title: Diastereoselective carbocyclization of 1,6-heptadienes triggered by rhodium-catalyzed activation of an olefinic C-H bond.
abstract: The use of α,ω-dienes as functionalization reagents for olefinic carbon-hydrogen bonds has been rarely studied. Reported herein is the rhodium(I)-catalyzed rearrangement of prochiral 1,6-heptadienes into [2,2,1]-cycloheptane derivatives with concomitant creation of at least three stereogenic centers and complete diastereocontrol. Deuterium-labeling studies and the isolation of a key intermediate are consistent with a group-directed C-H bond activation, followed by two consecutive migratory insertions, with only the latter step being diastereoselective.
authors.affiliation: Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD (UK). aissa@liverpool.ac.uk.
authors.forename: Christophe
authors.initials: C
authors.lastname: Aïssa
authors.forename: Kelvin Y T
authors.initials: KY
authors.lastname: Ho
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Tetlow
authors.forename: María
authors.initials: M
authors.lastname: Pin-Nó
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D012238:Rhodium
keywords: CH activation; diastereoselectivity; diene; rearrangement; rhodium