Green synthesis of tertiary alkylselanylphosphine chalcogenides via catalyst- and solvent-free addition of secondary phosphine chalcogenides to vinyl selenides

3H-Phosphaallenes are accessible on a new and facile route and show a fascinating chemical behavior. The thermally induced rearrangement of Mes*PCC(H)R′ (R′ = tBu, Ad) afforded by C–H activation, isobutene elimination, and C–C and P–H bond formation bicyclic 1-benzo-dihydrophosphetes (2) with PC3 heterocycles. DFT calculations suggest a mechanism with intramolecular nucleophilic aromatic substitution and replacement of an alkyl group by the nucleophilic α-C atom of the phosphaallene. These bicycles formed W(CO)5 complexes (3) or afforded 1,2-dihydrophosphetes with P-bound alkenyl groups by catalyst-free hydrophosphination of alkynes (4 and 5). The resulting bulky phosphines formed complexes with IrCp*Cl2, RuCl2, AuCl, or CuO3SCF3. The Ru atom is coordinated by the P atom and a phenyl group. Irradiation of TripPCC(H)tBu led by the insertion of the central C atom of the PCC group into the α-C–H bond of an iPr substituent and by C–C and P–C bond formation to a new isomer of phosphaallenes, 10, which features a strained PC2 heterocycle. It formed adducts with M(CO)5 (M = Cr, Mo, W) and AuCl and reacted with SO2Cl2 by cleavage of one of the phosphirane P–C bonds to yield PC4 or PC5 heterocycles. Hydrolysis yielded a PC5 compound with a P(O)Cl group.

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Aspects of Phosphaallene Chemistry: Heat-Induced Formation of 1,2-Dihydrophosphetes by Intramolecular Nucleophilic Aromatic Substitution and Photochemical Generation of Tricyclic Phosphiranes

Tendyck

Klöcker

Schürmann

et al. 2020

J. Org. Chem.

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Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

et al. 2016

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UV induced hydrophosphination of dimethyl 2-vinylcyclopropane-1,1-dicarboxylate towards phosphine chalcogenides

2023

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Green synthesis of tertiary alkylselanylphosphine chalcogenides via catalyst- and solvent-free addition of secondary phosphine chalcogenides to vinyl selenides

Abstract: Secondary phosphine sulfides and phosphine selenides react with vinyl selenides under mild conditions (80-82°C, without catalyst and solvent) to form regioselectively functionalized anti-Markovnikov adducts in high yield.

Cited by 7 publications

References 33 publications

Aspects of Phosphaallene Chemistry: Heat-Induced Formation of 1,2-Dihydrophosphetes by Intramolecular Nucleophilic Aromatic Substitution and Photochemical Generation of Tricyclic Phosphiranes

Aspects of Phosphaallene Chemistry: Heat-Induced Formation of 1,2-Dihydrophosphetes by Intramolecular Nucleophilic Aromatic Substitution and Photochemical Generation of Tricyclic Phosphiranes

Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

UV induced hydrophosphination of dimethyl 2-vinylcyclopropane-1,1-dicarboxylate towards phosphine chalcogenides

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