title: Novel Ring Contraction Reaction for the Synthesis of Functionalized Tetrathiamacrocyclic Ligand Molecules.
abstract: Chlorination of [14]aneS(4)-ol (1,4,8,11-tetrathiatetradecan-6-ol) and cis/trans-[14]aneS(4)-diol (cis/trans-1,4,8,11-tetrathiatetradecane-6,13-diol) yields the corresponding dichloro-substituted macrocycles [14]aneS(4)-Cl (1,4,8,11-tetrathiatetradecane 6-chloride) and cis/trans-[14]aneS(4)-Cl(2) (cis/trans-1,4,8,11-tetrathiatetradecane 6,13-dichloride) in good yield. Thiomethylation of the chlorides produces the ring-contracted pendent thioether macrocycles [13]aneS(4)-CH(2)SCH(3) (1,4,7,10-tetrathiatridecane-5-(methylthio)methane) and cis/trans-anti-[12]aneS(4)-(CH(2)SCH(3))(2) (1,4,7,10-tetrathiadodecane-5,11-bis((methylthio)methane)). The mechanism of the ring contraction reaction is discussed in terms of the reactivity of the monochlorinated macrocycle toward ring contraction and the stereochemistry of the chlorinated intermediates and the thiomethylated products, which are based on the X-ray crystal structure analyses of trans-[14]aneS(4)-Cl(2) and trans-anti-[12]aneS(4)-(CH(2)SCH(3))(2).
authors.affiliation: Anorganisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Comba
authors.forename: Andreas
authors.initials: A
authors.lastname: Fath
authors.forename: Bernd
authors.initials: B
authors.lastname: Nuber
authors.forename: Alexander
authors.initials: A
authors.lastname: Peters