = 6.8 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 166.8, 150.3, 121.4, 109.0, 76.4, 73.5, 64.9, 51.6, 39.2, 26.6, 25.2, 14.3. HRMS (ESI): m/z calcd for C12H21O5 [M + H]+: 245.1389; found: 245.1396.
17It was crucial to sublime 1,1′-thiocarbonyldiimidazole prior to use.
19Methyl ketone 8: R f = 0.33 (n-hexane-EtOAc, 4:1); [α]D 23 +19.3 (c 1.01, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 4.17 (dddd, J = 8.9, 7.0, 5.9, 4.1 Hz, 1 H), 4.07 (d, J = 7.3 Hz, 1 H), 4.04 (dd, J = 8.0, 6.1 Hz, 1 H), 4.01 (dd, J = 7.3, 4.4 Hz, 1 H), 3.49 (dd-like, J = 7.7, 7.3 Hz, 1 H), 2.27 (s, 3 H), 2.04-1.95 (m, 1 H), 1.72 (ddd, J = 13.7, 9.1, 4.4 Hz, 1 H), 1.44 (s, 3 H), 1.42-1.35 (m, 1 H), 1.38 (s, 3 H), 1.37 (s, 3 H), 1.33 (s, 3 H), 1.00 (d, J = 6.8 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 209.2, 110.2, 108.7, 83.0, 81.3, 73.8, 69.8, 37.6, 32.5, 27.0, 26.8, 26.5, 26.1, 25.8, 13.8. HRMS (ESI): m/z calcd for C15H27O5 [M + H]+: 287.1858; found: 287.1857.