MS/GC study of the imide-amide rearrangement

Lewis Acid or Alkyl Halide Promoted Rearrangements of Phosphor- and Phosphinimidates to N,N-Disubstituted Phosphor- and Phosphinamidates

“…1 H NMR (400 MHz, CDCl 3 ): d = 1.02-1.06 (m, 3 H, NCH 3 ), 1.28-1.32 (m, 6 H, OCH 3 ), 2.99-3.00 (m, 2 H, NCH 2 ), 3.97-4.11 (m, 4 H, OCH 2 ), 4.21 (d, J = 9.6 Hz, 2 H, CH 2 ), 7.23-7.24 (m, 5 H, Ph). 13 C NMR (101 MHz, CDCl 3 ): d = 13.3 (d, J = 1.5 Hz, NCH 3 ), 16.3 (d, J = 7.3 Hz, OCH 3 ), 39.5 (d, J = 3.8 Hz, NCH 2 ), 48.7 (d, J = 5.0 Hz, CH 2 ), 62.3 (d,J = 5.8 Hz,OCH 2 ),127.3,128.3,128.5,138.3 (d,J = 3.8 Hz) (Ph Dibenzyl N,N-Dibenzylphosphoramidate (3c) Prepared according to general procedure I from BnN 3 (399, 3.00 mmol) and P(OBn) 3 (1.06 g, 3.00 mmol). A second column chromatography (CH 2 Cl 2 ) gave the product; yield: 975 mg (71%).…”

“…Prepared according to general procedure II or IV from BnN 3 (399 mg, 3.00 mmol) and Ph 2 POEt (648 mL, 691 mg, 3.00 mmol) as a colorless oil; yield: 604 mg (60%) (GPII) and 513 mg (51%) (GPIV 20 H,Ph). 13 C NMR (500 MHz, CDCl 3 ): d = 48.6 (d,J = 3.6 Hz,CH 2 Ph,127.2,127.8,128.4,128.7 (d,J = 12.5 Hz),128.9,131.4,131.6,131.6,131.9 (d,J = 2.6 Hz), 132.7 (d, J = 9.3 Hz), 136.6 (d, J = 3.6 Hz) (Ph…”

“…Prepared according to general procedure III from 4-methoxyphenyl azide (447 mg, 3.00 mmol) and P(OMe) 3 (354 mL, 372 mg, 3.00 mmol) as a colorless oil; yield: 647 mg (88%). 1 H NMR (400 MHz, CDCl 3 ): d = 3.10 (d, J = 9.0 Hz, 3 H, NCH 3 ), 3.69 (d,J = 11.2 Hz,6 H,POCH 3S,4R,5R,6R)-5-Acetamido-3,4-diacetoxy-2-(acetoxymethyl)-6-[(dimethoxyphosphoryl)(methyl)amino]tetrahydro-2Hpyran (3h) Prepared according to general procedure III from 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-b-D-glucopyranosyl azide (50.0 mg, 0.134 mmol) and P(OMe) 3 (15.0 mL, 16.0 mg, 0.134 mmol); for solubility reasons benzene (1.5 mL) was used as solvent with additional MeCN (200 mL) to give the product as a white solid; yield: 37.1 mg (67%…”

“…Prepared according to general procedure V from cinnamyl bromide (985 mg, 5.00 mmol) as a pale-yellow oil; yield 1.02 g (80%). 1 H NMR (400 MHz, CDCl 3 ): d = 2.58 (d,J = 9.7 Hz,3 H,NCH 3 ), 3.63 (d,J = 11.1 Hz,6 H,OCH 3 ), 3.69 (ddd, J = 10.0, 6.5, 0.9 Hz, 2 H, NCH 2 ), 6.07 (dt, J = 15.8, 6.6 Hz, 1 H, CH), 6.46 (d, J = 15.9 Hz, 1 H, CH), 7.14-7.31 (m, 5 H, Ph). 13 Dimethyl N-Allyl-N-methylphosphoramidate (3j) Prepared according to general procedure V from allyl bromide (434 mL, 605 mg, 5.00 mmol) as a colorless oil; yield: 457 mg (51%).…”

“…13 Dimethyl N-Allyl-N-methylphosphoramidate (3j) Prepared according to general procedure V from allyl bromide (434 mL, 605 mg, 5.00 mmol) as a colorless oil; yield: 457 mg (51%). 1 H NMR (400 MHz, CD 3 CN): d = 2.56 (d, J = 9.6 Hz, 3 H, NCH 3 ), 3.54-3.60 (m, 2 H, CH 2 ), 3.59 (d,J = 11.1 Hz,6 H, OCH 3 ), 5.17 (ddtd, J = 10.2, 1.8, 1.3, 0.6 Hz, 1 H, CH 2 ), 5.22 (ddd, J = 17.2, 3.2, 1.6 Hz, 1 H, CH 2 ), 5.79 (ddt, J = 17.1, 10.2, 6.1 Hz, 1 H, CH). 13…”