Catalytic asymmetric synthesis of allylic aryl ethers

Organic Letters

Volumn 9, Issue 5, 2007, Pages 911-913

  Kirsch, Stefan F ^a,b   Overman, Larry E ^a   White, Nicole S ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b TECHNICAL UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33947181428     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol070110b     Document Type: Article

References (36)

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14. A number of useful catalytic asymmetric methods for the synthesis of allylic alkyl ethers have been developed also; representative examples include: (a) Lyothier, I.; Defieber, C.; Carreira, E. M. Angew. Chem., Int. Ed. 2006, 45, 6204-6207.
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21. 8
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24. For a discussion of various ways to prepare allylic trichloroacetimidates, see: Overman, L. E.; Carpenter, N. E. The Allylic Trichloroacetimidate Rearrangement. In Organic Reactions; Overman, L. E., Ed.; Wiley: Hoboken, NJ, 2005; Vol. 66, pp 1-107.
25. 2, 36 h). Enantiomeric excess was determined by HPLC analysis; see Supporting Information for details.
26. 2, has the Sp,R absolute configuration.
27. The convention of Schlögl is used: Schlögl, K. Top. Stereochem. 1967, 1, 39-91.
28. Reaction conditions: 3 equiv of phenol, 38°C, [4a] = 1 M, 36 h; all reactions provided (R)-5a in high enantiopurity (92-94% ee).
29. 2 provided ent-5a in 86% yield and 92% enantiopurity.
30. The enantiopurity of 5j decreased to 38% ee when 3 equiv of 3-nitrophenol was employed.
31. 2 at 38°C for 72 h, the corresponding allylic ether 5a was obtained in low yields. These experiments and NMR studies of catalyst compositions show that these 2-substituted phenols deactivate the catalyst.
32. 17
33. (a) Landor, S. R.; Miller, B. J.; Tatchell, A. R. J. Chem. Soc. (C) 1971, 2339-2341.
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35. The limits of detection of the branched products by this method were 0.01%.
36. Studies to optimize this transformation are underway.