Abstract
A formal synthesis of the insecticidal natural product AB3217-A
involving an unusual diastereoselective benzylic oxidation is described.
Key words
natural product - anisomycin - AB3217-A - benzylic
oxidation - insecticide
References and Notes
1a Kanbe K.
Mimura Y.
Tamamura T.
Yatagai S.
Sato Y.
Takahashi A.
Sato S.
J.
Antibiot.
1992,
45:
548
1b Kanbe K.
Takahashi A.
Tamamura T.
Sato K.
Naganawa H.
Takeuchi T.
J. Antibiot.
1992,
45:
568
1c Kim W.-G.
Kim J.-P.
Park D.-J.
Kim Ch.-J.
Kwak SS.
Yoo I.-D.
Agric. Chem. Biotech.
1996,
39:
153
2a Nakata M.
Tamai T.
Kamio T.
Kinoshita M.
Tatsuta K.
Bull. Chem. Soc. Jpn.
1994,
67:
3057
2b Nakata M.
Tamai T.
Kamio T.
Kinoshita M.
Tatsuta K.
Tetrahedron
Lett.
1994,
35:
3099
3 Hungerbuehler E.
Seebach D.
Helv. Chim. Acta
1981,
64:
687
4a Beereboom JJ.
Butler K.
Pennington E.-C.
J. Org. Chem.
1965,
30:
2334
4b Butler K.
J.
Org. Chem.
1966,
31:
317
4c Sobin BA.
Tanner FW.
J.
Am. Chem. Soc.
1954,
76:
4053
4d Macias-Silva M.
Vazquez-Victorio G.
Hernandez-Damian J.
Curr. Chem. Biol.
2010,
4:
124
5a Shimamoto K.
Ohfune Y.
Tetrahedron
Lett.
1988,
29:
5177
5b Bulman Page PC.
Buckley BR.
Rassias GA.
Blacker AJ.
Eur. J. Org. Chem.
2006,
803
trans intramolecular
acetyl migration, see:
6a Deng S.
Chang C.-WT.
Synlett
2006,
756
6b Markad SD.
Schmidt RR.
Eur.
J. Org. Chem.
2009,
5002
7 The hypothesis that the migration of
the acetate proceeds via formation of an epoxide was ruled out.
If an epoxide was formed and re-opened by the acetate, the stereochemistry
of the two hydroxy groups on the pyrrolidine moiety would be inverted,
which is not the case as can be observed on the crystal structure
of 6 (Figure
[³
8a Dake G.
Fenster MDB.
Hurley PB.
Patrick BO.
J.
Org. Chem.
2004,
69:
5668
8b Berry JM.
Hall LD.
Carbohydr.
Res.
1976,
47:
307
8c Fleming I.
Leslie CP.
J. Chem. Soc., Perkin
Trans. 1
1996,
1197
9 Haddad M.
Imogaï H.
Larchevêque M.
J. Org. Chem.
1998,
63:
5680
