Asymmetric Transformations of α-Hydroxy Enamides Catalyzed by Chiral Brønsted Acids

2-Aminoallyl cations are reactive intermediates that undergo diverse reactions, such as cycloadditions, direct nucleophilic additions, Nazarov electrocyclizations, and rearrangements. We review recent development in asymmetric catalytic reactions (nucleophilic additions and Nazarov electrocyclizations) based on chiral counteranion-paired 2-aminoallyl cation intermediates generated through activation of α-hydroxy enamides in the presence of chiral Brønsted acid catalysts. With an understanding of their asymmetric catalysis modes and mechanisms, we expect more asymmetric catalytic reactions will be developed on the basis of this strategy in the near future.

Key words

aminoallyl cations - hydroxy enamides - chiral anion catalysis - Brønsted acids - indole addition - Nazarov electrocyclization

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References

1a Harmata M. Acc. Chem. Res. 2001; 34: 595
1b Harmata M. Chem. Commun. 2010; 46: 8886
1c Li H, Wu J. Synthesis 2015; 47: 22
1d Lohse AG, Hsung RP. Chem. Eur. J. 2011; 17: 3812

2a Harmata M, Ghosh SK, Hong X, Wacharasindhu S, Kirchhoefer P. J. Am. Chem. Soc. 2003; 125: 2058
2b Huang J, Hsung RP. J. Am. Chem. Soc. 2005; 127: 50
2c Topinka M, Zawatzky K, Barnes CL, Welch CJ, Harmata M. Org. Lett. 2017; 19: 4106
2d Villar L, Uria U, Martínez JI, Prieto L, Reyes E, Carrillo L, Vicario JL. Angew. Chem. Int. Ed. 2017; 56: 10535

3a Vander Wal MN, Dilger AK, MacMillan DW. C. Chem. Sci. 2013; 4: 3075
3b Liu C, Oblak EZ, Vander Wal MN, Dilger AK, Almstead DK, MacMillan DW. C. J. Am. Chem. Soc. 2016; 138: 2134

4a Kende AS, Huang H. Tetrahedron Lett. 1997; 38: 3353
4b Prié G, Prévost N, Twin H, Fernandes SA, Hayes JF, Shipman M. Angew. Chem. Int. Ed. 2004; 43: 6517
4c Kim H, Ziani-Cherif C, Oh J, Cha JK. J. Org. Chem. 1995; 60: 792
4d Stoll AH, Blakey SB. Chem. Sci. 2011; 2: 112
4e Schmid R, Schmid H. Helv. Chim. Acta 1974; 57: 1883
4f De Kimpe N, Stevens C. Tetrahedron 1990; 46: 6753

5a Bonderoff SA, Grant TN, West FG, Tremblay M. Org. Lett. 2013; 15: 2888
5b Ma Z.-X, He S, Song W, Hsung RP. Org. Lett. 2012; 14: 5736

6 Saputra MA, Dange NS, Cleveland AH, Malone JA, Fronczek FR, Kartika R. Org. Lett. 2017; 19: 2414
7 Schlegel M, Schneider C. J. Org. Chem. 2017; 82: 5986
8 Griffin K, Montagne C, Hoang CT, Clarkson GJ, Shipman M. Org. Biomol. Chem. 2012; 10: 1032

9a Feast GC, Page LW, Robertson J. Chem. Commun. 2010; 46: 2835
9b Stoll AH, Blakey SB. J. Am. Chem. Soc. 2010; 132: 2108

10a Lacour J, Hebbe-Viton V. Chem. Soc. Rev. 2003; 32: 373
10b Lacour J, Moraleda D. Chem. Commun. 2009; 7073
10c Phipps RJ, Hamilton GL, Toste FD. Nat. Chem. 2012; 4: 603
10d Brak K, Jacobsen EN. Angew. Chem. Int. Ed. 2013; 52: 534
10e Mahlau M, List B. Angew. Chem. Int. Ed. 2013; 52: 518

11 Akiyama T, Itoh J, Yokota K, Fuchibe K. Angew. Chem. Int. Ed. 2004; 43: 1566
12 Uraguchi D, Terada M. J. Am. Chem. Soc. 2004; 126: 5356

13a Akiyama T. Chem. Rev. 2007; 107: 5744
13b Terada M. Synthesis 2010; 1929
13c Parmar D, Sugiono E, Raja S, Rueping M. Chem. Rev. 2014; 114: 9047
13d Li X, Song Q. Chin. Chem. Lett. 2018; 29: 1181

14 Rajkumar S, Wang J, Zheng S, Wang D, Ye X, Li X, Peng Q, Yang X. Angew. Chem. Int. Ed. 2018; 57: 13489
15 Saputra MA, Nepal B, Dange NS, Du P, Fronczek FR, Kumar R, Kartika R. Angew. Chem. Int. Ed. 2018; 57: 15558
16 Jin J, Zhao Y, Gouranourimi A, Ariafard A, Chan PW. H. J. Am. Chem. Soc. 2018; 140: 5834