Straightforward access to 2-iminoisoindolines via three-component coupling of arynes, isocyanides and imines

Tetrahedron Letters

Volumn 45, Issue 47, 2004, Pages 8659-8662

  Yoshida, Hiroto ^a   Fukushima, Hiroyuki ^a   Ohshita, Joji ^a   Kunai, Atsutaka ^a  

^a HIROSHIMA UNIVERSITY   (Japan)

Author keywords

Arynes; Isocyanides; Multicomponent couplings; Nitrogen heterocycles

Indexed keywords

2 IMINOISOINDOLINE; ALKYNE DERIVATIVE; CYANIDE; IMINE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; ISOLATION PROCEDURE; REACTION ANALYSIS; SYNTHESIS;

EID: 7044231369     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2004.09.144     Document Type: Article

References (21)

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3. Three-component couplings of an aryne were mainly achieved using an anionic nucleophile thus far: A.I. Meyers, and P.D. Pansegrau Tetrahedron Lett. 24 1983 4935
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7. We have also reported electrophilic couplings of arynes using neutral nucleophiles: H. Yoshida, S. Sugiura, and A. Kunai Org. Lett. 4 2002 2767
8. H. Yoshida, E. Shirakawa, Y. Honda, and T. Hiyama Angew. Chem., Int. Ed. 41 2002 3247
9. For recent reviews on the isonitrile-based multicomponent synthesis of heterocycles, see: V. Nair, C. Rajesh, A.U. Vinod, S. Bindu, A.R. Sreekanth, J.S. Mathen, and L. Balagopal Acc. Chem. Res. 36 2003 899
10. J. Zhu Eur. J. Org. Chem. 2003 1133
11. Three-component couplings of dimethyl acetylenedicarboxylate, isocyanides and electrophiles have been reported: V. Nair, and A.U. Vinod Chem. Commun. 2000 1019
12. V. Nair, A.U. Vinod, and C. Rajesh J. Org. Chem. 66 2001 4427
13. V. Nair, A.U. Vinod, N. Abhilash, R.S. Menon, V. Santhi, L.R. Varma, S. Viji, S. Mathew, and R. Srinivas Tetrahedron 59 2003 10279
14. V. Nair, R.S. Menon, P.B. Beneesh, V. Sreekumar, and S. Bindu Org. Lett. 6 2004 767
15. The Merck Index, 13th ed., 2001
16. Y. Himeshima, T. Sonoda, and H. Kobayashi Chem. Lett. 1983 1211
17. Crystallographic data for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 247264. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(0)-1223-336033 or e-mail: deposit@ccdc.cam.ac.uk]
18. a as well as the general regioselectivity in the electrophilic coupling of 3-methoxybenzyne should support the assignment of the stereochemistry of 4s
19. R. Knorr Chem. Ber. 98 1965 4038
20. The three-component coupling of 3-methylbenzyne, 2a and 4-methoxybenzaldehyde proceeded faster (0°C, 8 h) than the reaction using 3b with a perfect regioselectivity to give the single product, which holds the imine moiety at the meta position of the methyl group (Ref. 3). The different regioselectivities can be explained by the reversibility in the nucleophilic addition of 2a to 3-methylbenzyne. The zwitterion bearing the anionic moiety at the meta position of the methyl group would be thermodynamically stable among two possible zwitterions owing to the electron-donating character of the methyl group. In contrast, formation of another zwitterion should be kinetically favoured because of less steric repulsion between the methyl group and 2a. Therefore, imine 3b of lower reactivity gave 4t predominantly, since kinetically generated zwitterion should isomerize to thermodynamically stable one prior to the reaction with the imine. For the reversibility in the addition of nucleophiles to arynes, see Ref. 1a
21. The electronic effects of the substituents (methoxy or methyl) would depend considerably upon their inductive effects compared with their resonance effects, since the triple bond of the arynes is orthogonal to the ring π-system. Thus, the methoxy group would exert electron-withdrawing effect, whereas opposite electronic effect would be induced by the methyl group