Since the first example was reported by Claisen in 1912. the catalytic asymmetric Claisen rearrangement1 has enjoyed unparalleled value because of the utility of the products. However, the enantioselective catalytic version of the propargyl Claisen rearrangement2 continues to be relatively rare. Considering the synthetical value of functionalized allenes3 and the lack of asymmetric version, our main researches are focused on the development of enantioselective propargyl Claisen rearrangement.4 In the presence of the chiral N,N'-dioxide/Ni(II) complex, a wide range of allenyl/allyl substituted all-carbon quaternary β-ketoesters5 was obtained in generally good yield (up to 99%) and high diastereoselectivity (up to 99:1 d.r.) with excellent enantioselectivity (up to 98% ee). In addition, it was developed that the first kinetic resolution of racemic propargyl vinyl ethers via Claisen rearrangement.6 Trisubstituted allene derivatives and chiral propargyl vinyl ethers were isolated in high enantioselectivities and good yields. Keywords Claisen rearrangement; asymmetric catalysis; nickel; allene; kinetic resolution References [1] For reviews: (a) Martín Castro, A. M. Chem. Rev. 2004, 104, 2939. (b) Ilardi, E. A.; Stivala, C. E.; Zakarian, A. Chem. Soc. Rev. 2009, 38, 3133. (c) Rehbein, J.; Hiersemann, M. Synthesis 2013, 1121. [2] Tejedor, D.; Méndez-Abt, G.; Cotos, L.; García-Tellado, F. Chem. Soc. Rev. 2013, 42, 458. [3] (a) Yu, S.; Ma, S. Angew. Chem. Int. Ed. 2012, 51, 3074. (b) Lu, T.; Lu, Z.; Ma, Z.-X.; Zhang, Y.; Hsung, R. P. Chem. Rev. 2013, 113, 4862. (c) Ye, J. Ma, S. Acc. Chem. Res. 2014, 47, 989. [4] Cao, T.; Deitch, J.; Linton, E. C.; Kozlowski, M. C. Angew. Chem. Int. Ed. 2012, 51, 2448. [5] Liu, Y. B.; Hu, H. P.; Zheng, H. F.; Xia, Y.; Liu, X. H.; Lin, L. L.; Feng, X. M. Angew. Chem. Int. Ed. 2014, 53, 11579. [6] Liu, Y. B.; Liu, X. H.; Hu, H. P.; Guo, J.; Xia, Y.; Lin, L. L.; Feng, X. M. In Submission.

Enantioselective propargyl and allyl Claisen rearrangements catalyzed by chiral nickel(II)/ N,N'-dioxide complex

251st National Meeting (2016)

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