Diisopropylamine → (6RS,7SR)-7-[(SR)-1-(tert-Butyldimethylsilyl)-1-hydroxyethyl]-2,2-dimethyl-1-azabicyclo[4.2.0]octan-8-one

HRID 1194994노트

반응식

HRID 1194994 반응식
[CH3:1][C:2]1([CH3:11])[CH2:9][CH2:8][CH2:7][CH:6]2[N:3]1[C:4](=[O:10])[CH2:5]2.C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.C([Li])CCC.[Si:32]([C:39]([CH3:41])=[O:40])([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33].[Cl-].[NH4+]>O1CCCC1.CCCCCC>[Si:32]([C:39]([CH:5]1[C:4](=[O:10])[N:3]2[CH:6]1[CH2:7][CH2:8][CH2:9][C:2]2([CH3:11])[CH3:1])([OH:40])[CH3:41])([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33]

참가 물질

9

반응물 6

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 11367157HCID 11367157, 화합물HCID 15614335(6RS)-2,2-dimethyl-1-azabicyclo[4.2.0]octan-8-oneHCID 178418339Butyllithium

생성물 1

HCID 15614336(6RS,7SR)-7-[(SR)-1-(tert-Butyldimethylsilyl)-1-hydroxyethyl]-2,2-dimethyl-1-azabicyclo[4.2.0]octan-8-one

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

실험 절차

A solution of (6RS)-2,2-dimethyl-1-azabicyclo[4.2.0]octan-8-one (104 mg, 0.671 mmol) in 1 ml of tetrahydrofuran is added to a solution of lithium diisopropylamide (0.705 mmol made from 99 μl of diisopropylamine and 320 ml of a 2.2M solution of n-butyllithium in n-hexane) in 4 ml of tetrahydrofuran at -78° C. The enolate solution is aged for a period of 12 minutes and then methyl tert-butyldimethylsilyl ketone is added and stirring is continued for a period of 19 minutes. The reaction mixture is poured into a separatory funnel containing 5 ml of a saturated aqueous solution of ammonium chloride and shaken. The mixture is extracted with 10 ml of diethyl ether and the ether solution is dried over magnesium sulfate. Removal of the solvents in vacuo gives 206 mg of a colorless oil. Plate-layer chromatography of this material on silica gel (1:1 ethyl acetate/cyclohexane) provides 171 mg (81%) of (6RS,7SR)-7-[(SR)-1-(tert-butyldimethylsilyl)-1-hydroxyethyl]-2,2-dimethyl-1-azabicycylo[4.2.0]octan-8-one (Rf 0.41-0.65): m.p. 60°-3° C. (recrystallized from pentane); ir (CH2Cl2) cm-1 3608 (br), 1739; nmr (CDCl3) δ0.03 (s, 3), 0.06 (s, 3), 1.00 (s, 9), 1.34 (s, 3), 1.42 (s, 3), 1.76 (s, 3), 1.85 (m, 2), 3.24 (d, 1, J=1.9 Hz), 3.40 (ddd, 1, J=1.9, 4.9 and 10.6 Hz), 3.88 (m, 2); ms m/e 314 (M+1)+, 298, 198; anal. (C16H31NO3Si)C, H, N.

후처리

  1. customat -78° C
  2. additionThe reaction mixture is poured into a separatory funnel
  3. stirringshaken
  4. extractionThe mixture is extracted with 10 ml of diethyl ether
  5. dry with materialthe ether solution is dried over magnesium sulfate
  6. customRemoval of the solvents in vacuo

출처 및 근거

ORD 기록
ord-880e2961f8014e099018c731a0ba7344
출처 데이터셋
uspto-grants-1989_03
특허 번호
US04816578

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