Convenient Hydrophosphorylation of Dibenzo[b,f][1,4]oxa‐/thiazepines by Acid Catalysis

Abstract

A protocol for the acid-catalyzed synthesis of phosphorylated dihydrodibenzoxa-/thiazepine derivatives from dibenzo[b,f][1,4]oxa-/thiazepines has been established. The reaction appears compatible with a range of functional groups in both the dibenzo[b,f][1,4]oxa-/thiazepine, H-phosphonate and especially diarylphosphine oxide phosphorylation partners, affording moderate to excellent yields of the corresponding products. The present method further expands the utility of Pudovik reaction.

Recent Progress in Transformations of Azepine/Oxazepine/Thiazepine Derivatives

“…In 2022, Wang and co‐workers found that hydrophosphorylation of tri‐cyclic seven‐membered imines 1 , 11 can be catalyzed by a Lewis acid, or a Brønsted acid as a catalyst (Scheme 13). [37] The reaction of dibenzo[ b , f ][1,4]oxazepines 1 with diarylphosphine oxides 34 , or H‐phosphites was performed in the presence of La(OTf) 3 as a Lewis acid catalyst. While pentafluorobenzoic acid (PFBA) as a Brønsted acid was selected as the best catalyst for the coupling reaction between dibenzo[ b , f ][1,4]thiazepines 11 with phosphorylating reagents 34 .…”

Phospha-Mannich reactions of phosphinous acids R 2 P–OH and their derivatives

“…Figure S10. P(O),NH-acetals, obtained by reactions of dibenzo[b,f][1,4]-oxa-and -thi-azepines with SPOs [193]. …”