Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: Construction of stereogenic quaternary centers

Angewandte Chemie - International Edition

Volumn 44, Issue 9, 2005, Pages 1376-1378

  D'Augustin, Magali ^a   Palais, Laëticia ^a   Alexakis, Alexandre ^a  

^a UNIVERSITY OF GENEVA   (Switzerland)

Author keywords

Aluminum; Asymmetric catalysis; Conjugate addition; Enones; Phosphoramidite ligands

Indexed keywords

AROMATIC COMPOUNDS; CATALYSIS; COPPER; SALTS;

CATALYTIC AMOUNTS; CYCLOHEXENONES; PHOSPHORAMIDITE LIGANDS; TRIETHYLALUMINUM;

KETONES;

2 CYCLOHEXENONE DERIVATIVE; ALUMINUM DERIVATIVE; COPPER; PHOSPHORAMIDOUS ACID; TRIETHYLALUMINUM; TRIMETHYLALUMINUM; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; ASYMMETRIC CATALYSIS; CATALYST; CHEMICAL STRUCTURE; CHIRALITY; CONJUGATION; ENANTIOMER; ENANTIOSELECTIVITY; ISOMERISM; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 14844320728     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200462137     Document Type: Article

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47. Typical procedure: A flame-dried Schlenk tube was charged with CuTC (3.9 mg, 2.0 mol%) and L4 (19.8 mg, 4.0 mol%). Diethyl ether (2.0 mL) was then added and the mixture was stirred at room temperature for 30 min before being cooled to -30°C. Trimethylaluminum (1.0 mL of a 2m solution in heptane, 2.0 equiv) was added dropwise at such a rate that the temperature did not rise above -30°C, and the reaction mixture was stirred at -30°C for a further 5 min before enone 3 (124.1 mg, 1.0 mmol) in diethyl ether (0.5 mL) was added dropwise. Once the addition was complete the reaction mixture was held at -30°C overnight. The reaction was quenched at -30°C by addition of MeOH (0.5 mL) and then water. Workup followed by flash chromatography afforded the product as a colorless oil (109.4 mg, 78% yield). Chiral GC analysis (Lipodex E) showed an enantiomeric excess of 94% ee.