Benzaldehyde dimethyl acetal → (2r,4s,5r)-2,4-Diphenyl-3-(9-anthracenesulfonamido)-5-methoxycarbonyl-1,3-oxazolidine

HRID 567424Notes

Reaction equation

HRID 567424 reaction equation
[CH:1]1[C:14]2[C:5](=[CH:6][C:7]3[C:12]([C:13]=2[S:15]([NH:18][C@@H](C2C=CC=CC=2)[C@@H](O)C(OC)=O)(=[O:17])=[O:16])=[CH:11][CH:10]=[CH:9][CH:8]=3)[CH:4]=[CH:3][CH:2]=1.C[O:33][CH:34]([O:41][CH3:42])[C:35]1C=CC=CC=1.[C:43]1([CH3:53])[C:44](S([O-])(=O)=O)=[CH:45][CH:46]=[CH:47][CH:48]=1.[NH+:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1.[C:60](#N)[CH3:61].[OH2:63]>C1(C)C=CC=CC=1.[Hg]>[C:43]1([C@@H:53]2[N:54]([NH:18][S:15]([C:13]3[C:12]4[C:7]([CH:6]=[C:5]5[C:14]=3[CH:1]=[CH:2][CH:3]=[CH:4]5)=[CH:8][CH:9]=[CH:10][CH:11]=4)(=[O:16])=[O:17])[C@@H:59]([C:58]3[CH:61]=[CH:60][CH:55]=[CH:56][CH:57]=3)[C@H:35]([C:34]([O:41][CH3:42])=[O:33])[O:63]2)[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=1

Participants

7

Reactant 4

HCID 62375Benzaldehyde dimethyl acetalHCID 18373917Acetonitrile--water (1/1)HCID 57078772HCID 57078772, compoundHCID 865878692-Methylbenzenesulfonate;pyridin-1-ium

Product 1

HCID 54455394(2r,4s,5r)-2,4-Diphenyl-3-(9-anthracenesulfonamido)-5-methoxycarbonyl-1,3-oxazolidineYield 70.2%

Reagents, catalysts & solvents 2

HCID 23931MercuryCatalystHCID 1140TolueneSolvent

Procedure

A suspension of methyl (2R,3S)-3-(9-anthracenesulfonamido)-3-phenyl-2-hydroxypropionate (II, EXAMPLE 11C, 45 mg, 0.1 mmol) in dry toluene (1 ml) is treated with benzaldehyde dimethylacetal (45 μl, 0.3 mmol) in the presence of a catalytic amount of pyridinium toluenesulfonate (2.5 mg, 0.01 mmol) and stirred at 75° under reduced pressure of 15 inch/mercury for 2 hr. HPLC analysis (silica gel with a C-18 group attached; acetonitrile/water, 65/35, flow 1 ml/min and UV 254 nm) showed the final product (70.2%, retention time 15.0 mins) and the (3S)-diasteriomer (3.5%, retention time 17.0 mins). The resulting reaction mixture is diluted with ethyl acetate (15 ml) and washed with water (10 ml). The aqueous phase is extracted again with ethyl acetate (10 ml). The combined organic phase is dried over magnesium sulfate, filtered and the solvent is removed under reduced pressure. Purification by silica gel column chromatography (ethyl acetate/hexane, 10/90) gives the title compound, mp=71-73°; IR (mineral oil) 1762, 1737, 1332, 1216, 1158, 1146, 1116, 1106, 1089, 1076, 1027, 755, 739, 697 and 681 cm−1; NMR (300 MHz, CDCl3) 9.02, 8.39, 7.86, 7.57-7.50, 7.43, 7.30-7.25, 7.07, 6.88, 6.67-6.51, 6.51-6.44, 6.27, 5.94, 4.84 and 3.77 δ; CMR (300 MHz, CDCl3) 170.0, 137.1, 136.2, 133.5, 130,9, 130.5, 128.9, 128.8, 128.6, 128.1, 128.0, 126.9, 125.2, 124.9, 93.1, 81.6, 68.7 and 52.6 δ; MS (m/z) 524 (M++1), 523 (M+), 369, 354, 346, 282,265, 241, 209, 193, 178, 165, 121 and 91; HRMS (m/z) calculated C31H25N1O5S1+H1=524.1531, observed=524.1530.

Sources & evidence

ORD record
ord-655908e77d484c539efa93a0fe3c08ca
Source dataset
uspto-grants-2001_01
Patent number
US06177573B1

Reaction notes

Loading…