Metal‐Free, N‐Iodosuccinimide‐Induced Regioselective Iodophosphoryloxylation of Alkenes with P(O)−OH Bonds

Abstract

A simple and efficient method for the regioselective iodophosphoryloxylation of alkenes with P(O)−OH bonds has been established by using NIS (N‐iodosuccinimide) as the iodination reagent under transition‐metal‐free conditions. The present protocol is compatible with different functional groups, and suitable for various alkenes and P(O)−OH compounds. A variety of functionalized β‐iodo‐1‐ethyl phosphinic/phosphoric acid esters are obtained in good to excellent yields, which could be further transformed to diversified building blocks for the synthesis of bioactive compounds, pharmaceuticals and functional materials.

Recent Progress in N-Iodosuccinimide (NIS)-Mediated Iodination Reactions

“…唐课文课题组 [38] 以 NIS 为碘化试剂, 建立了一种简 便高效的烯烃选择性碘磷酰氧化反应方法(Scheme 23). 该策略适用于多种烯烃和 P(O)-OH 化合物, 能够得到 多种功能化的 β-碘-1-乙基膦酸/磷酸酯类化合物, 其收 率较高, 且可以进一步转化为多种生物活性化合物、药 物分子和功能材料.…”

P-Chloride-Free Synthesis of Phosphoric Esters: Microwave-Assisted Esterification of Alkyl- and Dialkyl Phosphoric Ester-Acids Obtained from Phosphorus Pentoxide

“…29 The esterification of P-acids, especially that of phosphinic acids, is a hot topic. Xiong and Tang together with co-workers elaborated the esterification of phosphinic acids applying coupling agents, such as N,N′-carbonyl diimidazole 30,31 or uronium-based salts, 30,32 or using cyclic diaryliodonium salts as the reactant, leading to diphenylation. 33 Our group has experience in the microwave (MW)-assisted direct esterification of P-acids.…”