Catalytic Enantioselective Synthesis of Aryl–Methyl Organophosphorus Compounds

Abstract

A catalytic enantioselective protocol for the synthesis of aryl−methyl organophosphorus compounds is reported. Utilizing a chiral phosphoric acid as a catalyst, a wide range of indole derivatives reacted with phosphorylated quinomethanes in high yield with excellent enantioselectivity. This is the first report on the application of phosphorylated quinomethanes in asymmetric synthesis.

Metal‐free, Phosphoric Acid‐catalyzed Regioselective 1,6‐Hydroarylation of para‐Quinone Methides with Indoles in Water

“…According to the Tripathi's report, we synthesized diethyl ((3,5‐di‐ tert ‐butyl‐4‐oxocyclohexa‐2,5‐dien‐1‐ylidene)methyl) phosphonate ( 1 af ) as the substrate to react with indole under the optimized reaction conditions [16a] . As monitored by GC‐MS and NMR analysis, the corresponding 1,6‐hydroarylation product 3 af was generated in 53% yield.…”

“…Diethyl((3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)(1H‐indol‐3‐yl) methyl)phosphonate (3 af) : According to the general procedure, work‐up and flash column chromatography (Hexane/EtOAc: 3 : 1) gave product 3 af (50.1 mg, 0.106 mmol, 53%) as a colorless oil [16a] . 1 H NMR (400 MHz, CDCl 3 , 25 °C, TMS): δ=8.42 (s, 1H), 7.59–7.61 (m, 2H), 7.34–7.36 (m, 3H), 7.07–7.18 (m, 2H), 5.08 (s, 1H), 4.64 (d, J =25.2 Hz, 1H), 3.66–4.00 (m, 4H), 1.39 (s, 18H), 1.02–1.11 (m, 6H).…”

Tandem Cyclization Reaction of Diphenyl 3,5-Di-tert-butyl-p-quinone Phosphonate Catalyzed by Trifluoromethanesulfonic Acid: Introduce a Comprehensive Experiment of Organic Chemistry

“…通过 1 H NMR、 13 C NMR和 31 P NMR表征了化合物6的分子结构 [8] 。 1 H NMR中δ 1.31为两个叔丁基 上的氢，δ 2.07是苄位甲基氢，δ 4.87是与磷相连的碳上的氢，被磷原子耦合裂分为两重峰。δ 9.79是 羟基上的活泼氢，δ 6.52-7.42中包括了芳香氢和另一个羟基活泼氢，通过氘水交换实验发现δ 9.79处 的氢信号消失，δ 6.52-7.42少了一个氢，从而验证了两个活泼氢(酚羟基)的存在。 13 通过查阅文献 [8,9]…”

Photocatalytic formation of P–S bonds via CdSeS/CdZnS quantum dots under visible light irradiation

“…Organophosphorus chemistry plays a pivotal role in numerous scientific domains. 1 It finds extensive use in organic chemistry, [2][3][4][5][6] materials science, 7,8 biomedicine, and other fields. [9][10][11] In particular, the inclusion of the P-S or P(O)-S bond in organophosphorus compounds imparts distinctive physicochemical properties, structural characteristics, and biological activities.…”