Trimethylsilyl triflate → HCID 86634646, compound

HRID 1965993Notes

Reaction equation

HRID 1965993 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C@@H:9]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@@H:8]([CH2:27][O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[O:7][C@H:6]1[O:36][C@@H:37]1[C@@H:66]([CH2:67][O:68][CH2:69][C:70]2[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=2)[O:65][C@H:40]([O:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][N:47]([CH2:58][C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[C:48]([O:50][CH2:51][C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)=[O:49])[C@H:39]([N:76]=[N+:77]=[N-:78])[C@H:38]1[OH:79])(=[O:3])[CH3:2].[CH3:80][O:81][C@@H:82]1[C@@H:91]([O:92][CH2:93][C:94]2[CH:99]=[CH:98][CH:97]=[CH:96][CH:95]=2)[C@@H:90]([OH:100])[C@@H:89]([CH3:101])[O:88][C@@H:83]1OCC=C.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>C1(C)C=CC=CC=1>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C@@H:9]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C@@H:8]([CH2:27][O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[O:7][C@H:6]1[O:36][C@@H:37]1[C@@H:66]([CH2:67][O:68][CH2:69][C:70]2[CH:71]=[CH:72][CH:73]=[CH:74][CH:75]=2)[O:65][C@H:40]([O:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][N:47]([CH2:58][C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[C:48]([O:50][CH2:51][C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)=[O:49])[C@H:39]([N:76]=[N+:77]=[N-:78])[C@H:38]1[O:79][C@H:83]1[O:88][C@H:89]([CH2:101][O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C@H:90]([O:100][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C@H:91]([O:92][CH2:93][C:94]2[CH:95]=[CH:96][CH:97]=[CH:98][CH:99]=2)[C@H:82]1[O:81][CH2:80][C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 67419528HCID 67419528, compoundHCID 86634644HCID 86634644, compound

Product 1

HCID 86634646HCID 86634646, compoundYield 115.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-50 °C

Procedure

A mixture of 6 (0.098 g, 0.14 mmol) and 7 (0.1 g, 0.092 mmol) was co-evaporated with dry toluene (3×7 mL) and dried in vacuo for 4 h. The dried compounds were dissolved in a mixture of diethyl ether and dichloromethane (7 mL, 5/1, v/v) and 4 Å MS (0.28 g) was added. The mixture was stirred under an atmosphere of argon for 30 min and then cooled (−50° C.). TMSOTf (2.5 μL, 0.014 mmol) was added and the reaction mixture was allowed to reach 0° C. gradually over a period of 1 h. The reaction was then quenched by the addition of pyridine (20 μL), diluted with dichloromethane (7 mL), and filtered through celite. The filtrate was washed with aqueous NaHCO3 (sat., 7 mL) and the organic layer was dried (MgSO4) and filtered, and the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1, v/v) to give 8 (0.13 g, 86%) as a clear oil. Rf=0.35 (hexane/ethyl acetate, 4/1, v/v). [α]25D=+59.4 (c 1.72, CHCl3); 1H (500 MHz, CDCl3): δ 7.35-7.14 (m, 50H, aromatic), 5.76 (d, 1H, J1,2=3.0 Hz, H-1″), 5.28 (t, 1H, J2,3=9.5 Hz, J1,2=8.0 Hz, H-2′), 5.18-5.16 (bd, 2H, CH2-LCbz), 4.89-4.84 (m, 2H, CHH, OBn, H-1), 4.80-4.71 (dd, 3H, 3×CHH, OBn), 4.68-4.62 (m, 5H, 3×CHH, OBn, H-1′), 4.54-4.39 (m, 8H, 3×CH2, OBn, CH2-LBn), 4.35-4.24 (m, 3H, CHH, OBn, H-3, H-5″), 4.18-4.04 (m, 5H, CH2, OBn, H-4, H-3″, H-2″), 3.99 (bs, 1H, H-4″), 3.84 (bs, 1H, H-4′), 3.80-3.74 (m, 2H, H-6a, H-5), 3.65-3.51 (m, 4H, H-6b, H-6′a, H-6″a,b), 3.44-3.30 (m, 5H, CH2-L, H-2, H-5′, H-6′), 3.23-3.17 (m, 3H, CH2-L, H-3′), 1.90 (s, 3H, COCH3), 1.51-1.46 (m, 4H, 2×CH2-L), 1.26-1.20 (m, 2H, CH2-L). 13C (75 MHz, CDCl3): δ 169.26, 139.36, 139.18, 138.70, 138.28, 138.24, 138.15, 138.12, 137.08, 128.77, 128.68, 128.63, 128.59, 128.48, 128.42, 128.37, 128.36, 128.34, 128.29, 128.05, 127.95, 127.93, 127.82, 127.80, 127.70, 127.60, 127.53, 127.41, 127.35, 127.30, 99.64 (C-1′), 97.63 (C-1), 96.22 (C-1″), 81.04, 78.64, 76.84, 76.51, 76.28, 75.54, 74.92, 74.68, 73.68, 73.58, 73.45, 73.23, 72.51, 72.40, 72.19, 71.96, 70.49, 70.16, 69.17, 68.76, 68.33, 68.22, 67.37, 62.64, 53.66, 29.13, 23.41, 21.26. HR-MALDI-TOF/MS (m/z) calcd for C96H104N4O18[M+Na]+: 1623.7246. found: 1623.7242.

Workup

  1. customdried in vacuo for 4 h
  2. dissolutionThe dried compounds were dissolved in a mixture of diethyl ether and dichloromethane (7 mL, 5/1
  3. additionv/v) and 4 Å MS (0.28 g) was added
  4. waitto reach 0° C. gradually over a period of 1 h
  5. customThe reaction was then quenched by the addition of pyridine (20 μL)
  6. additiondiluted with dichloromethane (7 mL)
  7. filtrationfiltered through celite
  8. washThe filtrate was washed with aqueous NaHCO3 (sat., 7 mL)
  9. dry with materialthe organic layer was dried (MgSO4)
  10. filtrationfiltered
  11. concentrationthe filtrate was concentrated in vacuo
  12. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1

Sources & evidence

ORD record
ord-96b03e74aba04b7c9668d7bf877d79a8
Source dataset
uspto-grants-2013_04
Patent number
US08420607B2

Reaction notes

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