title: Solvent-dependent enantiodivergence in the chlorocyclization of unsaturated carbamates.
abstract: A remarkable solvent-controlled enantiodivergence is seen in the hydroquinidine 1,4-phthalazinediyl diether ((DHQD)2PHAL)-catalyzed chlorocyclization of unsaturated carbamates. Eyring plot analyses of this previously unreported reaction are used to probe and compare the R- and S-selective pathways. In the CHCl3/hexanes solvent system, the pro-R process shows a surprising increase in selectivity with increasing temperature. These studies point to a strongly solvent-dependent entropy-enthalpy balance between the pro-R and pro-S pathways.
authors.affiliation: Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA.
authors.forename: Atefeh
authors.initials: A
authors.lastname: Garzan
authors.forename: Arvind
authors.initials: A
authors.lastname: Jaganathan
authors.forename: Nastaran
authors.initials: N
authors.lastname: Salehi Marzijarani
authors.forename: Roozbeh
authors.initials: R
authors.lastname: Yousefi
authors.forename: Daniel C
authors.initials: DC
authors.lastname: Whitehead
authors.forename: James E
authors.initials: JE
authors.lastname: Jackson
authors.forename: Babak
authors.initials: B
authors.lastname: Borhan