Abstract
Intramolecular nucleophilic epoxidation reactions of γ-amino-α,β-unsaturated esters have been studied for the first time with a hydroperoxymethyl group attached to the nitrogen atom. The epoxidation was fast under mild basic conditions and highly anti selective (>20:1) when the alkyl group is small.
Key words
asymmetric synthesis - ring-opening - peroxides - nucleophile - intramolecular epoxidation - amino epoxide
References
1 Katsuki T.
Jacobsen EN.
Wu MH.
Aggarwal VK. In
Comprehensive Asymmetric Catalysis
Vol. II:
Jacobsen EN.
Pfaltz A.
Yamamoto H.
Springer-Verlag;
Berlin:
1999.
Chap. 18.1-18.3.
2a Hoveyda AH.
Evans DA.
Fu GC.
Chem. Rev.
1993,
93:
1307
2b Itami K.
Koike T.
Yoshida J.
J. Am. Chem. Soc.
2001,
123:
6957
2c Donohoe TJ.
Blades K.
Moore PR.
Waring MJ.
Winter JJG.
Helliwell M.
Newcombe NJ.
Stemp G.
J. Org. Chem.
2002,
67:
7946
2d Dick AR.
Hull KL.
Sanford MS.
J. Am. Chem. Soc.
2004,
126:
2300
3a Scholz D.
Billich A.
Charpiot B.
Ettmayer P.
Lehr P.
Rosenwirth B.
Schreiner E.
Gstach H.
J. Med. Chem.
1994,
37:
3079
3b Ettmayer P.
Billich A.
Hecht P.
Rosenwirth B.
Gstach H.
J. Med. Chem.
1996,
39:
3291
3c Ager DJ.
Prakash I.
Schaad DR.
Chem. Rev.
1996,
96:
835
3d Bergmeier SC.
Tetrahedron
2000,
56:
2561
4 Smith MB.
March J.
March’s Advanced Organic Chemistry
5th ed.:
Wiley and Sons;
New York:
2001.
p.1052 and references therein
5a Reetz MT.
Lauterbach EH.
Tetrahedron Lett.
1991,
32:
4477
5b Lanier M.
Haddach M.
Pastor R.
Riess JG.
Tetrahedron Lett.
1993,
34:
2469
5c Yadav V.
Kapoor KK.
Tetrahedron
1995,
51:
8573
5d Rodríguez S.
Vidal A.
Monroig JJ.
González FV.
Tetrahedron Lett.
2004,
45:
5359
6a Kogen H.
Nishi TJ.
J. Chem. Soc., Chem. Commun.
1987,
311
6b Sakai N.
Ohfune Y.
J. Am. Chem. Soc.
1992,
114:
998
6c Mordini A.
Valacchi M.
Nardi C.
Bindi S.
Poli G.
Reginato G.
J. Org. Chem.
1997,
62:
8557
7 Presented in part at the 226th American Chemical Society National Meeting, ORGN No. 294, New York, NY, USA, September 7-11, 2003.
8a Corey EJ.
Niwa H.
Falck JR.
J. Am. Chem. Soc.
1979,
101:
1586
8b Rebek J.
McCready R.
J. Am. Chem. Soc.
1980,
102:
5602
8c Saito I.
Mano T.
Nagata R.
Matsuura T.
Tetrahedron Lett.
1987,
28:
1909
8d Furber M.
Mander LN.
J. Am. Chem. Soc.
1987,
109:
6389
8e Armstrong A.
Draffan AG.
J. Chem. Soc., Perkin Trans. 1
2001,
2861
9 Yoo D.
Oh JS.
Kim YG.
Org. Lett.
2002,
4:
1213
10a Hyun SI.
Kim YG.
Tetrahedron Lett.
1998,
39:
4299
10b Yoo D.
Oh JS.
Lee D.-W.
Kim YG.
J. Org. Chem.
2003,
68:
2979
11 Massa A.
Palombi L.
Scettri A.
Tetrahedron Lett.
2001,
42:
4577
12a Otsubo K.
Inanaga J.
Yamaguchi M.
Tetrahedron Lett.
1987,
28:
4437
12b Yuste F.
Díaz A.
Ortiz B.
Sánchez-Obregón R.
Walls F.
Garcia Ruano JL.
Tetrahedron: Asymmetry
2003,
14:
549
13 Langlois N.
Moro A.
Eur. J. Org. Chem.
1999,
3483 ; and references therein
14a Futagawa S.
Inui T.
Shiba T.
Bull. Chem. Soc. Jpn.
1973,
46:
3308
14b Thoen JC.
Morales-Ramos AI.
Lipton MA.
Org. Lett.
2002,
4:
4455
15 Dauban P.
de Saint-Fuscien C.
Dodd RH.
Tetrahedron
1999,
55:
7589
