Diastereoselective catalytic asymmetric nitroaldol reaction utilizing rare earth-Li-(R)-BINOL complex. A highly efficient synthesis of norstatine

Recent synthetic developments in the nitro to carbonyl conversion (Nef reaction)

“…The presence of small amounts of chiral rare earth -Li -BINOL complexes, however, exerts a powerful effect on the diastereoselection (Scheme 83). 154 The a-aminoaldehyde 329 reacts with nitromethane in the presence of La -Li -(R)-BINOL as the catalyst (3.3 mol%) to give the nitroalcohol 330 practically as the sole erythro diastereomer in 96% ee.…”

Medicinal Chemistry of α‐Hydroxy‐β‐Amino Acids

“…Nitroaldol 56 was formed from the catalytic reaction of aldehyde 55 with nitromethane in the presence of La-Li(S)-BINOL (1,1 0 -bi-2-naphthol) complex as catalyst. Hydrolysis gave one enantiomer, (2S,3S)-AHPA [58]. Herranz et al described a one-pot procedure for the stereoselective synthesis of (2R,3R)-and (2S,3R)-AHPA starting also from a protected amino aldehyde and after formation of cyanohydrins the mixture of isomers was created, which was then transformed into 2-hydroxyester.…”

“…Regarding AHPA, one efficient synthetic approach is the transformation of L-phenylalanine to the corresponding N,N-dibenzylamino aldehyde followed by the diastereoselective nucleophilic addition of trimethylsilyl cyanide to produce cyanohydrins [89,91]. This strategy has gained wide recognition and several different modifications have been reported [58,66,[91][92][93][94][95][96]. Although some of those methods seemed to be promising, practical industrial processes still required more investigations.…”

Chiral Cu(II) Complexes as Recyclable Catalysts for Asymmetric Nitroaldol (Henry) Reaction in Ionic Liquids as Greener Reaction Media

“…In spite of many applications, the catalytic enantioselective version of nitroaldol reaction is relatively less explored as compared to its aldol counterpart due to the non-availability of enantioselective catalysts. Shibasaki has reported the first asymmetric version of nitroaldol reaction in 1992 [3][4][5][6][7][8][9][10][11]. Since then various metals [3][4][5][6][7][12][13][14][15][16][17] and non-metal based catalysts [18,19] have been investigated for the asymmetric nitroaldol reaction with chiral ligands such as BINOL [5,10,20], amino alcohol [21,22], bis(oxazoline) [23][24][25][26][27][28][29][30][31], bis(thiazoline) [32], bis(imidazoline) [33][34][35], sulfonyl diamine [36], salen [37][38][39][40], Schiff bases [41]…”