Abstract
Palladium-catalyzed umpolung type-II cyclization of allylic carbonate-aldehydes leading to 3-methylenecycloalkanol derivatives was developed. The formate reductant was effective for the cyclization without causing a reduction of the η3-allylpalladium intermediate. One-pot decarboxylative allylation of aldehyde-containing malonate with 2-[(acetyloxy)methyl]-2-propenyl methyl carbonate followed by the cyclization of the allyl acetate-aldehyde formed in situ was also achieved. The high diastereoselectivities observed in the cyclization of branched substrates indicates that a chair-chair transition state should be involved. Based on the presumed transition state, we could predict the enantioselectivity of the cyclization using SEGPHOS as a chiral diphosphine ligand and obtain optically active alcohols in up to 95:5 er. (Figure presented.).
Original language | English |
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Pages (from-to) | 3733-3738 |
Number of pages | 6 |
Journal | Advanced Synthesis and Catalysis |
Volume | 361 |
Issue number | 16 |
DOIs | |
Publication status | Published - 2019 |
Keywords
- allylic carbonate
- diastereoselectivity
- enantioselectivity
- one-pot
- palladium
- umpolung cyclization
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry