J. Dupont, Adriane S. Gruber, Gledison S. Fonseca
2001
Citations
0
Influential Citations
45
Citations
Journal
Organometallics
Abstract
Racemic sulfur chloro-bridged palladacycles (rac-4b−6b), derived from the orthopalladation of (1-tert-butylsulfanylethyl)benzene, (1-methylsulfanylethyl)benzene, and 2-(1-tert-butylsulfanylethyl)naphthalene (rac-1−3), have been synthesized in good yields using palladium acetate as the metalation agent and followed by reaction with LiCl. Palladacycles rac-4b and rac-6b have been isolated as single isomers, whereas rac-5b has been obtained as a mixture of two diastereoisomers (3:1). Variable-temperature 1H NMR showed that the S-t-Bu palladacycle 4b is configurationally stable over a large range of temperatures (from −20 to 100 °C). On the other hand, S-Me analogue 5b undergoes facile sulfur pyramidal inversion with an energy barrier of 18 kcal/mol. Moreover, the optically active (1-alkylsufanylethyl)benzenes, (R)-1 and (R)-2, respectively, have been prepared in 91% and 97% ee, respectively, from the reaction of sodium methylthiolate and sodium tert-butylthiolate, respectively, with non-racemic (S)-(−)-1-phe...