Mobilizing Cu(I) for Carbon-Carbon Bond Forming Catalysis in the Presence of Thiolate. Chemical Mimicking of Metallothioneins

• Authors: Zhihui Zhang, Emory University; Matthew G. Lindale, Emory University; Lanny S Liebeskind, Emory University
• Journal Title: Journal of the American Chemical Society
• Volume: Volume 133, Number 16
• Publisher: American Chemical Society | 2011-04-27, Pages 6403-6410
• Type of Work: Article | Post-print: After Peer Review
• Publisher DOI: http://doi.org/10.1021/ja200792m
• Subjects: Chemistry, General

Abstract

Metal binding proteins are essential to many life-sustaining processes. The non-thermodynamic binding selectivity and specificity of metals to proteins in living systems has captured the focus of much research effort. Equally essential to life-sustaining processes are the biomolecular mechanisms by which tightly bound metals are selectively transferred, or released from a thermodynamically strong coordination sphere within a protein. As mechanistic knowledge of these metal mobilizing biological processes is uncovered, occasions may arise for translating the biological processes into ones useful in chemical catalysis in the laboratory. In particular, the biomolecular mechanisms by which Nature releases catalytically important thiophilic metals like Cu from high-sulfur binding sites within proteins should be useful points of inspiration from which to develop novel preparative protocols where the catalytic turnover of a thiophilic metal in a sulfur-containing environment is essential. Opportunities for productive metal catalysis in sulfur-rich systems are found in energy-related research (metal-catalyzed desulfurization of carbon-based fuels), detoxification of nerve gas agents (metal-catalyzed transformations of phosphonothioate and phosphorothioates), as well as in the synthesis of fine chemicals through desulfitative transformations.