Trimethylsilyl triflate → HCID 86634645, compound

HRID 628186Notes

Reaction equation

HRID 628186 reaction equation
[N:1]([C@@H:4]1[C@@H:33]([O:34][CH2:35][C:36]2[CH:45]=[CH:44][C:43]3[C:38](=[CH:39][CH:40]=[CH:41][CH:42]=3)[CH:37]=2)[C@H:32]([OH:46])[C@@H:31]([CH2:47][O:48][CH2:49][C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[O:30][C@H:5]1[O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][N:12]([CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:13]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:14])=[N+:2]=[N-:3].[CH2:56]1[C:61](=[O:62])N(I)[C:58](=[O:59])[CH2:57]1.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>ClCCl>[C:5]([O:30][C@@H:31]1[C@@H:58]([O:59][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@@H:57]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@@H:56]([CH2:61][O:62][CH2:35][C:36]2[CH:45]=[CH:44][CH:43]=[CH:38][CH:37]=2)[O:46][C@H:32]1[O:46][C@@H:32]1[C@@H:31]([CH2:47][O:48][CH2:49][C:50]2[CH:51]=[CH:52][CH:53]=[CH:54][CH:55]=2)[O:30][C@H:5]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][N:12]([CH2:23][C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[O:14])[C@H:4]([N:1]=[N+:2]=[N-:3])[C@H:33]1[O:34][CH2:35][C:36]1[CH:45]=[CH:44][C:43]2[C:38](=[CH:39][CH:40]=[CH:41][CH:42]=2)[CH:37]=1)(=[O:6])[CH3:4]

Participants

5

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 120273N-IodosuccinimideHCID 131735342HCID 131735342, compound

Product 1

HCID 86634645HCID 86634645, compoundYield 170.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of galactosyl donor 3 (0.18 g, 0.35 mmol), glucosyl acceptor 4 (0.20 g, 0.27 mmol), and 4 Å MS (0.4 g) in dichloromethane (5 mL) was stirred at room temperature under an atmosphere of argon for 30 min. The reaction mixture was cooled (0° C.) and then NIS (78.7 mg, 0.35 mmol) and TMSOTf (7.0 μL, 0.035 mmol) were sequentially added. The reaction mixture was stirred for 10 min and then quenched with pyridine (50 μL). The reaction mixture was diluted with dichloromethane (5 mL) filtered through celite and washed with aqueous solution of Na2S2O3 (15%, 10 mL), NaHCO3 (sat., 7 mL), and water (7 mL). The organic layer was dried (MgSO4), filtered and the filtrate concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1, v/v) to give 5 (0.28 g, 87%) as a clear oil. Rf=0.35 (hexane/ethyl acetate, 4/1, v/v). [α]25D=+46.3 (c 1.05, CHCl3); 1H (500 MHz, CDCl3): δ 7.69-6.92 (m, 37H, aromatic), 5.28 (dd, 1H, J1′,2′=8.0 Hz, J2′,3′=8.5 Hz, H-2′), 5.19 (d, 1H, JHaHb=11.0 Hz, CHaHb, napthylmethyl), 5.11-5.08 (bd, 2H, CH2-LCbz), 4.86 (d, 1H, CHH, OBn), 4.74-4.72 (bd, 2H, CHaHb, napthylmethyl, H—), 4.63-4.55 (dd, 2H, CH2, OBn), 4.44-4.42 (bd, 2H, CH2-LBn), 4.37-4.31 (dd, 3H, CH2, OBn), 4.28 (d, 1H, J1′,2′=8.0 Hz, H-1′), 3.89-3.81 (m, 5H, H-4′, H-3, H-4, CH2, OBn), 3.69-3.67 (m, 1H, H-5′), 3.59-3.50 (m, 3H, H-5, H-6a, b), 3.23-3.14 (m, 6H, H-2, H-3′, H-6′a, b, 3×CHH-L), 3.04-3.02 (m, 1H, CHH-L), 1.88 (s, 3H, COCH3), 1.52-1.48 (m, 4H, 2×CH2-L), 1.27-1.18 (m, 2H, CH2-L). 13C (75 MHz, CDCl3): δ 169.55, 138.97, 138.27, 138.19, 138.05, 136.62, 133.53, 133.10, 128.77, 128.68, 128.65, 128.52, 128.47, 128.28, 128.24, 128.15, 128.10, 128.07, 127.95, 127.92, 127.82, 127.80, 127.76, 127.51, 126.51, 125.82, 101.03 (C-1′), 97.99 (C-1), 80.70, 78.01, 77.68, 77.46, 77.26, 76.83, 75.21, 74.84, 73.81, 73.54, 73.35, 72.74, 72.17, 71.89, 70.82, 68.42, 68.04, 67.80, 67.39, 63.23, 29.24, 23.52, 21.32. HR-MALDI-TOF/MS (m/z) calcd for C73H78N4O13[M+Na]+: 1241.5455; found: 1241.5457.

Workup

  1. temperatureThe reaction mixture was cooled (0° C.)
  2. stirringThe reaction mixture was stirred for 10 min
  3. customquenched with pyridine (50 μL)
  4. additionThe reaction mixture was diluted with dichloromethane (5 mL)
  5. filtrationfiltered through celite
  6. washwashed with aqueous solution of Na2S2O3 (15%, 10 mL), NaHCO3 (sat., 7 mL), and water (7 mL)
  7. dry with materialThe organic layer was dried (MgSO4)
  8. filtrationfiltered
  9. concentrationthe filtrate concentrated in vacuo
  10. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1

Sources & evidence

ORD record
ord-7835aac5e06e4db1982662c548d2c321
Source dataset
uspto-grants-2016_04
Patent number
US09310366B2

Reaction notes

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