N-silyl oxyketene imines are underused yet highly versatile reagents for catalytic asymmetric synthesis.
The reactions of acyl anion equivalents (d1 synthons) with carbonyl electrophiles allow for the construction of a wide range of molecules useful for the synthesis of biologically active compounds, natural products and chiral ligands. Despite their utility, significant challenges still exist for developing catalytic, enantioselective variants of these reactions. For example, the asymmetric benzoin process, arguably the most characteristic reaction of d synthetic equivalents, finds no general solution for reactions involving aliphatic acyl anions. In this Article, we introduce a new class of stable, isolable silyl ketene imines derived from protected cyanohydrins. These nucleophiles serve as acyl anion equivalents in Lewis base catalysed aldol addition reactions and allow for the preparation of cross-benzoin and glycolate-aldol products in high yield and with exceptional diastereo- and enantioselectivities.
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA. sdenmark@illinois.edu
Scott E
SE
Denmark
Tyler W
TW
Wilson
D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D007097:Imines / Q000737:chemistry*; D007700:Kinetics; D013237:Stereoisomerism
D000447:Aldehydes; D007097:Imines; C116609:3-hydroxybutanal