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Edited by Russell J. Hemley, Carnegie Institution of Washington, Washington, DC, and approved July 1, 2014 (received for review December 30, 2013)
Significance
Organic compound transformations in the Earth commonly take place in the presence of minerals and aqueous solutions, but a mechanistic understanding of how minerals influence hydrothermal organic reactivity is virtually nonexistent. We present the first description of mineral catalysis of a fundamental organic reaction—carbon−hydrogen bond activation. The discovery that a common mineral, sphalerite (ZnS), can readily accomplish this reaction will interest not only geochemists but also the organic catalysis and green chemistry communities, because the solvent for organic reactions under these conditions is water. This work highlights the importance of aqueous processes in organic chemistry and shows how common minerals could be used as catalysts for organic reactions.
Abstract
Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth’s deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon−hydrogen bond in the dimethylcyclohexanes.
Footnotes
- ↵1To whom correspondence should be addressed. Email: h.hartnett{at}asu.edu.
Author contributions: J.A.S., I.R.G., E.L.S., L.B.W., and H.E.H. designed research; J.A.S. performed research; J.A.S., I.R.G., E.L.S., L.B.W., and H.E.H. analyzed data; and J.A.S. wrote the paper.
The authors declare no conflict of interest.
This article is a PNAS Direct Submission.
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1324222111/-/DCSupplemental.
Sphalerite catalyzes C−H bond activation
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