Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes

Abstract

Straightforward access to bidentate phosphorus ligands and bis(phosphineoxide)ethanes is described based on atom-economic addition reaction. A practical approach was developed to incorporate 2H and 13C labels using easily available reagents.

Calcium carbide residue – a promising hidden source of hydrogen

“…To check the H/D exchange during the treatment of CCR- d 2 , the nucleophilic addition of diphenylphosphine oxide to acetylene- d 2 generated in situ from carbide was performed. 88 This addition was chosen as a representative example, since the reaction occurs both in the absence of a base (CCR2- d 2 , Scheme 1D) and in the presence of a base (CCR3- d 2 , Scheme 1E). CCR3- d 2 was additionally washed with water to remove the rest of KF (see the ESI† for details).…”

Ligand Control of Copper-Mediated Cycloadditions of Acetylene to Azides: Chemo- and Regio-Selective Formation of Deutero- and Iodo-Substituted 1,2,3-Triazoles

“…13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 150. 9,132.8,129.9,125.8,125.4 (t,J = 30.0 Hz),125.0,120.8,112.1,55.7. HRMS (ESI-Q-Orbitrap) m/z: [M + H] + Calcd for C 9 H 8 DN 3 O: 177.0882; found: 177.0872.…”

“…13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 138. 9,134.7,134.1 (t,J = 30.0 Hz),134.1,133.8,130.2,121.7,120.5 1-(4-Chlorophenyl)-1H-1,2,3-triazole-4-d (3e). Purified by flash chromatography on silica gel (eluted with petroleum ether/ ethyl acetate = 6:1) as pale yellow solid; 116.6 mg; mp: 111−113 °C; 64% yield; 1 H NMR (400 MHz, CDCl 3 ) δ 7.99 (s, 1H), 7.81 (d, J = 1.2 Hz, 0.02H), 7.66 (d, J = 8.9 Hz, 2H), 7.45 (d, J = 8.9 Hz, 2H).…”

“…13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 137. 9,135.6,134.5 (t,J = 30.8 Hz),130.9,128.9,121.7,120.9,118.6 Purified by flash chromatography on silica gel (eluted with petroleum ether/ethyl acetate = 10:1) as white solid; 172.0 mg; mp: 58−60 °C; 80% yield; 1 H NMR (400 MHz, CDCl 3 ) δ 8.10 (s, 1H), 8.05−7.99 (m, 1H), 7.94 (dt, J = 6.9, 2.3 Hz, 1H), 7.85 (d, J = 1.2 Hz, 0.09H), 7.73−7.58 (m, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 137.4, 134.7 (t, J = 29.7 Hz), 132.4 (q, J = 21.1 Hz), 130.7, 125.4 (q, J = 3.8 Hz), 123.7, 123.4 (q, J = 270.8 Hz), 121.8, 117.6 (q, J = 3.9 Hz).…”

Photoinduced synthesis of C2-linked phosphine oxides via radical difunctionalization of acetylene

“…3 For example, 1,2-bis(diphenylphosphino)ethane (DPPE) is an important biphosphine ligand for transition metal catalysis. 3 a Recently, the dioxide of DPPE (DPPE-dioxide) and its analogues have also received attention in the synthesis of mononuclear metal complexes 4 and the assembly of coordination polymers. 5 Traditional strategies for the synthesis of DPPE primarily rely on the substitution reactions of highly reactive alkali metal diphenylphosphides (Ph 2 PM) with 1,2-dihaloethanes in an SN 2 fashion 6 or alkoxide-base-catalyzed hydrophosphination.…”