C([Si](C)(C)[O:6][CH:7]1[CH2:12][C@@H:11]2[CH2:13][C@H:8]1[CH2:9][C@:10]2([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:14]#[N:15])(C)(C)C.[CH2:24]([Mg]Br)[CH3:25].C(O)C.[BH4-].[Na+]>C1(C)C=CC=CC=1.C1COCC1>[NH2:15][CH:14]([C@@:10]1([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH2:9][C@@H:8]2[CH2:13][C@H:11]1[CH2:12][CH:7]2[OH:6])[CH2:24][CH3:25]930 mg (2.8 mmol) of (1S,2S,4S)-5-(tert-Butyl-dimethyl-silanyloxy)-2-phenyl-bicyclo[2.2.1]heptane-2-carbonitrile (88) were dissolved in 10 mL of anhydrous toluene. Afterwards, 5.7 mL of a 1M solution of ethylmagnesium bromide in THF was added and the mixture was heated under reflux for 12 h. The mixture was then treated with 3 mL ethanol and evaporated. The residue was dissolved in 20 mL of ethanol and 215 mg (5.7 mmol) of NaBH4 was added. The mixture was stirred at ambient temperature for 3 h and then evaporated. The residue was dissolved using 100 mL of water, the pH adjusted to 3 using aqueous HCl-solution to remove excess NaBH4 and then adjusted to pH=12 using saturated aqueous Na2CO3-solution. The mixture was extracted three times using 30 mL of t-butylmethylether each. Afterwards, the organic layer was extracted twice using 20 mL of a 1N aqueous HCl-solution each, the aqueous layer was adjusted to pH>11 using saturated aqueous Na2CO3-solution and extracted three times using 30 mL t-butylmethylether each. The organic layer was dried using MgSO4 and evaporated yielding 200 mg of the desired product 89, used without further purification. Rt=0.58 min (Method 18).
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