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On the Influence of the Bite Angle of Bidentate Phosphane Ligands on theRegioselectivity in Allylic Alkylation

1999; Wiley; Volume: 1999; Issue: 8 Linguagem: Inglês

10.1002/(sici)1099-0682(199908)1999

1099-0682

Richard J. van Haaren, Henk Oevering, Betty Coussens, Gino P. F. van Strijdonck, Joost N. H. Reek, Paul C. J. Kamer, Piet W. N. M. van Leeuwen,

Chemical Synthesis and Analysis

European Journal of Inorganic ChemistryVolume 1999, Issue 8 p. 1237-1241 Full Paper On the Influence of the Bite Angle of Bidentate Phosphane Ligands on theRegioselectivity in Allylic Alkylation Richard J. van Haaren, Richard J. van Haaren Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorHenk Oevering, Henk Oevering D. S. M. Research N. V., P.O. Box 18, NL-6160 MD, Geleen, The NetherlandsSearch for more papers by this authorBetty B. Coussens, Betty B. Coussens D. S. M. Research N. V., P.O. Box 18, NL-6160 MD, Geleen, The NetherlandsSearch for more papers by this authorGino P. F van Strijdonck, Gino P. F van Strijdonck Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorJoost N. H. Reek, Joost N. H. Reek Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorPaul C. J. Kamer, Paul C. J. Kamer Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorPiet W. N. M. van Leeuwen, Piet W. N. M. van LeeuwenSearch for more papers by this author Richard J. van Haaren, Richard J. van Haaren Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorHenk Oevering, Henk Oevering D. S. M. Research N. V., P.O. Box 18, NL-6160 MD, Geleen, The NetherlandsSearch for more papers by this authorBetty B. Coussens, Betty B. Coussens D. S. M. Research N. V., P.O. Box 18, NL-6160 MD, Geleen, The NetherlandsSearch for more papers by this authorGino P. F van Strijdonck, Gino P. F van Strijdonck Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorJoost N. H. Reek, Joost N. H. Reek Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorPaul C. J. Kamer, Paul C. J. Kamer Institute for Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The NetherlandsSearch for more papers by this authorPiet W. N. M. van Leeuwen, Piet W. N. M. van LeeuwenSearch for more papers by this author First published: 15 July 1999 https://doi.org/10.1002/(SICI)1099-0682(199908)1999:8 3.0.CO;2-YCitations: 45AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract The natural bite angle of bidentate phosphane ligands influences the isomer distribution (syn and anti) in (1-methylallyl)(bisphosphane)Pd OTf complexes. It was found (31P- and 1H-NMR studies) that the syn/anti ratio changes from 12 (dppp) to 1.3 (sixantphos). Molecular orbital calculations [PM3(tm) level] indicate that for ligands inducing a large bite angle, the phenyl rings of the ligand embrace the allyl moiety, thus influencing the syn/anti ratio. This bite-angle effect on the syn/anti ratio is transferred to the regioselectivity in stoichiometric allylic alkylation. Ligands inducing large bite angles direct the regioselectivity towards the formation of the branched product 2. Catalytic alkylation of (E)-2-butenyl acetate showed that for ligands with a small bite angle the regioselectivity of the catalytic and stoichiometric alkylation are in good agreement. This correspondence is worse for ligands with a larger bite angle, which is rationalised in terms of the relative rates of syn/anti isomerisation and alkylation. The ligand with the largest bite angle (sixantphos) gives the most active catalytic species. Citing Literature Volume1999, Issue8August 1999Pages 1237-1241 RelatedInformation