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C(sp3)–H functionalizations of light hydrocarbons using decatungstate photocatalysis in flow

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Science  03 Jul 2020:
Vol. 369, Issue 6499, pp. 92-96
DOI: 10.1126/science.abb4688

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Using hydrocarbons as reagents

Adding small alkyl groups to complex molecules usually relies on alkyl halide reagents. Laudadio et al. now report a convenient method to add ethane and propane directly across conjugated olefins with no prefunctionalization or byproducts (see the Perspective by Oksdath-Mansilla). The C–H bond scission in this hydroalkylation is accomplished by a decatungstate photocatalyst that also acts as a hydrogen atom transfer agent to complete the process. The reaction, optimized under flow conditions, works with methane as well, albeit with lower efficiency.

Science, this issue p. 92; see also p. 34

Abstract

Direct activation of gaseous hydrocarbons remains a major challenge for the chemistry community. Because of the intrinsic inertness of these compounds, harsh reaction conditions are typically required to enable C(sp3)–H bond cleavage, barring potential applications in synthetic organic chemistry. Here, we report a general and mild strategy to activate C(sp3)–H bonds in methane, ethane, propane, and isobutane through hydrogen atom transfer using inexpensive decatungstate as photocatalyst at room temperature. The corresponding carbon-centered radicals can be effectively trapped by a variety of Michael acceptors, leading to the corresponding hydroalkylated adducts in good isolated yields and high selectivity (38 examples).

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