Lithium diisopropylamide → HCID 88609167, compound

HRID 2166296Notes

Reaction equation

HRID 2166296 reaction equation
C([N-]C(C)C)(C)C.[Li+].[F:9][CH:10]([P:12](=[O:19])([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15])[F:11].C(P(C([Li])(F)F)(CC)=O)C.[C:30]1([CH2:36][O:37][C@@H:38]([C@@H:42]([C@@H:51]([CH2:53][O:54][CH2:55][C:56]2[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=2)O)[O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C:39]([OH:41])=[O:40])[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>O1CCCC1.C(O)(=O)C>[CH2:17]([O:16][P:12]([O:13][CH2:14][CH3:15])([C:10]([F:11])([F:9])[C:39]1([O:41][C@H:51]([CH2:53][O:54][CH2:55][C:56]2[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=2)[C@@H:42]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:38]1[O:37][CH2:36][C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)[OH:40])=[O:19])[CH3:18]

Participants

7

Reactant 4

HCID 2724682Lithium diisopropylamideHCID 2758305Phosphonic acid, (difluoromethyl)-, diethyl esterHCID 54253136HCID 54253136, compoundHCID 178506810HCID 178506810, compound

Product 1

HCID 88609167HCID 88609167, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

In accordance with M. Obayashi et al., Tetrahedron Letters, 2323-2326 (1982), to a solution of lithium diisopropylamide (prepared from 17.2 ml of 1.6M n-butyllithium in hexane and 2.78 g of diisopropylamine in 50 ml of tetrahydrofuran) at -78° C., was added a solution of 4.70 g of diethyl difluoromethylphosphonate in 10 ml of tetrahydrofuran during 10 minutes, thereby forming (diethylphosphinyl)difluoromethyllithium. After 15 minutes, a solution of 2,3,5-tris-O-(phenylmethyl)-D-arabinonic acid, gamma-lactone [Y. Rabinsohn & H. G. Fletcher, J. Org. Chem., 32, 3452-3457 minutes. The solution was stirred at -78° C. for 1 hour, warmed to -15° C. during 15 minutes, recooled to -78° C. and treated with 3 ml of glacial acetic acid. The mixture was partitioned with ether and water. The ether layer was washed with water, sodium bicarbonate solution and brine, dried and concentrated. The residue was subjected to column chromatography on silica gel (heptane-ethyl acetate) giving the desired compound as an oil; CMR δ 100.7 (major anomer) and 104.0 (minor anomer); (multiplets, anomeric carbon atom).

Workup

  1. custom32, 3452-3457 minutes
  2. temperaturewarmed to -15° C. during 15 minutes
  3. customrecooled to -78° C.
  4. customThe mixture was partitioned with ether and water
  5. washThe ether layer was washed with water, sodium bicarbonate solution and brine
  6. customdried
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-8d99ee938ff34febabf594932d0a254d
Source dataset
uspto-grants-1990_07
Patent number
US04943629

Reaction notes

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