Controllable Phosphorylation of Thioesters: Selective Synthesis of Aryl and Benzyl Phosphoryl Compounds

Abstract

The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.

Highly Chemoselective Reduction of Phosphine Oxides through Electrophilic Activation of the P=O Bond with Anhydride

“…The data that support the findings of this study are available in the supplementary material of this article. Additional references cited within the Supporting Information [8e,14,19–39] …”

The concise synthesis and resolution of planar chiral [2.2]paracyclophane oxazolines by C–H activation

“…It is possible to subject the enantiomerically enriched 4carboxylic acid 13a to a decarboxylative phosphorylation to give the phosphine oxide 14 in 8-20% (along with 50% unreacted starting material with no erosion of enantiopurity (Scheme 3). [35][36][37] So far, we have been unable to react the pseudoortho-diacid under the same conditions. Although the preliminary results are low yielding, they demonstrate that it is possible to isolate enantiomerically enriched phosphine oxide in just four steps.…”

Reductive Coupling of P(O)–H Compounds and Aldehydes for the General Synthesis of Phosphines and Phosphine Oxides

“…22 White solid; yield 91% (89.0 mg); eluent, 1/1 petroleum ether/EtOAc; 1 H NMR (400 MHz, CDCl (4-Bromobenzyl)diphenylphosphine Oxide (4i). 23 White solid; yield 82% (91. Diphenyl [4-(trifluoromethyl)benzyl]phosphine Oxide (4j).…”

“…27 Yellow solid; yield 58% (54.3 mg); eluent, 1/1 petroleum ether/EtOAc; 1 H NMR (400 MHz, CDCl 3 ) δ 7.71−7.66 (m, 4H), 7.52−7.40 (m, 6H), 7.16−7.14 (m, 1H), 6.97−6.95 (m, 1H), 6.86−6.84 (m, 1H), 3.68 (d, J = 13.4 Hz, 2H); 13 Benzyldi-p-tolylphosphine Oxide (4p). 23 White solid; yield 87% (83.6 mg); eluent, 1/1 petroleum ether/EtOAc; 1 H NMR (400 MHz, CDCl 3 ) δ 7.57−7.53 (m, 4H), 7.21−7.14 (m, 7H), 7.09−7.07 (m, 2H), 3.59 (d, J = 14.0 Hz, 2H), 2.36 (s, 6H); 13 Benzylbis(4-chlorophenyl)phosphine Oxide (4q). 28 White solid; yield 79% (85.6 mg); eluent, 1/1 petroleum ether/EtOAc Dibenzyl(phenyl)phosphine Oxide (4r).…”