Enantioselective synthesis of quaternary stereocenters via a catalytic asymmetric stetter reaction

Journal of the American Chemical Society

Volumn 126, Issue 29, 2004, Pages 8876-8877

  Kerr, Mark S ^a   Rovis, Tomislav ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONIC ACID DERIVATIVE; ETHER DERIVATIVE; KETONE; SULFIDE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; ENANTIOSELECTIVITY; REACTION ANALYSIS; STEREOCHEMISTRY; STETTER REACTION; STRUCTURE ANALYSIS;

EID: 3242812738     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja047644h     Document Type: Article

References (25)

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15. Intramolecular Stetter: (c) Ciganek, E. Synthesis 1995, 1311-1314.
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17. (e) Enders, D.; Balensiefer, T. Acc. Chem. Res. 2004, published online March 25, http://dx.doi.org/10.1021/ar030050j.
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21. This product is prone to racemization, presumably through a phenoxide elimination/conjugate addition sequence. Stirring a toluene solution of 6 of 98% ee for 24 h with DBU results in quantitative recovery of 6 of 66% ee.
22. Catalyst screening was also performed under these conditions. Triazolium chloride 31 provided product 6 in quantitative yield, although with a modest 86% ee. Catalyst 5b gave only trace amounts of product.
23. 3N in i-PrOH for one week provides a 78% yield of 6 with 83% ee. Toluene provides consistently high yields and enantioselectivity.
24. Triethylamine provided the product in 90% yield and 88% ee.
25. The apparent reversal in stereoinduction between the aliphatic and aromatic series is presently under investigation.