Ultrasonic Activation for the N  →  O Phosphoryl Migration of Phosphoryl‐Serine and ‐Threonine

Abstract

Ultrasonic irradiation on N‐phosphoryl‐serine and ‐threonine in acetonitrile at 30°C, 8 and 3 hr, yielded 82% and 86% O‐phosphoryl‐serine and ‐threonine, respectively.

Keywords:

• Serine
• Threonine
• Phosphorylation
• Ultrasonic irradiation

Acknowledgment

We thank the financial supports from the Chinese National Natural Science Foundation (No. 20132020), The Ministry of Science and Technology, The Chinese Ministry of Education and Zhengzhou University.

Notes

^aSpectral data for the representative products (3a) ³¹P NMR (400 MHz, CDCl₃), δ 5.85; ¹H NMR (400 MHz, CDCl₃), δ 1.28 (d, J = 6.16 Hz, 12H), 3.86 (d, J = 3.84 Hz, 2H), 3.90 (br, 1H), 4.12 (dd, J = 4.28 Hz, 1H), 4.51 (br, 1H), 4.62 (m, 2H), 11.94 (br, 1H); ¹³C NMR (400 MHz, CDCl₃), δ 23.70, 56.17, 64.43, 71.90, 173.76; ESI‐MS: 270 (M + H)⁺, 292 (M + Na)⁺. (3b) ³¹P NMR (400 MHz, CDCl₃), δ 6.19; ¹H NMR (400 MHz, CDCl₃), δ 1.26 (d, J = 6.08 Hz, 12H), 1.34 (d, J = 4.78 Hz, 3H), 4.06 (m, 1H), 4.12 (dd, J = 4.48 Hz, 1H), 4.26 (br, 1H), 4.59 (br, 1H), 4.62 (m, 2H), 10.56 (br, 1H); ¹³C NMR (400 MHz, CDCl₃), δ 19.13, 23.65, 59.65, 68.56, 71.86, 174.48; ESI‐MS: 284 (M + H)⁺, 306 (M + Na)⁺. (4a) ³¹P NMR (400 MHz, CDCl₃) δ −2.78; ¹H NMR (400 MHz, D₂O), δ 1.16 (d, J = 6.26 Hz, 12H), 3.95 (m, 2H), 4.19 (m, 1H), 4.35 (d, J = 6.36 Hz, 2H); ¹³C NMR (400 MHz, D₂O), δ 22.6, 60.7, 67.7, 69.4, 177.0; ESI‐MS: 270 (M + H)⁺, 292 (M + Na)⁺. (4b) ³¹P NMR (400 MHz, CDCl₃), δ −3.881; ¹H NMR (400 MHz, D₂O), δ 1.15 (d, J = 6.24 Hz, 12H), 1.25 (d, J = 6.33 Hz, 3H), 3.91 (m, 2H), 4.24 (m, 1H), 4.35 (d, J = 6.35 Hz, 1H); ¹³C NMR (400 MHz, D₂O), δ 14.7, 22.6, 65.3, 67.7, 72.5, 176.0; ESI‐MS: 284 (M + H)⁺, 306 (M + Na)⁺.