Lithium Hexamethyldisilazide → N,N-Bis(trimethylsilyl)-(1R)-1-[(3aS,4S,6S,7aR)-hexahydro-3a,5,5-trimethyl-4,6-methano-1,3,2-benzodioxaborol-2-yl]-3-methylbutylamine

HRID 556292Notes

Reaction equation

HRID 556292 reaction equation
[CH3:1][Si:2]([N-:5][Si:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])[CH3:3].[Li+].Cl[C@@H:12]([B:17]1[O:21][C@@H:20]2[CH2:22][C@@H:23]3[CH2:26][C@H:25]([C@:19]2([CH3:29])[O:18]1)[C:24]3([CH3:28])[CH3:27])[CH2:13][CH:14]([CH3:16])[CH3:15]>O1CCCC1>[CH3:1][Si:2]([CH3:4])([CH3:3])[N:5]([C@H:12]([B:17]1[O:21][C@@H:20]2[CH2:22][C@@H:23]3[CH2:26][C@H:25]([C@:19]2([CH3:29])[O:18]1)[C:24]3([CH3:27])[CH3:28])[CH2:13][CH:14]([CH3:16])[CH3:15])[Si:6]([CH3:9])([CH3:8])[CH3:7]

Participants

4

Reactant 2

HCID 2733832Lithium HexamethyldisilazideHCID 21103224(3aS,4S,6S,7aR)-2-[(1S)-1-chloro-3-methylbutyl]-3a,5,5-trimethylhexahydro-4,6-methano-1,3,2-benzodioxaborole

Product 1

HCID 21103230N,N-Bis(trimethylsilyl)-(1R)-1-[(3aS,4S,6S,7aR)-hexahydro-3a,5,5-trimethyl-4,6-methano-1,3,2-benzodioxaborol-2-yl]-3-methylbutylamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A 1.0 M solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran (189 ml, 0.189 mol) was added, over 30 minutes, to a solution of crude 2-[(1S)-1-chloro-3-methylbutyl]-(3aS,4S,6S,7aR)-hexahydro-3a,5,5-trimethyl-4,6-methano-1,3,2-benzodioxaborole of Step 2 (59.0 g, 91% purity, 0.189 mol) in tetrahydrofuran (580 ml) while cooling at −78° C. The reaction mixture was allowed to slowly warm to room temperature overnight. The solvent was removed by rotary evaporation and the residue taken up with dry hexane (800 ml). The resulting suspension was stirred at room temperature for 2 hours, then the solid was removed by filtration on a celite cake, which was washed with dry hexane (3×100 ml). The filtrate was concentrated giving a satisfactorily pure product as a brown oil (79 g) in practically quantitative yield. The product was used for the subsequent step without further purification.

Workup

  1. temperatureto slowly warm to room temperature overnight
  2. customThe solvent was removed by rotary evaporation
  3. customthe solid was removed by filtration on a celite cake, which
  4. washwas washed with dry hexane (3×100 ml)
  5. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-b2423b5ae7f443d48e7d97d57b083a30
Source dataset
uspto-grants-2011_11
Patent number
US08058262B2

Reaction notes

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