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DOI: 10.1055/s-0028-1083361
Enantioselective Synthesis of Flavan-3-ols Using a Mitsunobu Cyclization
Publikationsverlauf
Publikationsdatum:
11. Februar 2009 (online)
Abstract
The synthesis of four flavan-3-ols with different substitution patterns and electron densities has been achieved in high stereo- and regioselectivity by a one-step Mitsunobu reaction from the corresponding diols, which were prepared by enantioselective Sharpless dihydroxylation of suitable olefins. The six-membered flavan-3-ols were the only cyclization products and the theoretically possible formation of five-membered rings during the Mitsunobu cyclization was not observed. The flavanols are important starting materials for the synthesis of dimers such as the procyanidins or other coupling products such as the flavan part of the potent DNA polymerase β inhibitor myristinin A. The enantioselectivities of both the Sharpless dihydroxylation and the Mitsunobu cyclization steps were monitored by chiral HPLC.
Key words
myristinin A - Sharpless dihydroxylation - flavanol synthesis - Mitsunobu reaction
- 1
Yoneda S.Kawamoto H.Nakatsubo F. J. Chem. Soc., Perkin Trans. 1 1997, 1025 - 2
Botha JJ.Ferreira D.Roux DG. J. Chem. Soc., Perkin Trans. 1 1981, 1235 -
3a
Erasto P.Bojase-Moleta G.Majinda RT. Phytochemistry 2004, 65: 875 -
3b
Tang S.Bremner P.Kortenkamp A.Schlage C.Gray AI.Gibbons S.Heinrich M. Planta Med. 2003, 69: 247 - 4
Dumontet V.Van Hung N.Adeline MT.Riche C.Chiaroni A.Sevenet T.Gueritte F. J. Nat. Prod. 2004, 67: 858 - 5
Xie DY.Dixon RA. Phytochemistry 2005, 66: 2127 - 6
Lee JS.Kim HJ.Lee YS. Planta Med. 2003, 69: 859 - 7
Aron PM.Kennedy JA. Mol. Nutr. Food Res. 2008, 52: 79 - 8
Williamson G.Manach C. Am. J. Clin. Nutr. 2005, 81: 243S - 9
Deng J.-Z.Starck SR.Li S.Hecht SM. J. Nat. Prod. 2005, 68: 1625 - 10
Akira M.Hirokazu Y.Takebayashi Y.Harumitsu I.Kazuo H. J. Pharmacol. Exp. Ther. 1992, 263: 1302 - 11
Sawadjoon S.Kittakoop P.Kirtikara K.Vichai V.Tanticharoen M.Thebtaranonth Y. J. Org. Chem. 2002, 67: 5470 - 12
Maloney DJ.Deng J.-Z.Starck SR.Gao Z.Hecht SM. J. Am. Chem. Soc. 2005, 127: 4140 - 13
Starck SR.Deng J.-Z.Hecht SM. Biochemistry 2000, 39: 2413 -
14a
Sharpless KB.Amberg W.Beller M.Chen H.Hartung J.Kawanami Y.Lübben D.Manoury E.Ogino Y.Shibata T.Ukita T. J. Org. Chem. 1991, 56: 4585 -
14b
Kolb HC.VanNieuwenhze MS.Sharpless KB. Chem. Rev. 1994, 94: 2483 - 15
van Rensburg H.van Heerden PS.Bezuidenhoudt BCB.Ferreira D. Tetrahedron Lett. 1997, 38: 3089 - 16
Saito A.Nakajima N.Tanaka A.Ubukata M. Tetrahedron 2002, 58: 7829 - 17
Minami N.Kijima S. Chem. Pharm. Bull. 1979, 27: 1490 - 18
Wan SB.Chen D.Dou QP.Chan TH. Bioorg. Med. Chem. 2004, 12: 3521 -
19a
Mitsunobu O. Synthesis 1981, 1 -
19b
Hughes DL. Org. React. (N.Y.) 1992, 42: 335 -
19c
Hughes DL. Org. Prep. Proced. Int. 1996, 28: 127 -
19d
Dembinski R. Eur. J. Org. Chem. 2004, 2763 -
19e
Jew S.Lim D.Bae S.Kim H.Kim J.Lee J.Park H. Tetrahedron: Asymmetry 2002, 13: 715 -
19f
Jew S.Kim H.Bae S.Kim J.Park H. Tetrahedron Lett. 2000, 41: 7925 - 20
Alcantara AR.Marinas JM.Sinisterra JV. Tetrahedron Lett. 1987, 28: 1515 - 21
Old KB.Main L. J. Chem. Soc., Perkin Trans. 2 1982, 1309 - 22
Ali SM.Ilyas M. J. Org. Chem. 1986, 51: 5415 - 23
Peter A.Bradshaw J.Warren RF. Phytochemistry 1971, 10: 835 - 24
Zaveri NT. Org. Lett. 2001, 3: 843 - 25
Jimenez MC.Marquez F.Miranda MA.Tormos R. J. Org. Chem. 1994, 59: 197 - 26
Clark-Lewis JW.McGarry EJ. Aust. J. Chem. 1973, 26: 809 - 27
Li L.Chan TH. Org. Lett. 2001, 3: 739 - 28
Brown BR.Shaw MR. J. Chem. Soc., Perkin Trans. 1 1974, 2036 - 29
Patil AD.Deshpande VH. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1982, 21: 626