1-Ethynylnaphthalene → 12-(4-Naphthalen-1-yl-[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 74833Notes

Reaction equation

HRID 74833 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]([C:122]1[C:131]2[C:126](=[CH:127][CH:128]=[CH:129][CH:130]=2)[CH:125]=[CH:124][CH:123]=1)#[CH:121].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:121]=[C:120]([C:122]5[C:131]6[C:126](=[CH:127][CH:128]=[CH:129][CH:130]=6)[CH:125]=[CH:124][CH:123]=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 1233571-EthynylnaphthaleneHCID 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 4510411812-(4-Naphthalen-1-yl-[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 26%

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 6386tert-ButanolSolvent

Procedure

In a 1 mL HPLC sample vial was loaded the azide 5 (86 mg, 50.3 μmol), t-butanol (100 μL, 0.4 M), 1-ethynylnaphthalene (83 μmol, 2 eq), copper sulfate solution (0.3 M in water, 14 μL, 4.2 μmol, 10 mol %) and sodium ascorbate solution (1 M in water, 12.4 μL, 12.4 μmol, 30 mol %) in that order. The mixture was stirred at room temperature for 11 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 naphthyltriazole 9 as a colourless gum (24.2 mg, 26%). 1H NMR (CDCl3, 400 MHz) δ 8.38-8.33 (m, 1H), 7.92-7.86 (m, 2H), 7.80 (s, 1H, triazole-CH), 7.72 (dd, 1H, J=7.3, 1.5), 7.54-7.48 (m, 3H), 5.31-5.15 (m, 8H), 5.03-4.87 (m, 8H), 4.47 (t, 2H, J=7.3, N—CH2), 4.30-3.77 (m, 19H), 3.64 (dt, 1H, J=9.7, 6.8, OCH2), 3.40 (dt, 1H, J=9.7, 6.8, OCH2), 2.17, 2.16, 2.16, 2.13, 2.12, 2.11, 2.11, 2.10, 2.09, 2.07, 2.06, 2.05, 2.02, 2.00, 1.97, 1.57 (15 s, each 3H, except 2.100 (6H), 16×Ac), 2.07-1.95 (m, overlapped with Ac singlets, 2H, CH2), 1.57 (m, 1H, CH2), 1.42-1.23 (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-656719492efc4a09a5ea0a24e13018c3
Source dataset
uspto-grants-2014_09
Patent number
US08828952B2

Reaction notes

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