Triethylamine → 2-tert-Butyldimethylsilyloxy-9H-fluoren-9-ylideneadamantane

HRID 1770351Notes

Reaction equation

HRID 1770351 reaction equation
[Si:1]([O:8][C:9]1[CH:21]=[CH:20][C:19]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12](=O)[C:11]=2[CH:10]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH:23]12[CH2:32]C3C[CH:29]([CH2:31][CH:25]([CH2:26]3)[C:24]1=O)[CH2:30]2.[H-].[H-].[H-].[H-].[Li+].[Al+3].C(N([CH2:45][CH3:46])CC)C>C1COCC1>[Si:1]([O:8][C:9]1[CH:21]=[CH:20][C:19]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12](=[C:26]3[CH:25]4[CH2:24][CH:23]5[CH2:30][CH:29]([CH2:45][CH:46]3[CH2:32]5)[CH2:31]4)[C:11]=2[CH:10]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 146455782-tert-Butyldimethylsilyloxy-9H-fluoren-9-oneHCID 21226445Aluminium lithium hydride

Product 1

HCID 146455692-tert-Butyldimethylsilyloxy-9H-fluoren-9-ylideneadamantane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 2-tert-butyldimethylsilyloxy-9H-fluoren-9-one (0.689 g, 2.2 mmol) and adamantanone (0.66 g, 4.4 mmol) in 30 mL of dry THF was added dropwise over a period of 7 h to a refluxing mixture of TiCl3 (6.8 g, 44 mmol), LAH (0.8 g, 21 mmol) and triethylamine (3 mL) in 80 mL of dry THF. The reaction was refluxed for an additional 12 h. The alkene was then isolated and purified as described above for 1a to give 0.65 g (68%) of 3b: mp 102°-105° C.; 1H NMR (CDCl3) delta 7.832-6.785 (m, 7H), 4.038 (s, 1H), 3.972 (s, 1H), 2.095-1.990 (m, 12H), 1.006 (s, 9H), 0.225 (s, 6H); 13C NMR (CDCl3) delta 159.91, 155.06, 140.64, 139.89, 139.13, 133.61, 126.29, 125.65, 124.31, 119.87, 118.71, 118.43, 116.35, 39.49, 39.40, 36.90, 35.99, 35.90, 27.83, 25.81, 25.73, 18.35, -4.33. ##STR33##

Workup

  1. temperatureThe reaction was refluxed for an additional 12 h

Sources & evidence

ORD record
ord-3a83dabb9de14200a0a69df749f6c4df
Source dataset
uspto-grants-1995_01
Patent number
US05386017

Reaction notes

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