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

<A NAME="RF03904SS-1">1</A> Ono N. The Nitro Group in Organic Synthesis   Wiley-VCH; New York: 2001.  Chap. 3. p.30 

<A NAME="RF03904SS-2A">2a</A> Yamada YMA. Yoshikawa N. Sasai H. Shibasaki M. Angew. Chem., Int. Ed. Engl.  1997,  36:  1871 

<A NAME="RF03904SS-2B">2b</A> List B. Lerner RA. Barbas CF. J. Am. Chem. Soc.  2000,  122:  2395 

<A NAME="RF03904SS-2C">2c</A> Trost BM. Ito H. Silcoff ER. J. Am. Chem. Soc.  2001,  123:  3367 

<A NAME="RF03904SS-2D">2d</A> Northrup AB. MacMillan DWC. J. Am. Chem. Soc.  2002,  124:  6798 

<A NAME="RF03904SS-3">3</A> Watanabe M. Murata K. Ikariya T. J. Org. Chem.  2002,  67:  1712 

<A NAME="RF03904SS-4">4</A> Chikasita H. Morita Y. Itoh K. Synth. Commun.  1987,  17:  677 

<A NAME="RF03904SS-5">5</A> Anbazhagan M. Kumaran G. Sasidharan M. J. Chem. Res., Synop.  1997,  9:  336 

<A NAME="RF03904SS-6A">6a</A> Rosini G. Ballini R. Synthesis  1988,  833 

<A NAME="RF03904SS-6B">6b</A> Pinnick HW. Organic Reactions   Vol. 38:  Paquette LA. Wiley; New York: 1990.  Chap. 3.

<A NAME="RF03904SS-7A">7a</A> Sasai H. Suzuki T. Arai S. Arai T. Shibasaki M. J. Am. Chem. Soc.  1992,  114:  4418 

<A NAME="RF03904SS-7B">7b</A> Shibasaki M. Yoshikawa N. Chem. Rev.  2002,  102:  2187 

<A NAME="RF03904SS-8A">8a</A> Christensen C. Juhl K. Jørgensen KA. Chem. Commun.  2001,  2222 

<A NAME="RF03904SS-8B">8b</A> Evans DA. Seidel D. Rueping M. Lam HW. Shaw JT. Downey CW. J. Am. Chem. Soc.  2003,  125:  12692 

<A NAME="RF03904SS-9">9</A> Trost BM. Yeh VSC. Angew. Chem. Int. Ed.  2002,  41:  861 

<A NAME="RF03904SS-10">10</A> Kezuka S. Mita T. Ohtsuki N. Ikeno T. Yamada T. Bull. Chem. Soc. Jpn.  2001,  74:  1333 

<A NAME="RF03904SS-11">11</A> Kezuka S. Kogami Y. Ikeno T. Yamada T. Bull. Chem. Soc. Jpn.  2003,  76:  49 

<A NAME="RF03904SS-12">12</A> Yamada T. Nagata T. Sugi KD. Yorozu K. Ikeno T. Ohtsuka Y. Miyazaki D. Mukaiyama T. Chem.-Eur. J.  2003,  9:  4485 

<A NAME="RF03904SS-13">13</A> Ohba S. Nagata T. Yamada T. Acta Crystallogr., Sect. E: Struct. Rep. Online  2001,  E57:  124 

<A NAME="RF03904SS-14">14</A> Kezuka S. Ohtsuki N. Mita T. Kogami Y. Ashizawa T. Ikeno T. Yamada T. Bull. Chem. Soc. Jpn.  2003,  76:  2197 

<A NAME="RF03904SS-15">15</A> Kogami Y. Nakajima T. Ashizawa T. Kezuka S. Ikeno T. Yamada T. Chem. Lett.  2004,  33:  614 

<A NAME="RF03904SS-16">16</A> Schaus SE. Brandes BD. Larrow JF. Tokunaga M. Hansen KB. Gould AE. Furrow ME. Jacobsen EN. J. Am. Chem. Soc.  2002,  124:  1307 

<A NAME="RF03904SS-17">17</A> Ready JM. Jacobsen EN. J. Am. Chem. Soc.  1999,  121:  6086 

<A NAME="RF03904SS-18">18</A>

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.