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R(E,Z) = 38.0 min; baseline separation with 200 mg/injection.
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R(E,Z) = 38.0 min; baseline separation with 200 mg/injection.
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For applications of the CAGC in total synthesis, see: d
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The relative and absolute configuration was assigned based on the established stereochemical course of the CAGC. The enantiomeric excess was determined by Mosher ester 1H NMR analysis. To synthesize Mosher esters, aldehydes 14 or 18 were reduced to the corresponding primary alcohols with NaBH4 in methanol, followed by esterification with Mosher's acid.17
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α-Keto Ester 6: To a solution of [Cu{(S,S)-tert- Bu-Box}(H2O)2](SbF6)2 (12; 81 mg, 0.094 mmol, 8 mol, in CH2Cl2 (3 mL, 3 mL/mmol 6) was added (Z,Z)-7 (0.5 g, 1.18 mmol, 1 equiv) in CH2Cl2 (3 mL, 3 mL/mmol 6) at r.t. The solution was stirred for 24 h, then the solvent was evaporated and the residue filtered through a short plug of silica gel (cyclohexane-EtOAc, 1:1, Evaporation of the solvent and purification by flash chromatography (cyclohexane-EtOAc, 50:1→20:1) furnished 6 (478 mg, 96, as a clear oil. R f, 0.34 (cyclohexane-EtOAc, 10:1, 1H NMR (CDCl 3, 400 MHz, δ, 7.62-7.64 (m, 4 H, 7.36-7.45 (m, 6 H, 5.81 (ddd, J, 8.7, 10.3, 17.3 Hz, 1 H, 5.00-5.08 (m, 2 H, 3.80 (s, 3 H, 3.65-3.67 (m, 2 H, 3.56-3.63 (m, 1 H, 2.67-2.73 (m, 1 H, 1.11 d, J, 6.8 Hz, 3
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