Organophosphorus chemistry: from model to application
This thematic issue encompasses diverse aspects of organophosphorus chemistry, an important field within organic chemistry. Well-known examples of organophosphorus compounds include phosphine oxides, phosphinates, and phosphonates, which are widely used as starting materials, intermediates, reagents, and P-ligands in transition metal catalysis or as organocatalysts, and even as solvents (ionic liquids). The relevance of this discipline is further highlighted by a series of famous named reactions applying different P-reactants that form an important toolbox in synthetic organic chemistry regarding P-functionalization.
As such, the scope of this interdisciplinary thematic issue spans from theoretical aspects (mechanisms, stereostructures, as well as conformations) to synthetic methods and useful applications, which all present challenging fields. This may include original methods to prepare important chiral organophosphorus compounds by enantioselective approaches or resolution, P-heterocyclic chemistry, green organophosphorus chemistry, and biologically active substrates, to name but a few examples.
- Letter
- Published 09 Sep 2022
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Scheme 1: Different strategies for phospha-Brook reactions.
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Scheme 2: Scope of 1 (secondary phosphine oxides and phosphonate). Reaction conditions: 1 (0.2 mmol), 2-pyrid...
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Scheme 3: Scope of 2 (α-pyridinealdehydes and α-pyridones). Reaction conditions: diphenylphosphine oxide (1a,...
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Scheme 4: Control experiments.
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Scheme 5: Proposed mechanism.
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- Full Research Paper
- Published 13 Sep 2022
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Figure 1: Structures of 2-phosphaindolizine (1) and indolizine (2).
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Figure 2: Structures of 1-aza-2-phosphaindolizines 3, 3-aza-2-phosphaindolizines 4, and 1,3-diaza-2-phosphain...
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Figure 3: Transfer of the nitrogen lone-pair in 2-phosphaindolizines.
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Figure 4: Energy gap (ΔE) between HOMO of 1,3-butadiene and LUMO of 2-phosphaindolizine.
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Figure 5: Kohn–Shan HOMO of 1,3-butadiene and LUMOs of 2-phosphaindolizines computed at the B3LYP/6-31+G(d) l...
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- Full Research Paper
- Published 27 Sep 2022
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Scheme 1: Synthesis of bis(chlorophenyl)acetylenes 3.
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Scheme 2: Synthesis of 1,2,3-tris(chlorophenyl)cyclopropenylium bromides 5 and tributyl(1,2,3-tris(chlorophen...
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Figure 1: ORTEP representations for cations 5c (a) and 6c (b) at the 50% probability level. Bromide anion and...
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Scheme 3: Synthesis of 3,4,5-tris(chlorophenyl)-1,2-diphosphacyclopentadienides 7 and 3,4,5-tris(chlorophenyl...
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Figure 2: Considered conformations of 8b-I and 8b-II.
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Figure 3: Top: experimental UV–vis spectra of 8с (black) and 8b (red). Bottom: broadened calculated UV–vis sp...
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Figure 4: Frontier orbitals of 8b-II contributing to absorption bands at about 380 nm.
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Figure 5: Cyclic voltammograms of 3,4,5-triaryl-1,2-diphosphaferrocenes 8b and 8c in CH3CN on glassy carbon e...
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- Full Research Paper
- Published 17 Oct 2022
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Figure 1: Chiral phosphorus acids (CPAs) derived from BINOL, VAPOL, and SPINOL. R = H, Ph, 4-PhC6H4-, 4-β-nap...
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Scheme 1: The thiolic/thionic tautomeric equilibrium in thiophosphorus acids.
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Figure 2: Project strategy and requirements for C1-symmetrical CPAs.
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Figure 3: BINOL CPA and C1-symmetrical CPA targets 1–4.
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Scheme 2: Synthesis of tryptophol-derived thiophosphorus acid 1.
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Scheme 3: Synthesis of indole-derived thiophosphorus acid 2.
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Scheme 4: Synthesis of N-biphenyl-DOPO CPA 4.
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Scheme 5: Transfer hydrogenation of 2-phenylquinoline and transition-state proposed by Guinchard and coworker...
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Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance
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- Published 25 Oct 2022
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Figure 1: ORTEP representation of triferrocenyl trithiophosphite showing 50% probability thermal ellipsoids.
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Figure 2: Optimized conformations and relative energies of four possible conformers of triferrocenyl trithiop...
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Figure 3: Calculated NBO charges on the Fe ions and hydrogen atoms for the optimized ttg conformer (left) and...
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Figure 4: Molecular structures in the solid state of a) (FcS)3P, b) (FcS)3PO [19], and c) (FcS)3PS [7] as establishe...
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Figure 5: Quantum chemically optimized conformations of the (PhS)3P molecule and their relative energies (kca...
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- Letter
- Published 07 Nov 2022
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Scheme 1: Scheme showing the transformation of the Br-substrates to phosphonate esters and then to phosphonic...
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Figure 1: Experimental setup for the improved C–P cross-coupling reaction.
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- Full Research Paper
- Published 10 Jan 2023
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Figure 1: Training set of tri- and tetracoordinate phosphorus compounds; chemical shifts are in ppm, referenc...
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Figure 2: (a) Plot of experimental vs calculated chemical shifts of tri- and tetracoordinate phosphorus compo...
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Figure 3: Plot of experimental vs calculated chemical shifts of training set compounds reported by Latypov et...
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Figure 4: “Large” compounds selected for 31P NMR calculation by Latypov [37].
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Figure 5: Stereoisomers and unusual phosphorus compounds used for chemical shift calculations.
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Figure 6: Phosphorus-catalyzed oxygen transfer reaction intermediates.
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Figure 7: Phosphirane reactions.
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Figure 8: (a) Plot of experimental vs scaled chemical shifts derived from the tri- and tetracoordinate phosph...
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