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DOI: 10.1055/s-0033-1340444
Enantioselective Palladium-Catalyzed Allylic Dearomatization
Publication History
Publication Date:
13 December 2013 (online)
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Significance
Chiral α-acyloxy-1-arylethanols are an important class of useful structural motifs (R. S. Bhondwea et al. Bioorg. Med. Chem. Lett. 2012, 22, 3656). The authors report a palladium catalyzed enantioselective reduction of α-acyloxy-1-arylethanones to access α-acyloxy-1-arylethanols in high enantioselectivities.
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Comment
The first synthesis of α-acyloxy-1-arylethanols was achieved using a chiral diamine ligand and SnCl2 (T. Mukaiyama, K. Tomimori, T. Oriyama Chem. Lett. 1985, 1359). Then, the use of enzymatic methods for their synthesis with excellent enantioselectivities but moderate regioselectivity was reported (A. Manzocchi, A. Fiecchi, E. Santaniello J. Org. Chem. 1988, 53, 4405; T. Ema, Y. Sugiyama, M. Fukumoto, H. Moriya, J.-N. Cui, T. Sakai, M. Utaka J. Org. Chem. 1988, 63, 4996; R. Hayakawa, M. Shimizu, T. Fujisawa Tetrahedron Asymmetry 1997, 8, 3201). With a palladium catalyst and a bisphosphine ligand, the authors were able to show excellent selectivities for a variety of substrates. In addition, catalyst loadings could be lowered to 0.2 mol% without affecting enantioselectivity.
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