Chris L Vonnegut1, Airlia M Shonkwiler1, Muhammad M Khalifa1, Lev N Zakharov2, Darren W Johnson3, Michael M Haley4. 1. Department of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, OR 97403-1253 (USA). 2. CAMCOR-Center for Advanced Materials Characterization in Oregon, University of Oregon, Eugene, OR 97403-1443 (USA). 3. Department of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, OR 97403-1253 (USA). dwj@uoregon.edu. 4. Department of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, OR 97403-1253 (USA). haley@uoregon.edu.
Abstract
Treatment of 2-ethynylanilines with P(OPh)3 gives either 2,2-diphenoxy-2-λ(5)-phosphaquinolines or 2-phenoxy-2-λ(5)-phosphaquinolin-2-ones under transition-metal-free conditions. This reaction offers access to an underexplored heterocycle, which opens up the study of the fundamental nature of the N=P(V) double bond and its potential for delocalization within a cyclic π-electron system. This heterocycle can serve as a carbostyril mimic, with application as a bioisostere for pharmaceuticals based on the 2-quinolinone scaffold. It also holds promise as a new fluorophore, since initial screening reveals quantum yields upwards of 40%, Stokes shifts of 50-150 nm, and emission wavelengths of 380-540 nm. The phosphaquinolin-2-ones possess one of the strongest solution-state dimerization constants for a D-A system (130 M(-1)) owing to the close proximity of a strong acceptor (P=O) and a strong donor (phosphonamidate N-H), which suggests that they might hold promise as new hydrogen-bonding hosts for optoelectronic sensing.
Treatment of 2-ethynylanilines with n class="Chemical">P(OPh)3 gives either 2,2-diphenoxy-2-λ(5)-phosphaquinolines or 2-phenoxy-2-λ(5)-phosphaquinolin-2-ones under transition-metal-free conditions. This reaction offers access to an underexplored heterocycle, which opens up the study of the fundamental nature of the N=P(V) double bond and its potential for delocalization within a cyclic π-electron system. This heterocycle can serve as a carbostyril mimic, with application as a bioisostere for pharmaceuticals based on the 2-quinolinone scaffold. It also holds promise as a new fluorophore, since initial screening reveals quantum yields upwards of 40%, Stokes shifts of 50-150 nm, and emission wavelengths of 380-540 nm. The phosphaquinolin-2-ones possess one of the strongest solution-state dimerization constants for a D-A system (130 M(-1)) owing to the close proximity of a strong acceptor (P=O) and a strong donor (phosphonamidateN-H), which suggests that they might hold promise as new hydrogen-bonding hosts for optoelectronic sensing.
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