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Diels-Alder Reactions oftert-Butylphosphaethyne with 1,3,2-Diaza- and 1,2-Azaphosphinines

1998; Wiley; Volume: 1998; Issue: 9 Linguagem: Inglês

10.1002/(sici)1099-0690(199809)1998

1434-193X

Narcis Avarvari, Louis Ricard, François Mathey, Pascal Le Floch, Oliver Löber, Manfred Regitz,

Asymmetric Hydrogenation and Catalysis

European Journal of Organic ChemistryVolume 1998, Issue 9 p. 2039-2045 Full Paper Diels-Alder Reactions of tert-Butylphosphaethyne with 1,3,2-Diaza- and 1,2-Azaphosphinines Narcis Avarvari, Narcis Avarvari Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorLouis Ricard, Louis Ricard Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorFrançois Mathey, François Mathey Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorPascal Le Floch, Pascal Le Floch lefloch@mars.polytechnique.fr Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorOliver Löber, Oliver Löber Fachbereich Chemie, Universität Kaiserslautern, Erwin-Schrödinger-Str., D-67663 Kaiserslautern, Germany Fax: (internat.) + 49(0)631/205-3921Search for more papers by this authorManfred Regitz, Manfred Regitz regitz@rhrk.uni-kl.de Fachbereich Chemie, Universität Kaiserslautern, Erwin-Schrödinger-Str., D-67663 Kaiserslautern, Germany Fax: (internat.) + 49(0)631/205-3921Search for more papers by this author Narcis Avarvari, Narcis Avarvari Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorLouis Ricard, Louis Ricard Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorFrançois Mathey, François Mathey Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorPascal Le Floch, Pascal Le Floch lefloch@mars.polytechnique.fr Laboratoire "Hétéroéléments et Coordination", UMR CNRS 7653, Ecole Polytechnique, F-91128 Palaiseau Cedex, France Fax: (internat.) + 33-1/6933-3990Search for more papers by this authorOliver Löber, Oliver Löber Fachbereich Chemie, Universität Kaiserslautern, Erwin-Schrödinger-Str., D-67663 Kaiserslautern, Germany Fax: (internat.) + 49(0)631/205-3921Search for more papers by this authorManfred Regitz, Manfred Regitz regitz@rhrk.uni-kl.de Fachbereich Chemie, Universität Kaiserslautern, Erwin-Schrödinger-Str., D-67663 Kaiserslautern, Germany Fax: (internat.) + 49(0)631/205-3921Search for more papers by this author First published: September 1998 https://doi.org/10.1002/(SICI)1099-0690(199809)1998:9 3.0.CO;2-PCitations: 12AboutPDF 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 tert-Butylphosphaethyne (2) undergoes a Diels-Alder reaction with the 1,3,2-diazaphosphinine 1 at room temperature to furnish the diazadiphosphabarrelene 3. In the presence of an excess of 2 in toluene under reflux compound 3 experiences elimination of a molecule of pivalonitrile to afford the 1-aza-2,4-diphosphinine 5 which, in turn, reacts with a further equivalent of 2 to form the transient azatriphosphabarrelene 6. Formation of the final product, the stable tetraphosphatetracyclic compound 4, is the result of a homo Diels-Alder reaction between 6 and yet another equivalent of 2. The structure of 4 has been confirmed by an X-ray crystallographic analysis of its pentacarbonyltungsten complex 7. As a consequence of the high steric overcrowding in 4, complexation occurs exclusively at its phosphaalkene phosphorus atom. The reactivity of 2 towards the four functionally substituted 1,2-azaphosphinines 8a–d has also been examined. At room temperature smooth [4 + 2] cycloaddition reactions proceed to yield the azadiphosphabarrelenes 9a–d. While thermolyses of the barrelenes 9a–c in toluene under reflux lead exclusively to the starting compounds 8a–c by a [4 + 2] cycloreversion process with concomitant elimination of 2, pyrolysis of 9d under the same conditions furnishes the 1,3-diphosphinine 10, also unambiguously identified by analysis of its tpentacarbonyltungsten complex 11. Citing Literature Volume1998, Issue9September 1998Pages 2039-2045 RelatedInformation