Primary Amination of Ar₂P(O)–H with (NH₄)₂CO₃ as an Ammonia Source under Simple and Mild Conditions and Its Extension to the Construction of Various P–N or P–O Bonds

Abstract

A facile and efficient method for the synthesis of primary phosphinamides from Ar2P­(O)–H reagents with stable and readily available ammonium carbonate as an ammonia source is disclosed herein for the first time. This ethyl bromoacetate-mediated primary amination proceeds smoothly under mild and simple conditions, without any metal catalyst or oxidant. Moreover, this method is also appropriate for the reaction of Ar2P­(O)–H with a variety of amines, alcohols, and phenols to construct P–N or P–O bonds, with features of handy operation, good functional group tolerance, and broad substrate scope.

Visible light photocatalytic phosphorylation of heteroatom nucleophiles triggered by phosphorus-centered radical cations

“…Significantly, the less nucleophilic anilines also afforded 4u and 4v in moderate yields, whereas anilines were normally incompatible with the conditions of the Atherton–Todd-type reactions. 8–10 Then, several cyclic secondary amines were examined, resulting in the desired products 4w–4y in good efficiency. Notably, the phosphinylation of biologically active tryptoline, a substrate containing both an aliphatic amine and an indole, occurred selectively with the aliphatic amine.…”

“…7 A partial solution to this problem is the Atherton–Todd reaction, which generates phosphoryl chlorides in situ from the chlorination of P(O)–H compounds in the presence of CCl 4 /base. 8 However, a stoichiometric amount of highly toxic polyhalomethanes, Selectfluor, 8 g or unusual halides 8 h , j as the halogenating reagents is indispensable for the Atherton–Todd-type reactions (Fig. 1b).…”

“…1b). 8 Several improvements on this protocol by the employment of iodide/oxidant systems 9 or iodide-mediated electrosynthesis 10 have recently emerged, while halides are still required for the formation of phosphoryl halide intermediates (Fig. 1b).…”

Ammonia surrogates in the synthesis of primary amines

“…Lastly, it is worth noting that although this review primarily focuses on reactions leading to primary amines, Zhang and Zhao demonstrated the synthesis of phosphinamides through a P–H bond reaction. 55 In their work, they used ammonium carbonate as the source of ammonia, showcasing the versatility of these salts as replacements in various contexts (see Fig. 17b).…”

Photocatalyzed Aerobic Cross-Dehydrogenative Coupling of Diarylphosphine Oxides with Alcohols and Phenols

“…However, the traditional Atherton–Todd reaction requires the use of highly toxic CCl 4 as the halogenating reagent and solvent (Scheme a) . Subsequently, some modified Atherton–Todd reactions using less toxic halogenating reagents (CHCl 3 , Selectfluor, Tf 2 O, or BrCH 2 COOEt) have been successively developed (Scheme b). Alternatively, catalytic Atherton–Todd-type reactions using halide catalysts (I 2 or CuCl 2 ) have been documented, but they require an excess of a strong oxidant (H 2 O 2 or K 2 S 2 O 8 ) and can be applied to only aliphatic alcohols (Scheme c).…”