- Synthesis, crystal structures and magnetic properties of a P-stereogenic: Ortho -(4-amino-tempo)phosphinic amide radical and its CuIIcomplex
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The synthesis of phosphinic amides containing one 4-amino-TEMPO substituent at the ortho position has been achieved through copper(i) catalyzed cross-coupling reactions of ortho-iodophosphinic amides with 4-amino-TEMPO. The method has been extended to the preparation of the first example of a P-stereogenic ortho-(4-amino-tempo)phosphinic amide radical 10. The reaction of 10 with Cu(hfac)2 afforded the P-stereogenic CuII complex 19. The crystal structure of both chiral compounds is reported. The molecular structure of 10 consists of a supramolecular zig-zag chain formed by intermolecular hydrogen bonds between the NH group of the phosphinic amide moiety and the nitroxide oxygen atom. In complex 19, the ligand acts as a bridge between two CuII ions coordinated to the oxygen atoms of the PO and N-O· groups leading to the formation of a polymeric helicate chain in which the metal ions exist in a distorted octahedral geometry. The magnetic behavior of ligand 10 is characterized by very weak intermolecular antiferromagnetic interactions, whereas ferro- and anti-ferromagnetic interactions are present in complex 19. This journal is
- Navarro, Yolanda,Guedes, Guilherme P.,Del águila-Sánchez, Miguel A.,Iglesias, María José,Lloret, Francisco,López-Ortiz, Fernando
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- Primary Amination of Ar2P(O)-H with (NH4)2CO3as an Ammonia Source under Simple and Mild Conditions and Its Extension to the Construction of Various P-N or P-O Bonds
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A facile and efficient method for the synthesis of primary phosphinamides from Ar2P(O)-H reagents with stable and readily available ammonium carbonate as an ammonia source is disclosed herein for the first time. This ethyl bromoacetate-mediated primary am
- Han, Ya-Ping,Tan, Yushi,Yang, Shang-Dong,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
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- A phosphoryl radical-initiated Atherton-Todd-type reaction under open air
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A phosphoryl radical-initiated Atherton-Todd-type reaction using air as the radical initiator and CHCl3 as the halogenating reagent for the phosphorylation of alcohols, phenols, and amines has been developed. This novel transformation provides a highly efficient route to important phosphinates, phosphinic amides, and phosphoramidates in up to 99% yield with a broad substrate scope under very mild conditions (48 examples).
- Ou, Yingcong,Huang, Yuanting,He, Zhenlin,Yu, Guodian,Huo, Yanping,Li, Xianwei,Gao, Yang,Chen, Qian
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supporting information
p. 1357 - 1360
(2020/02/11)
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- Phosphinamide-directed ortho metalations: Application to the desymmetrization of the diphenylphosphoryl group
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Diphenylphosphinamides have been regioselectively ortho-lithiated under mild conditions providing a simple access to ortho-functionalized derivatives in good yields. The application of the methodology to the diastereoselective desymmetrization of the phos
- Fernández, Ignacio,Burgos, Pascual O?a,Gómez, Gloria Ruiz,Bled, Caroline,García-Granda, Santiago,Ortiz, Fernando López
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p. 611 - 614
(2007/10/03)
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- SOME NEW PHOSPHINIC AMIDES R2P(O)NHR'
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P,P-Diorganylphosphinic amides R2P(O)NHR' (R = tBu, iPr, Ph; R' = Et, Pr, Cy, iPr, tBu, Ph, etc.) have been prepared by reaction of R2PCl with the corresponding lithiated amine followed by oxidation with H2O2.Th
- Brueck, A.,Kuchen, W.,Peters, W.
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p. 129 - 134
(2007/10/03)
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- PHOSPHORORGANISCHE VERBINDUNGEN 96. DIE SELECTIVE VERKNUEPFUNG BIOLOGISCH WICHTIGER FUNKTIONELLER GRUPPEN MIT PHOSPHORORGANISCHEN SAEUREN
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Derivatives of phosphinic, phosphonic, and phosphoric acids of the general type R1R2P(O)X show selectivity in their reactions with nucleophiles RYH (R = n-C4H9; Y = O, NR or S) according the Eq. (1); the selectivity depends on the nature of the leaving group (X = Cl, F, CN, N3 or OC6H4NO2(p)) and the base used.The nature of the ligands R1 and R2, exert a comparatively minor influence on the reaction.Method: (a) The phosphylating agent R1R2P(O)X was allowed to react with mixture of two nucleophiles RYH and RY'H in competition (Reagent ratio 1:1:1).The product mixture (R1R2P(O)YR + R1R2P(O)Y'R was then analyzed. (b) Compounds of the type HY-CH2-CH2-Y'H (serine-n-butylamide L-cysteinmethylester) were reacted with the phosphylating agent R1R2P(O)X (reagent ratio 1:1) according the Eqs. (3) and (4) respectively.The products were isolated, identified and the yields quantitatively determined.Results: For X = F, CN, OC6H4NO2 (p), the O-ester is formed virtually exclusively.For X = Cl, only amides are formed.Azides (X = N3) show no selectivity.In competition reactions using n-butylamine and n-butylthiol, the organophosphorus chlorides (X = Cl) were found to be N-selective,, whereas the corresponding cyanides (X = CN) were S-selective.In competition reactions using n-butanol and n-butylthiol, the organophosphorus fluorides (X = F) p-nitrophenylesters (X = OC6H4NO2(p)) and cyanides (X = CN) were all O-selective.
- Horner, L,Gehring, R.
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p. 157 - 176
(2007/10/02)
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