Communications
1347 – 1365; d) H. Stamm, J. Prakt. Chem. 1999, 341,319 – 331;
e) D. Tanner, Angew. Chem. 1994, 106,625 – 646; Angew. Chem.
Int. Ed. Engl. 1994, 33,599 – 619; f) P. Müller,C. Fruit, Chem.
Rev. 2003, 103,2905 – 2919; g) E. N. Jacobsen in Comprehensive
Asymmetric Catalysis, Vol. 2 (Eds.: E. N. Jacobsen,A. Pfaltz,H.
Yamamoto),Springer,Berlin,
1999,pp. 607 – 618; h) R. S.
Atkinson, Tetrahedron 1999, 55,1519 – 1559; i) H. M. I.
Osborn,J. Sweeney, Tetrahedron: Asymmetry 1997, 8,1693 –
1715.
[2] Moderate-to-high ee values have been reported only in the direct
aziridination of styrene: a) H. Nishikori,T. Katsuki, Tetrahedron
Lett. 1996, 37,9245 – 9248; b) Z. Li,K. R. Conser,E. N.
Jacobsen, J. Am. Chem. Soc. 1993, 115,5326 – 5327; c) D. A.
Evans,M. M. Faul,M. T. Bilodeau,B. A. Anderson,D. M.
Barnes, J. Am. Chem. Soc. 1993, 115,5328 – 5329.
[3] For a review of the synthesis of 1,2-amino alcohols, see: S. C.
Bergmeier, Tetrahedron 2000, 56,2561 – 2576.
[4] J. F. Larrow,S. E. Schaus,E. N. Jacobsen, J. Am. Chem. Soc.
1996, 118,7420 – 7421.
[5] C. Moberg,H. Adolfsson in Science of Synthesis, Vol. 4 (Ed.: I.
Fleming),Thieme,Stuttgart, 2002,pp. 435 – 449.
Scheme 6. Synthesis of N-SES-chloromethylaziridine (14)and its appli-
cations. SES=2-(trimethylsilyl)ethanesulfonyl.
[6] T. Fukuyama,M. Cheung,T. Kan, Synlett 1999,1301 – 1303.
[7] a) M. Tokunaga,J. F. Larrow,F. Kakiuchi,E. N. Jacobsen,
Science 1997, 277,936 – 938; b) L. P. C. Nielsen,C. P. Stevenson,
D. G. Blackmond,E. N. Jacobsen, J. Am. Chem. Soc. 2004, 126,
1360 – 1362; c) S. E. Schaus,B. D. Brandes,J. F. Larrow,M.
Tokunaga,K. B. Hansen,A. E. Gould,M. E. Furrow,E. N.
Jacobsen, J. Am. Chem. Soc. 2002, 124,1307 – 1315,and
references therein.
aminotetrahydroquinoline[18] (Scheme 7). The cuprate gener-
ated from the dianion of 19 and CuCN·LiCl underwent
reaction with 14 to afford the ring-opening product 20.
Deprotection followed by cyclization in the presence of added
iodide afforded 3-aminotetrahydroquinoline 21.
[8] Simultaneous addition of the two reagents led to inferior results,
consistent with the observation that the rates of epoxide
hydrolysis and ring-opening with 2 are competitive.
[9] Synthesis of 7b under Mitsunobu conditions proceeded in low
yield (44%) as a result of the instability of the nosylaziridine to
the reaction conditions.
[10] For racemic syntheses,see: a) R. S. Atkinson,E. Barker,S.
Ulukanli, J. Chem. Soc. Perkin Trans. 1 1998,583 – 589; b) R. S.
Atkinson,M. P. Coogan,C. L. Cornell, J. Chem. Soc. Perkin
Trans. 1 1996,157 – 166; c) R. S. Atkinson,B. J. Kelly, J. Chem.
Soc. Perkin Trans. 1 1989,1627 – 1630.
[11] P. E. Maligres,M. M. See,D. Askin,P. J. Reider,
Lett. 1997, 38,5253 – 5256.
[12] a) T. Fukuyama,C.-K. Jow,M. Cheung, Tetrahedron Lett. 1995,
Tetrahedron
Scheme 7. Synthesis of 3-aminotetrahydroquinoline 21. TBAI=tetrabu-
tylammonium iodide.
36,6373 – 6374; b) W. Kurosawa,T. Kan,T. Fukuyama,
Synth. 2002, 79,186 – 195.
Org.
In summary,a general asymmetric catalytic method for
the preparation of highly enantiomerically enriched N-
sulfonylated terminal aziridines has been devised. Enantio-
pure chloromethylaziridines 7e and 14 were synthesized for
the first time,and the synthetic utility of these difunctional
building blocks was demonstrated. Current efforts are
directed toward elucidation of the mechanism of the reaction
between epoxides and 2 and toward synthetic extensions and
applications of this methodology.
[13] Compound 7e undergoes decomposition upon storage as a neat
liquid,but was stored safely for prolonged periods as a frozen
0.78m solution in benzene at À308C.
[14] a) A. Ricci,M. Fochi, Angew. Chem. 2003, 115,1482 – 1484;
Angew. Chem. Int. Ed. 2003, 42,1444 – 1446; b) G. Kꢀbrich,P.
Buck, Angew. Chem. 1966, 78,1062 – 1063; Angew. Chem. Int.
Ed. Engl. 1966, 5,1044.
[15] a) S. M. Weinreb,D. M. Demko,T. A. Lessen,J. P. Demers,
Tetrahedron Lett. 1986, 27,2099 – 2102; b) S. M. Weinreb,C. E.
Chase,P. Wipf,S. Venkatraman, Org. Synth. 1997, 75,161 – 169.
[16] a) J. A. Campbell,D. J. Hart, J. Org. Chem. 1993, 58,2900 – 2903;
b) B. R. Neustadt, Tetrahedron Lett. 1994, 35,379 – 380.
[17] NaH was employed in the final cyclization step because the
corresponding reaction with Cs2CO3 proved much slower. Thus,
the NaH reaction was completed in 30 min,whereas the Cs 2CO3
reaction required 23 h.
[18] 3-Aminotetrahydroquinoline is the core structure of sumanirole,
a drug candidate for the treatment of Parkinsonꢁs disease.
a) P. G. M. Wuts,R. L. Gu,J. M. Northuis,T. A. Kwan,D. M.
Beck,M. J. White, Pure Appl. Chem. 2002, 74,1359 – 1368;
b) P. G. M. Wuts, Curr. Opin. Drug Discovery Dev. 1999, 2,557 –
564.
Received: April 20,2004 [Z460369]
Keywords: asymmetric catalysis · aziridines ·
.
nitrogen heterocycles · small ring systems · sulfonamides
[1] For reviews on the preparation and reactions of aziridines,see:
a) J. B. Sweeney, Chem. Soc. Rev. 2002, 31,247 – 258; b) V. H.
Dahanukar,I. A. Zavialov, Curr. Opin. Drug Discovery Dev.
2002, 5,918 – 927; c) W. McCoull,F. A. Davis, Synthesis 2000,
3954
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Angew. Chem. Int. Ed. 2004, 43, 3952 –3954