Highly regioselective allylic alkylation of dienyl acetates and enynyl acetates catalyzed by an iridium complex

Angewandte Chemie - International Edition

Volumn 39, Issue 11, 2000, Pages 1975-1978

  Takeuchi, Ryo ^a   Tanabe, Keisuke ^a  

^a YOKOHAMA CITY UNIVERSITY   (Japan)

Author keywords

Alkylations; Allyl complexes; Catalysts; Iridium; Nucleophilic additions

Indexed keywords

ACETIC ACID DERIVATIVE; IRIDIUM COMPLEX;

ALKYLATION; ARTICLE; CHEMICAL BOND; ORGANIC CHEMISTRY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0034595863     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000602)39:11<1975::AID-ANIE1975>3.0.CO;2-I     Document Type: Article

References (24)

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4. d) W: R. Pretot, G. C. Lloyd-Jones, A. Pfaltz, Pure Appl. Chem. 1998, 70, 1035;
5. e) Rh: R. Takeuchi, N. Kitamura, New J. Chem. 1998, 22, 659;
6. f) Rh: P. A. Evans, J. D. Nelson, J. Am. Chem. Soc. 1998, 120, 5581;
7. g) Ir: B. Bartels, G. Helmchen, Chem. Commun. 1999, 741;
8. h) Ru: Y. Morisaki, T. Kondo, T. Mitsudo, Organometallics 1999, 18, 4742.
9. a) Pd: Y. I. M. Nilsson, P. G. Andersson, J. E. Backvall, J. Am. Chem. Soc. 1993, 115, 6609;
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12. For the isomerization of a σ-propargylic complex to a σ-allenyl complex, see a) S. Ogoshi, Y. Fukunishi, K. Tsutsumi, H. Kurosawa, J. Chem. Soc. Chem. Commun. 1995, 2485;
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14. a) R. Takeuchi, M. Kashio, Angew. Chem. 1997, 109, 268; Angew. Chem. Int. Ed. Engl. 1997, 36, 263;
15. a) R. Takeuchi, M. Kashio, Angew. Chem. 1997, 109, 268; Angew. Chem. Int. Ed. Engl. 1997, 36, 263;
16. b) R. Takeuchi, M. Kashio, J. Am. Chem. Soc. 1998, 120, 8647;
17. c) R. Takeuchi, Polyhedron 2000, 19, 557;
18. d) for allylic amination, see R. Takeuchi, N. Shiga, Org. Lett. 1999, 1, 265.
19. R. Takeuchi, K. Tanabe, Abstr. Pap. 76th Annu. Meet. Chem. Soc. Jpn. (Yokohama, Japan) 1999, p. 2B734.
20. The electronegativity of an alkenyl group is bigger than that of an alkyl group, see N. Inamoto, S. Masuda, Chem. Lett. 1982, 1003.
21. For the stability of an alkenemetal complex, see J. P. Collman, L. S. Hegedus, J. R. Norton, R. G. Finke, Principles and Applications of Organotransition Chemistry, University Science Books, Mill Valley, 1987, p. 149.
22. The alkylation of enynyl acetates catalyzed by a Pd complex has been reported, see E. Keinan, E. Bosch, J. Org. Chem. 1986, 51, 4006.
23. A stereodivergent synthesis of (E)- and (Z)-2-alken-4-yn-1-ols from 2-propynoic acid has been reported, see R. Takeuchi, K. Tanabe, S. Tanaka, J. Org. Chem. 2000, 65, 1558.
24. When the central metal of an alkyne complex is in a high oxidation state, donation of electrons from an alkyne to the metal should be predominant over back donation from the metal to an alkyne. Oxidative additon of an allylic ester to an iridium(1) species gives an iridium(III) species. The Ir centers in intermediates 18 and 19 would be electron-rich because of the donation of electrons from a coordinated alkyne group.