Reactivity and Mechanistic Studies of the Reactions of Chlorodiphenylphosphine and Its Oxide with Methyl Glyoxylate, Glyoxylate Oximes, and Methyl Cyanoformate
Corresponding Author
Carlos A. D. Sousa
REQUIMTE, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
Correspondence to: Carlos A. D. Sousa; e-mail: [email protected].Search for more papers by this authorCarlos F. R. A. C. Lima
Centro de Investigação em Química, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
QOPNA, Department of Chemistry, University of Aveiro, Aveiro, Portugal
Search for more papers by this authorIvo E. Sampaio-Dias
Centro de Investigação em Química, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
Search for more papers by this authorXerardo Garcia-Mera
Departamento de Química Orgánica, Faculdade de Farmácia, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain
Search for more papers by this authorJosé E. Rodríguez-Borges
Centro de Investigação em Química, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
Search for more papers by this authorCorresponding Author
Carlos A. D. Sousa
REQUIMTE, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
Correspondence to: Carlos A. D. Sousa; e-mail: [email protected].Search for more papers by this authorCarlos F. R. A. C. Lima
Centro de Investigação em Química, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
QOPNA, Department of Chemistry, University of Aveiro, Aveiro, Portugal
Search for more papers by this authorIvo E. Sampaio-Dias
Centro de Investigação em Química, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
Search for more papers by this authorXerardo Garcia-Mera
Departamento de Química Orgánica, Faculdade de Farmácia, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain
Search for more papers by this authorJosé E. Rodríguez-Borges
Centro de Investigação em Química, Departamento de Química e Bioquímica da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal
Search for more papers by this authorContract grant sponsor: Fundação para a Ciência e Tecnologia (FCT). Contract grant numbers: PEst-C/EQB/LA0006/2013, FCOMP-01-0124-FEDER-037285, SFRH/BPD/80100/2011, SFRH/BPD/77972/2011 and SFRH/BD/93632/2013.
ABSTRACT
In this work, we describe the reactivity of chlorodiphenylphosphine and its oxide, as well as diphenylphosphine, with some glyoxylate derivative systems: methyl glyoxylate, methyl or 8-phenylneomenthyl glyoxylate oximes, and methyl cyanoformate. By analyzing the reactions outcomes and with the aid of computational chemistry, we propose some reaction mechanisms and molecular rearrangements.
Supporting Information
Disclaimer: Supplementary materials have been peer-reviewed but not copyedited.
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| hc21255-sup-0001-suppmat.doc1.6 MB | Figure S1. 1H-NMR spectrum of compound 4. Figure S2. 1H-NMR spectrum of compound 5. Figure S3. 13C{1H}-NMR spectrum of compound 5 (smaller peaks correspond to ethyl acetate). Figure S4. 1H-NMR spectrum of compound 9. Figure S5. 13C{1H}-NMR spectrum of compound 9. Figure S6. 1H-NMR spectrum of compound 15. Figure S7. 1H-NMR spectrum of compound 16. Figure S8. 13C{1H}-NMR spectrum of compound 16. Figure S9. Geometry optimization, at the B3LYP/6-311++G(d,p) level of theory, of complex A resulted in complex B, thus supporting that if intermediate 12 was formed (scheme 3 in the manuscript) it could lead to the breaking of the N-O bond and subsequent formation of the final product 9. Table S1. Torsional potential calculations for the internal rotation about the C=N double bond (C(=O)-C=N-O(R) dihedral angle) in compound trans-6 (R = H, ω = 0 º) calculated at the B3LYP/6-311++G(d,p) level of theory. Table S2. Torsional potential calculations for the internal rotation about the C=N double bond (C(=O)-C=N-O(R) dihedral angle) in compound trans-6 (R = H, ω = 0 º) calculated at the MP2/cc-pVDZ level of theory. Table S3. Torsional potential calculations for the internal rotation about the C=N double bond (C(=O)-C=N-O(R) dihedral angle) in compound cis-6 (R = H, ω = 0 º) calculated at the B3LYP/6-311++G(d,p) level of theory. Table S4. Torsional potential calculations for the internal rotation about the C=N double bond (C(=O)-C=N-O(R) dihedral angle) in compound 6 (R = H, ω = 90 º) calculated at the B3LYP/6-311++G(d,p) level of theory. Table S5. Barrier to internal rotation about the C=N double bond (C(=O)-C=N-O(R) dihedral angle) in compound cis-6 (R = P(CH3)2, ω = 0 º) calculated at the B3LYP/6-311++G(d,p) level of theory. Table S6. Barrier to internal rotation about the C=N double bond (C(=O)-C=N-O(R) dihedral angle) in compound cis-6 (R = P(Ph)2, ω = 0 º) calculated at the B3LYP/6-311++G(d,p) level of theory. Table S7. Electronic energies for some relevant molecules calculated at the B3LYP/6-311++G(d,p) level of theory. Table S8. Optimized geometries in Cartesian coordinates (x, y, z). |
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