6749-63-9Relevant articles and documents
Palladium-Catalyzed Umpolung Type-II Cyclization of Allylic Carbonate-Aldehydes Leading to 3-Methylenecycloalkanol Derivatives
Tsukamoto, Hirokazu,Kawase, Ayumu,Doi, Takayuki
supporting information, p. 3733 - 3738 (2019/07/17)
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.).
SCOPE AND LIMITATIONS OF THE STEREOSELECTIVE HOMOGENEOUS HYDROGENATION OF METHYLENECYCLOHEXANOLS BY CATIONIC RHODIUM COMPLEXES
Brown, John M.,Hall, Stephen A.
, p. 1393 - 1396 (2007/10/02)
Homogeneous catalytic hydrogenation of 3-methylenecyclohexanol gives trans-3-methylcyclohexanol with 98percent stereoselectivity, but low selectivity is observed for 2-methylenecyclohexanol and 2-methylenecyclohexanemethanol.
