Abnormal Aza-Baylis-Hillman Reaction of N-Tosylated Imines with Ethyl 2,3-Butadienoate and Penta-3,4-dien-2-one

Organic Letters

Volumn 5, Issue 24, 2003, Pages 4737-4739

  Zhao, Gui Ling ^a   Huang, Jin Wen ^a   Shi, Min ^a  

^a SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY   (China)

Author keywords

[No Author keywords available]

Indexed keywords

AZETIDINE DERIVATIVE; BUTANE; DIHYDROPYRIDINE DERIVATIVE; IMINE; KETONE DERIVATIVE; PENTA 3,4 DIEN 2 ONE; UNCLASSIFIED DRUG;

ARTICLE; AZA BAYLIS HILLMAN REACTION; CATALYSIS; CHEMICAL REACTION;

EID: 0348041984     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0359416     Document Type: Article

References (23)

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8. (a) Shi, M.; Xu, Y.-M. Chem. Commun. 2001, 1876.
9. (b) Shi, M.; Xu, Y.-M. Eur. J. Org. Chem. 2002, 696.
10. (c) Shi, M.; Xu, Y.-M.; Zhao, G.-L.; Wu, X.-F. Eur. J. Org. Chem. 2002, 3666.
11. (d) Shi, M.; Xu, Y.-M. J. Org. Chem. 2003, 68, 4784.
12. Using triphenylphosphine or tributylphosphine as a Lewis base in the reaction of allenoates with N-tosylated imines generates a [3 + 2] cycloaddition to give five-membered pyrrolidine derivatives, (a) Xu, Z.; Lu, X. Tetrahedron Lett. 1997, 38, 3461. (b) Xu, Z.; Lu, X. J. Org. Chem. 1998, 63, 5031. (c) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34, 535.
13. Using triphenylphosphine or tributylphosphine as a Lewis base in the reaction of allenoates with N-tosylated imines generates a [3 + 2] cycloaddition to give five-membered pyrrolidine derivatives, (a) Xu, Z.; Lu, X. Tetrahedron Lett. 1997, 38, 3461. (b) Xu, Z.; Lu, X. J. Org. Chem. 1998, 63, 5031. (c) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34, 535.
14. Using triphenylphosphine or tributylphosphine as a Lewis base in the reaction of allenoates with N-tosylated imines generates a [3 + 2] cycloaddition to give five-membered pyrrolidine derivatives, (a) Xu, Z.; Lu, X. Tetrahedron Lett. 1997, 38, 3461. (b) Xu, Z.; Lu, X. J. Org. Chem. 1998, 63, 5031. (c) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34, 535.
15. Reaction of 2-methyl-2,3-butadienoate with N-tosylated imines catalyzed by tributylphosphine gave six-membered tetrahydropyridines in high yields. Zhu, X.-F.; Lan, J.; Kwon, O. J. Am. Chem. Soc. 2003, 125, 4716.
16. Baylis-Hillman reaction of aldehydes with ethyl 2,3-butadienonate and penta-3,4-dien-2-one in the presence of DABCO gave the normal Baylis-Hillman adduct. See: Tsuboi, S.; Kuroda, H.; Takatsuka, S.; Fukawa, T.; Sakai, T.; Utaka, M. J. Org. Chem. 1993, 58, 5952.
17. MS 4 Å was used to get rid of ambient water or moisture to improve the isolated yields because the employed N-tosylated imines can decompose to the corresponding aldehydes and N-tosylated amines by ambient water or moisture during a prolonged reaction time (Table 1, entries 1-2).
18. Solvent and Lewis base effects for these abnormal aza-Baylis-Hillman reactions are summarized in Supporting Information.
19. w = 0.0568, 0.1278.
20. We believe that the nitrogen Lewis bases DABCO and DMAP should have different catalytic abilities in the Baylis-Hillman reaction as the promoters because they have different nucleophilicities and basicities. At the present stage, we cannot give a clear-cut explanation of this interesting Lewis base effect.
21. Chemla, F.; Hebbe, V.; Normant, J. F. Synthesis 2000, 1, 75.
22. Reaction of methylallene with N-tosylated imines gives alkylide-neazetidines in 3% yield at 130°C. See: Baumann, H.; Duthaler, R. O. Helv. Chem. Acta 1988, 71, 1025. The reaction of ketenes with imines gives azetidinones and 2:1 adducts. See: Mukerjee, A. K.; Srivastava, R. C. Synthesis 1973, 327.
23. Reaction of methylallene with N-tosylated imines gives alkylide-neazetidines in 3% yield at 130°C. See: Baumann, H.; Duthaler, R. O. Helv. Chem. Acta 1988, 71, 1025. The reaction of ketenes with imines gives azetidinones and 2:1 adducts. See: Mukerjee, A. K.; Srivastava, R. C. Synthesis 1973, 327.