Mercuric cyanide → HCID 20805659, compound

HRID 1072553Notes

Reaction equation

HRID 1072553 reaction equation
[C:1]1([O:7][P:8]([O:17][C@@H:18]2[C@@H:23]([CH2:24][O:25][C:26]([O:28][C:29]([CH3:35])([CH3:34])[C:30]([Cl:33])([Cl:32])[Cl:31])=[O:27])[O:22][C@H:21](Br)[C@H:20]([NH:37][C:38]([O:40][CH2:41][C:42]([Cl:45])([Cl:44])[Cl:43])=[O:39])[C@H:19]2[O:46][C:47](=[O:75])[CH2:48][C@H:49]([O:61][C:62](=[O:74])[CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH2:72][CH3:73])[CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH3:60])([O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:76]([O:89][C@H:90]([CH2:101][CH2:102][CH2:103][CH2:104][CH2:105][CH2:106][CH2:107][CH2:108][CH2:109][CH2:110][CH3:111])[CH2:91][C:92]([N:94]1[CH2:98][CH2:97][CH2:96][C@H:95]1[CH2:99][OH:100])=[O:93])(=[O:88])[CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][CH2:85][CH2:86][CH3:87].[Hg](C#N)C#N>ClCCCl.C(Cl)Cl>[C:1]1([O:7][P:8]([O:17][C@@H:18]2[C@@H:23]([CH2:24][O:25][C:26]([O:28][C:29]([CH3:34])([CH3:35])[C:30]([Cl:32])([Cl:31])[Cl:33])=[O:27])[O:22][C@@H:21]([O:100][CH2:99][C@@H:95]3[CH2:96][CH2:97][CH2:98][N:94]3[C:92](=[O:93])[CH2:91][C@H:90]([O:89][C:76](=[O:88])[CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][CH2:85][CH2:86][CH3:87])[CH2:101][CH2:102][CH2:103][CH2:104][CH2:105][CH2:106][CH2:107][CH2:108][CH2:109][CH2:110][CH3:111])[C@H:20]([NH:37][C:38]([O:40][CH2:41][C:42]([Cl:43])([Cl:44])[Cl:45])=[O:39])[C@H:19]2[O:46][C:47](=[O:75])[CH2:48][C@H:49]([O:61][C:62](=[O:74])[CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH2:72][CH3:73])[CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH3:60])([O:10][C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 3

HCID 11591Mercuric cyanideHCID 20805658HCID 20805658, compoundHCID 68768478HCID 68768478, compound

Product 1

HCID 20805659HCID 20805659, compoundYield 89.2%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-deoxy-4-O-diphenylphosphono-3-O-[(R)-3-dodecanoyloxytetradecanoyl]-6-O-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl bromide (1.60 g, 1.27 mmol) in dry 1,2-dichloroethane (3.2 mL) were added 4 Å molecular sieves (0.6 g), anhydrous CaSO4 (1.0 g, 7.3 mmol), and N-[(R)-3-dodecanoyloxytetradecanoyl]-(S)-2-pyrrolidinemethanol (0.58 g, 1.14 mmol). The resulting mixture was stirred for 1 h at room temperature, treated with Hg(CN)2 (0.58 g, 2.3 mmol), and heated to reflux for 6 h in the dark. The cooled reaction mixture was diluted with CH2Cl2 and filtered through a bed of celite. The filtrate was washed with 1 N aq KI, dried (Na2SO4), and concentrated. Flash chromatography on silica gel (gradient elution, 25→35% EtOAc/hexanes) afforded 1.72 g (82%) of N-[(R)-3-dodecanoyloxytetradecanoyl]-(S)-2-pyrrolidinylmethyl 2-deoxy-4-O-diphenylphosphono-3-O-[(R)-3-dodecanoyloxytetradecanoyl]-6-O-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside as a colorless oil.

Workup

  1. temperatureheated
  2. temperatureto reflux for 6 h in the dark
  3. customThe cooled reaction mixture
  4. filtrationfiltered through a bed of celite
  5. washThe filtrate was washed with 1 N aq KI
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-cf2538ec748c4dec8e5917d2837417d4
Source dataset
uspto-grants-2005_06
Patent number
US06911434B2

Reaction notes

Loading…