2,6-Lutidine → 3-Benzyloxy-10-[(tert-butyldimethylsilyl)oxy)-7,8,9,10-tetrahydro-phenanthridine

HRID 260389Notes

Reaction equation

HRID 260389 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[C:21]([CH:22]=1)=[N:20][CH:19]=[C:18]1[C:13]=2[CH:14]([OH:23])[CH2:15][CH2:16][CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C(C)=CC=CC=1C.FC(F)(F)S(O[Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])(=O)=O>C(Cl)Cl>[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[C:21]([CH:22]=1)=[N:20][CH:19]=[C:18]1[C:13]=2[CH:14]([O:23][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])[CH2:15][CH2:16][CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 150383433-Benzyloxy-10-hydroxy-7,8,9,10-tetrahydrophenanthridine

Product 1

HCID 110802833-Benzyloxy-10-[(tert-butyldimethylsilyl)oxy)-7,8,9,10-tetrahydro-phenanthridineYield 98%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

To a suspension of Compound 224 (1.10 g, 3.60 mmol) in dry CH2Cl2 (10 mL) under ice-cooling was added successively 2,6-lutidine (0.59 mL, 5.07 mmol) and tert-butyldimethylsilyl trifluromethanesulfonate (0.99 mL, 4.31 mmol), the resultant homogeneous solution was then stirred at 25° C. for 30 minutes. The reaction mixture was diluted with CH2Cl2 (20 mL), washed with brine, dried over anhydrous Na2SO4, and evaporated in vacuo. The residue was purified by flash column chromatography (silica gel, ethyl ether-petroleum ether-benzene=1:2:2) to give Compound 225 (1.475 g, 98 percent): white solid; mp 123°-125° C.; Rf =0.50 (silica, 33 percent ethyl ether in benzene); IR (CHCl3) νmax 2952, 2933, 1621, 1506, 1336, 1295, 1256, 1240, 1174, 1151, 1090, 1025, 838 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.61 (s, 1 H, H6), 7.98 (d, J=9.2 Hz, 1 H, H1), 7.55-7.48 (m, 3 H, H4 and aromatic), 7.46-7.34 (m, 3 H, aromatic), 7.27 (dd, J=9.2, 2.7 Hz, 1 H, H2), 5.42 (t, J=2.6 Hz, 1 H, H10), 5.20 (s, 2 H, benzylic), 3.04-2.93 (m, 1 H, H7), 2.87-2.72 (m, 1 H, H7), 2.26-2.05 (m, 2 H, H8 or H9), 1.92-1.76 (m, 2 H, H8 or H9), 0.84 (s, 9 H, SiC(CH3)3), 0.22 (s, 6 H, Si(CH3)2); MS (FAB+) m/e (rel intensity) 420 (M+H, 100), 362 (23), 330 (3), 288 (9); HRMS for C26H34NO2Si (M+H), calcd 420.2359, found 420.2360.

Workup

  1. temperaturecooling
  2. washwashed with brine
  3. dry with materialdried over anhydrous Na2SO4
  4. customevaporated in vacuo
  5. customThe residue was purified by flash column chromatography (silica gel, ethyl ether-petroleum ether-benzene=1:2:2)

Sources & evidence

ORD record
ord-fe8e20a06ef44650947040eb7bc7ee40
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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