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Synfacts 2014; 10(1): 0064
DOI: 10.1055/s-0033-1340444
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Palladium-Catalyzed Allylic Dearomatization

Contributor(s):
Mark Lautens
,
Zafar Qureshi
Chen J, Liu D, Butt N, Li C, Fan D, Liu Y, Zhang W * Shanghai Jiao Tong University, P. R. of China
Palladium-Catalyzed Asymmetric Hydrogenation of α-Acyloxy-1-arylethanones.

Angew. Chem. Int. Ed. 2013;
52: 11632-11636
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Publication History

Publication Date:
13 December 2013 (online)

 
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Key words

palladium - bisphosphine ligands - asymmetric hydrogenation

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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