Lewis base activation of Lewis acids. Vinylogous aldol addition reactions of conjugated N,O-silyl ketene acetals to aldehydes.
N,O-Silyl dienyl ketene acetals derived from unsaturated morpholine amides have been developed as highly useful reagents for vinylogous aldol addition reactions. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-3, N,O-silyl dienyl ketene acetal 8 undergoes high-yielding and highly site-selective addition to a wide variety of aldehydes with excellent enantioselectivity. Of particular note is the high yields and selectivities obtained from aliphatic aldehydes. Low catalyst loadings (2-5 mol %) can be employed. The morpholine amide serves as a useful precursor for further synthetic manipulation.
Denmark
Scott E
SE
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, 61801, USA. denmark@scs.uiuc.edu
Heemstra
John R
JR
D000080:Acetals / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
D000080:Acetals; D000447:Aldehydes; D005030:Ethylenes; D007659:Ketones; D012821:Silanes; D014753:Vinyl Compounds; C008223:ketene