title: Role of anions in the synthesis of cyclobutane derivatives via [2 + 2] cycloaddition reaction in the solid state and their isomerization in solution.
abstract: trans-3-(4'-Pyridyl)acrylic acid (4-PA) is inert to photodimerization reaction both in solution and solid state. It is made photoreactive by forming salts with various acids. The anions of these salts play a key role in directing the packing of 4-PAH(+) in the solid state. The anions CF(3)CO(2)(-), Cl(-), ClO(4)(-), and BF(4)(-) direct the parallel alignments of 4-PAH(+) in head-to-tail (HT) fashion and lead to the formation of HT-photodimer. On the other hand, bivalent anion SO(4)(2-) directs parallel alignment of 4-PAH(+) in head-to-head (HH) fashion and lead to the formation of HH-photodimer. The details of the anion-controlled stereoselective syntheses of these two cyclobutane derivatives are presented. Interestingly, both cyclobutane compounds undergo isomerization from rctt-form to rctc-form in solution catalyzed by acid.
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543.
authors.forename: Goutam Kumar
authors.initials: GK
authors.lastname: Kole
authors.forename: Geok Kheng
authors.initials: GK
authors.lastname: Tan
authors.forename: Jagadese J
authors.initials: JJ
authors.lastname: Vittal