Phenylacetylene → 12-(4-Phenyl-[1,2,3]triazol-1-yl)dodecyl 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->2)-3,4,6-tri-O-acetyl-alpha-D-mannopyranoside

HRID 74832Notes

Reaction equation

HRID 74832 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1[O:24][C@H:25]1[C@H:30]([O:31][C:32](=[O:34])[CH3:33])[C@@H:29]([CH2:35][O:36][C:37](=[O:39])[CH3:38])[O:28][C@H:27]([O:40][C@H:41]2[C@H:46]([O:47][C:48](=[O:50])[CH3:49])[C@@H:45]([CH2:51][O:52][C:53](=[O:55])[CH3:54])[O:44][C@H:43]([O:56][C@H:57]3[C@H:62]([O:63][C:64](=[O:66])[CH3:65])[C@@H:61]([CH2:67][O:68][C:69](=[O:71])[CH3:70])[O:60][C@H:59]([O:72][C@H:73]4[C@@H:94]([O:95][C:96](=[O:98])[CH3:97])[C@H:93]([O:99][C:100](=[O:102])[CH3:101])[C@@H:92]([CH2:103][O:104][C:105](=[O:107])[CH3:106])[O:91][C@@H:74]4[O:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][CH2:85][CH2:86][CH2:87][N:88]=[N+:89]=[N-:90])[C@H:58]3[O:108][C:109](=[O:111])[CH3:110])[C@H:42]2[O:112][C:113](=[O:115])[CH3:114])[C@H:26]1[O:116][C:117](=[O:119])[CH3:118])(=[O:3])[CH3:2].[C:120]1([C:126]#[CH:127])[CH:125]=[CH:124][CH:123]=[CH:122][CH:121]=1.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>S([O-])([O-])(=O)=O.[Cu+2].C(O)(C)(C)C>[C:1]([O:4][C@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1[O:24][C@H:25]1[C@H:30]([O:31][C:32](=[O:34])[CH3:33])[C@@H:29]([CH2:35][O:36][C:37](=[O:39])[CH3:38])[O:28][C@H:27]([O:40][C@H:41]2[C@H:46]([O:47][C:48](=[O:50])[CH3:49])[C@@H:45]([CH2:51][O:52][C:53](=[O:55])[CH3:54])[O:44][C@H:43]([O:56][C@H:57]3[C@H:62]([O:63][C:64](=[O:66])[CH3:65])[C@@H:61]([CH2:67][O:68][C:69](=[O:71])[CH3:70])[O:60][C@H:59]([O:72][C@H:73]4[C@@H:94]([O:95][C:96](=[O:98])[CH3:97])[C@H:93]([O:99][C:100](=[O:102])[CH3:101])[C@@H:92]([CH2:103][O:104][C:105](=[O:107])[CH3:106])[O:91][C@@H:74]4[O:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][CH2:85][CH2:86][CH2:87][N:88]4[CH:127]=[C:126]([C:120]5[CH:125]=[CH:124][CH:123]=[CH:122][CH:121]=5)[N:90]=[N:89]4)[C@H:58]3[O:108][C:109](=[O:111])[CH3:110])[C@H:42]2[O:112][C:113](=[O:115])[CH3:114])[C@H:26]1[O:116][C:117](=[O:119])[CH3:118])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 10821PhenylacetyleneHCID 23667548Sodium AscorbateHCID 4510504612-Azidododecyl 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->2)-3,4,6-tri-O-acetyl-alpha-D-mannopyranoside

Product 1

HCID 4510442012-(4-Phenyl-[1,2,3]triazol-1-yl)dodecyl 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl-(1->2)-3,4,6-tri-O-acetyl-alpha-D-mannopyranosideYield 62%

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 6386tert-ButanolSolvent

Procedure

In a 1 mL HPLC sample vial was loaded the azide 5 (71 mg, 41.5 μmol), t-butanol (100 μL, 0.4 M), phenylacetylene (83 μmol, 2 eq), copper sulfate solution (0.3 M in water, 14 μL, 4.2 μmol, 10 mol %) and sodium ascorbate solution (1M in water, 12.4 μL, 12.4 μmol, 30 mol %) in that order. The mixture was stirred at room temperature for 2 days. The mixture was then evaporated onto silica gel and purified by flash column chromatography (1×18 cm, gradient elution with hexane-ethyl acetate 6:1, 4:1, 2:1, 1:1, 1:2 to 1:3) to give the phenyltriazole 6 as a colourless gum (46.3 mg, 62%). 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, 2H, J=7.2, Ph), 7.75 (s, 1H, triazole), 7.41 (t, 2H, J=7.2, Ph), 7.31 (t, 1H, J=7.2, Ph), 5.30-5.15 (m, 8H), 5.03-4.87 (m, 8H), 4.38 (t, 2H, J=7.2, NCH2), 4.29-3.77 (m, 19H), 3.64 (dt, 1H, J=9.6, 6.8, OCH2), 3.40 (dt, 1H, J=9.6, 6.8, OCH2), 2.17, 2.16, 2.16, 2.13, 2.11, 2.11, 2.11, 2.10, 2.09, 2.07, 2.05, 2.05, 2.02, 2.00, 1.96 (each s, total 48H, 16×Ac), 1.93 (m, 2H, CH2), 1.57 (m, 2H, CH2), 1.34-1.24 (m, 16H, 8×CH2).

Workup

  1. customThe mixture was then evaporated onto silica gel
  2. custompurified by flash column chromatography (1×18 cm, gradient elution with hexane-ethyl acetate 6:1, 4:1, 2:1, 1:1, 1:2 to 1:3)

Sources & evidence

ORD record
ord-9a361ae4abcf4c10bc2bee54b713b7a6
Source dataset
uspto-grants-2014_09
Patent number
US08828952B2

Reaction notes

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