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- Title
Efficient Access to All-Carbon Quaternary and Tertiary α-Functionalized Homoallyl-type Aldehydes from Ketones.
- Authors
Pace, Vittorio; Castoldi, Laura; Mazzeo, Eugenia; Rui, Marta; Langer, Thierry; Holzer, Wolfgang
- Abstract
β,γ-Unsaturated aldehydes with all-carbon quaternary or tertiary α-centers were rapidly assembled from ketones through a unique synthetic operation consisting of 1) C1 homologation, 2) Lewis acid mediated epoxide-aldehyde isomerization, and 3) electrophilic trapping. The synthetic equivalence of a vinyl oxirane and a β,γ-unsaturated aldehyde is the key concept of this previously undisclosed tactic. Mechanistic studies and labeling experiments suggest that an aldehyde enolate is a crucial intermediate. The homologating carbenoid formation plays a critical role in determining the chemoselectivity.
- Subjects
ALDEHYDES; KETONES; CARBON; QUATERNARY structure; TERTIARY structure; FUNCTIONAL groups
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 41, p12851
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201706236