Tris(trimethylsilyl)silyl-Governed Aldehyde Cross-Aldol Cascade Reaction
Citations Over TimeTop 10% of 2005 papers
Abstract
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.
Related Papers
- → N,N-bis(trimethylsilyl)methoxymethylamine as a convenient synthetic equivalent for +CH2NH2: N,N-bis(trimethylsilyl)aminomethylation of silyl sulphides and phosphites(1984)14 cited
- → ChemInform Abstract: TRIS‐(TRIS‐(TRIMETHYLSILYL‐METHYL)‐STANNYL)‐THALLIUM(1973)
- → ChemInform Abstract: 1,3λ3‐Azaphosphinines by Reaction of 3‐Azapyrylium Salts with Tris(trimethylsilyl)phosphane.(1987)
- → ChemInform Abstract: The Wagner‐Meerwein Analogous 1,2‐Shift of a Trimethylsilyl Group from Silicon to Carbon During Cleavage of ((Trimethylsilyl)silyl)methyl Ethers.(1987)
- → ChemInform Abstract: Preparation and Structure of Aluminum Derivatives of the Extremely Bulky Tris(trimethylsilyl)silyl Group. The Molecular Structure of the (Me3Si)3SiAl(C6H5)2·THF Adduct.(1990)