A novel, highly enantioselective ketone alkynylation reaction mediated by chiral zinc aminoalkoxides

Angewandte Chemie - International Edition

Volumn 38, Issue 5, 1999, Pages 711-713

  Tan, Lushi ^a   Chen, Cheng Yi ^a   Tillyer, Richard D ^a   Grabowski, Edward J J ^a   Reider, Paul J ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

Alkynylations; Amino alcohols; Ketones; Nucleophilic additions; Zinc

Indexed keywords

AMINOALCOHOL; ANILINE DERIVATIVE; EFAVIRENZ; KETONE; NOREPHEDRINE; ZINC DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHIRALITY; CONFORMATIONAL TRANSITION; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY; STEREOSPECIFICITY;

EID: 0033105506     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990301)38:5<711::AID-ANIE711>3.0.CO;2-W     Document Type: Article

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20. 13C NMR studies of the solution showed a very complicated system. The observed chiral amplification supported the formation of dimer or higher order aggregates: the enantiomeric excess of the product was 97.5, 94.4, and 79.6%, respectively, when (1R,2S)-N-pyrrolidinylnorephedrine with 100, 80, and 50% ee was used for the reaction at room temperature.
21. The enantiomeric excess was determined by HPLC assay on a chiralcel-AD column (hexane/isopropyl alcohol, 3/1)
22. Trifluoroethanol is preferred to neopentyl alcohol because it gives a faster reaction.
23. 3 (%): C 47.88, H 3.71, N 4.29; found: C 48.14, H 3.39, N 4.15.
24. 3 (%): C 53.80, H 3.77, N 4.72; found: C 53.67, H 3.80, N 4.67.
25. 2 (%): C 56.87, H 3.27, N 3.49; found: C 56.99, H 2.98, N 3.42.