Intermediates in the Intermolecular, Asymmetric Heck Arylation of Dihydrofurans

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 9, 1997, Pages 984-987

  Hii, King Kuok ^a   Claridge, Timothy D W ^a   Brown, John M ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

Asymmetric synthesis; Heck reactions; NMR spectroscopy; Palladium

Indexed keywords

EID: 0005864080     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199709841     Document Type: Article

References (28)

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16. [2-D]1 was prepared by a modified procedure: F. T. Oakes, J. F. Sebastian, J. Org. Chem. 1980, 45, 4959-4961. The intermediate organolithium was isolated by evacuation and washed extensively with pentane (caution!).
17. J. Stonehouse, P. Adell, J. Keeler, A. J. Shaka, J. Am. Chem. Soc. 1994, 116, 6037-6038; P. Adell, T. Parella, F. Sanchez-Ferrando, A. Virgili, J. Magn. Res. B 1995, 108, 77-80.
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19. H. Adams, N. A. Bailey, P. Cahill, D. Rogers, M. J. Winter, J. Chem. Soc. Dalton Trans. 1986, 2119-2126. We wish to acknowledge a useful discussion with Prof A. Vasella (ETH, Zurich) on this topic.
20. The methine protons (H2) of the two diastereomeric complexes appear at δ = 4.60 [J(P,H) = 15.8, J(H,H) = 3.8 Hz] and δ = 5.14 [J(P,H) = 17.5, J(H,H) = 3.5 Hz].
21. Dynamic NMR spectra were simulated with the gNMR package (Ivorysoft): Cherwell Scientific, The Magdalen Centre, Oxford Science Park, Oxford OX44G (UK).
22. For related, fluxional square-planar hydrides, see F. Cecconi, P. Innocenti, S. Midollini, S. Moneti, A. Vacca, J. A. Ramirez, J. Chem. Soc. Dalton Trans. 1991, 1129-1134; A. R. Siedle, R. A. Newmark, W. B. Gleason, Inorg. Chem. 1991, 30, 2005-2009.
23. For related, fluxional square-planar hydrides, see F. Cecconi, P. Innocenti, S. Midollini, S. Moneti, A. Vacca, J. A. Ramirez, J. Chem. Soc. Dalton Trans. 1991, 1129-1134; A. R. Siedle, R. A. Newmark, W. B. Gleason, Inorg. Chem. 1991, 30, 2005-2009.
24. 3 in THF gave complete reaction in 21 h (100% 3, 75% ee).
25. 3 or proton sponge to give 3 as the sole product. The ratio of 3 to 2 decreased with increasing amounts of tetra-n-butylammonium acetate. The reverse result was achieved (97% 2) when acetate was added as the base in stoichiometric amount.
26. A. Ashimori, T. Matsuura, L. E. Overman, D. J. Poon, J. Org. Chem. 1993, 58, 6949-6951.
27. H. Doucet, Dyson Perrins Laboratory unpublished results.
28. Prepared according to J. M. Brown, P. J. Guiry, Inorg. Chim. Acta 1994, 220, 249-60.