Tris(trimethylsilyl)silyl-governed aldehyde cross-aldol cascade reaction.
The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.
Boxer
Matthew B
MB
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA.
Yamamoto
Hisashi
H
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry*; D008968:Molecular Conformation; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D000447:Aldehydes; D014297:Trimethylsilyl Compounds