Enantioselective Henry Reaction Catalyzed by Salen-Cobalt Complexes

Abstract

The enantioselective Henry reaction catalyzed by the optically active salen-cobalt complexes, proceeded to afford β-hydroxynitroalkanes­ in good-to-high yields with high enantio­selectivity.

aldehyde - asymmetric catalysis - salen-cobalt complexes - direct nitroaldol reaction - β-hydroxynitroalkanes

References

1 Ono N. The Nitro Group in Organic Synthesis   Wiley-VCH; New York: 2001.  Chap. 3. p.30 

2a Yamada YMA. Yoshikawa N. Sasai H. Shibasaki M. Angew. Chem., Int. Ed. Engl.  1997,  36:  1871 

2b List B. Lerner RA. Barbas CF. J. Am. Chem. Soc.  2000,  122:  2395 

2c Trost BM. Ito H. Silcoff ER. J. Am. Chem. Soc.  2001,  123:  3367 

2d Northrup AB. MacMillan DWC. J. Am. Chem. Soc.  2002,  124:  6798 

3 Watanabe M. Murata K. Ikariya T. J. Org. Chem.  2002,  67:  1712 

4 Chikasita H. Morita Y. Itoh K. Synth. Commun.  1987,  17:  677 

5 Anbazhagan M. Kumaran G. Sasidharan M. J. Chem. Res., Synop.  1997,  9:  336 

6a Rosini G. Ballini R. Synthesis  1988,  833 

6b Pinnick HW. Organic Reactions   Vol. 38:  Paquette LA. Wiley; New York: 1990.  Chap. 3.

7a Sasai H. Suzuki T. Arai S. Arai T. Shibasaki M. J. Am. Chem. Soc.  1992,  114:  4418 

7b Shibasaki M. Yoshikawa N. Chem. Rev.  2002,  102:  2187 

8a Christensen C. Juhl K. Jørgensen KA. Chem. Commun.  2001,  2222 

8b Evans DA. Seidel D. Rueping M. Lam HW. Shaw JT. Downey CW. J. Am. Chem. Soc.  2003,  125:  12692 

9 Trost BM. Yeh VSC. Angew. Chem. Int. Ed.  2002,  41:  861 

10 Kezuka S. Mita T. Ohtsuki N. Ikeno T. Yamada T. Bull. Chem. Soc. Jpn.  2001,  74:  1333 

11 Kezuka S. Kogami Y. Ikeno T. Yamada T. Bull. Chem. Soc. Jpn.  2003,  76:  49 

12 Yamada T. Nagata T. Sugi KD. Yorozu K. Ikeno T. Ohtsuka Y. Miyazaki D. Mukaiyama T. Chem.-Eur. J.  2003,  9:  4485 

13 Ohba S. Nagata T. Yamada T. Acta Crystallogr., Sect. E: Struct. Rep. Online  2001,  E57:  124 

14 Kezuka S. Ohtsuki N. Mita T. Kogami Y. Ashizawa T. Ikeno T. Yamada T. Bull. Chem. Soc. Jpn.  2003,  76:  2197 

15 Kogami Y. Nakajima T. Ashizawa T. Kezuka S. Ikeno T. Yamada T. Chem. Lett.  2004,  33:  614 

16 Schaus SE. Brandes BD. Larrow JF. Tokunaga M. Hansen KB. Gould AE. Furrow ME. Jacobsen EN. J. Am. Chem. Soc.  2002,  124:  1307 

17 Ready JM. Jacobsen EN. J. Am. Chem. Soc.  1999,  121:  6086 

18

In case of contamination with the cobalt-salen complex after the purification by the column chromatography, the pure product could be obtained as follows: To the CH₂Cl₂ solution of the contaminated product (ca. 0.5 mmol), silver hexafluoroantimonate (34.3 mg, 0.1 mmol) was added at -78 °C. After stirring for 30 min, the mixture was purified by a short column chromatography to afford the pure product.