Lithium Hexamethyldisilazide → HCID 10424859, compound

HRID 861281Notes

Reaction equation

HRID 861281 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[P:11]([O:19][CH:20]([O:23][C:24](=[O:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[CH2:21]I)([O:16][CH2:17][CH3:18])([O:13][CH2:14][CH3:15])=[O:12].CCOCC.C(Cl)Cl>C1(C)C=CC=CC=1.CCOCC>[P:11]([O:19][C:20]([O:23][C:24](=[O:31])[C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)=[CH2:21])([O:16][CH2:17][CH3:18])([O:13][CH2:14][CH3:15])=[O:12]

Participants

6

Reactant 3

HCID 2733832Lithium HexamethyldisilazideHCID 11732693HCID 11732693, compoundHCID 21881112Ethyl ether methylene chloride

Product 1

HCID 10424859HCID 10424859, compoundYield 44.8%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

Lithium bis(trimethylsilyl)amide (1.0M solution in hexanes, 1.752 ml, 1.752 mmol) was added dropwise to a solution of the iodobenzoate XIX (0.250 g, 0.584 mmol) in toluene (50 ml) at -78° C. and allowed to stir for 30 min. The reaction mixture was then diluted with Et2O (150 ml), washed with saturated aqueous NaHSO4 (3×25 ml), 10% aqueous sodium phosphate buffer (pH=7) (1×25 ml), dried (MgSO4), and concentrated in vacuo. Flash chromatography (5% Et2O/CH2Cl2) afforded the geminal benzoate XX (78.6 mg, 44.8% yield) as a clear, colorless oil: 1H NMR (CDCl3, 400 MHz) d 8.10 (d, 2 H, J=7.5 Hz, C7 - and C8 -H), 7.63 (t, 1 H, J=7.5 Hz, C9 - and C8 -H, C9 - and C7 -H), 7.48 (t, 2 H, J=7.5 Hz, C8 - and C7 -H, C8 - and C9 -H), 4.78 (dd, 1 H, J=3.5 Hz, C2b - and C2a -H; J=2.2 Hz, C2b -H and P), 4.54 (dd, 1 H, J=3.5 Hz, C2a - and C2b -H; J=1.1 Hz, C2a -H and P), 4.23 (m, 4 H), 1.34 (dt, 6 H, J=7.0 Hz, C4- and C3 -H; J=1.1 Hz, C4 -H and P); 13C NMR (CDCl3, 100 MHz) d 164.0, 149.3 (d, J=5 Hz), 134.9, 131.1, 129.4, 128.9, 86.1 (d, J=3 Hz), 65.4 (d, J=6 Hz), 16.1 (d, J=7 Hz); 31P NMR (H3PO4, 146 MHz) d -7.19; IR (NaCl solution cell, CDCl3) 2988, 2932, 1752, 1672, 1277, 1204, 1177, 1063, 1034, 999, 916, 706; LRMS, m/e (relative intensity) 301.1 (15.8), 259.0 (55.9), 155.0 (6.7), 106.0 (22.1), 105.0 (100.0), 81.0 (7.3), 77.0 (37.7), 51.0 (10.3); HRMS for C13H17O6P [M+H+ ], calcd. 301.0763; found, 301.0843.

Workup

  1. washwashed with saturated aqueous NaHSO4 (3×25 ml), 10% aqueous sodium phosphate buffer (pH=7) (1×25 ml)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-4e0ec2ee678c45ca9c213719b88a37c2
Source dataset
uspto-grants-1998_02
Patent number
US05714361

Reaction notes

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