HCID 1950, compound → HCID 53677329, compound

Participants

Reaction Steps

To a solution of (2S,3R,4S,5S)-4-methoxy-5-methyl-2-[(E)-1-nonenyl]tetrahydro-2H-pyran-3-ol (0.5 g), dimethylamino-pyridine (0.03 g) and (N-carbobenzoxy-amino)methylphosphonic acid (0.7 g) in dry pyridine (30 ml) there was added 2,4,6-triiso=propyl benzenesulfonyl chloride (0.74 g). The reaction mixture was stirred for 12 hr at room temperature and evaporated to dryness under reduced pressure. The residue was partitioned between ether (50 ml) and 0.1N-HCl (50 ml). The ether layer was dried over anhydrous sodium sulfate, evaporated to dryness under reduced pressure. The resultant yellow oil was dissolved in ether (30 ml) and methanol (5 ml). 10%-trimethylsilyldiazomethane solution in hexane was added to the solution until the evolution of gas ceased. The reaction mixture was evaporated to dryness and purified by silica gel chromatography eluted with CH2Cl2 /AcOEt (7:3) to give (2S,3R,4S,5S)-4-methoxy-5-methyl-2-[(E)-1-nonenyl]tetrahydro-2H-pyran-3-yl methyl (benzyloxy=carbonylamino)methylphosphonate (0.8 g, y. 84%) as a colorless oil; EI-MS: m/z 511 (M+) b) A solution of (2S,3R,4S,5S)-4-methoxy-5-methyl-2-[(E)-1 -nonenyl]tetrahydro-2H-pyran-3-yl methyl (benzyloxycarbonyl=amino)methylphosphonate (0.8 g) in methanol (20 ml) was stirred under hydrogen atmosphere in the presence of Pd-black (50 mg) at room temperature for 4 hr. The catalyst was removed by filtration and washed with methanol (10 ml×2). The combined filtrate and washings were evaporated to dryness under reduced pressure to give (2S,3R,4S,5S)-4-methoxy-5-methyl-2-nonyl=tetrahydro-2H-pyran-3-yl methyl (aminomethyl)phosphonate (0.534 g, y. 90%) as colorless oil; FAB-MS: m/z 380 (MH+); 1H-NMR (CDCl3)d: 0.88 (3H,t,J=6 Hz), 1.0 (3H,d,J=6.3 Hz), 1.24 (14H,br.s), 1.54 (1H,m), 1.7 (1H,m), 2.31 (1H,m), 3.1-3.3 (5H,br.m), 3.37 (1.5H,s), 3.40 (1.5H, s), 3.47-3.54 (2H,m), 3.79 (1H,m), 3.85 (1.5 H, d,J=12 Hz), 3.91 (1.5H,d,J=12 Hz), 4.2 (1H,m). (2S,3R,4S,5S)-4-Methoxy-5-methyl-2-nonyltetrahydro-2H-pyran-3-yl (aminomethyl)phosphonate could also be obtained by the same manner as Example 57 without O-methylation.

Provenance & Evidence