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      Synthesis of Anionic Phosphorus-Containing Heterocycles by Intramolecular Cyclizations Involving N-Functionalized Phosphinecarboxamides

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          Abstract

          We report that the 2-phosphaethynolate anion (PCO ) reacts with propargylamines in the presence of a proton source to afford novel N-derivatized phosphinecarboxamides bearing alkyne functionalities. Deprotonation of these species gives rise to novel five- and six-membered anionic heterocycles resulting from intramolecular nucleophilic attack of the resulting phosphide at the alkyne functionality (via 5- exo-dig or 6- endo-dig cyclizations, respectively). The nature of the substituents on the phosphinecarboxamide can be used to influence the outcome of these reactions. This strategy represents a unique approach to phosphorus-containing heterocylic systems that are closely related to known organic molecules with interesting bio-active properties.

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          Most cited references 39

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          Gold catalysis: mild conditions for the synthesis of oxazoles from N-propargylcarboxamides and mechanistic aspects.

          2,5-Disubstituted oxazoles are synthesized from the corresponding propargylcarboxamides under mild reaction conditions via homogeneous catalysis by AuCl(3). While monitoring the conversion via (1)H NMR spectroscopy, an intermediate 5-methylene-4,5-dihydrooxazole can be observed and accumulated up to 95%, being the first direct and catalytic preparative access to such alkylidene oxazolines. The intermediate was fully characterized and can be trapped at -25 degrees C for several weeks. Deuteration experiments show a stereospecific mode of the two first steps of the reaction.
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            Cyclizations of alkynes: revisiting Baldwin's rules for ring closure.

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              Phosphinecarboxamide: a phosphorus-containing analogue of urea and stable primary phosphine.

              Reactions of the 2-phosphaethynolate anion (PCO(-), 1) with ammonium salts quantitatively yielded phosphinecarboxamide (PH2C(O)NH2, 2). The molecular structure and chemical properties of 2 were studied by single-crystal X-ray diffraction and multielement NMR spectroscopy. This phosphorus-containing analogue of urea is a rare example of an air-stable primary phosphine.
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                Author and article information

                Contributors
                Role: Dr.
                Role: Prof. Dr.
                Journal
                Chemistry
                Chemistry
                chem
                Chemistry (Weinheim an Der Bergstrasse, Germany)
                WILEY-VCH Verlag (Weinheim )
                0947-6539
                1521-3765
                07 April 2015
                03 March 2015
                : 21
                : 15
                : 5727-5731
                Affiliations
                [[a] ]Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road, Oxford, OX1 3TA (UK)
                Author notes
                * Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA (UK) E-mail: jose.goicoechea@ 123456chem.ox.ac.uk
                Article
                10.1002/chem.201500628
                4405058
                25736217
                © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

                This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

                Categories
                Communications

                Chemistry

                2-phosphaethynolate anion, propargyl-phosphines, phosphorus, phosphides, heterocycles

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