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Transition metal-free direct dehydrogenative arylation of activated C(sp3)-H bonds: synthetic ambit and DFT reactivity predictions.

ABSTRACT: A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp3)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses tert-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of ?-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp3)-H bond with a sufficiently low pK a value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp3)-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.

SUBMITTER: Lovato K 

PROVIDER: S-EPMC6202766 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Transition metal-free direct dehydrogenative arylation of activated C(sp<sup>3</sup>)-H bonds: synthetic ambit and DFT reactivity predictions.

Lovato Kaitlyn K   Guo Lirong L   Xu Qing-Long QL   Liu Fengting F   Yousufuddin Muhammed M   Ess Daniel H DH   Kürti László L   Gao Hongyin H  

Chemical science 20180827 41

A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp<sup>3</sup>)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses <i>tert</i>-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of α-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states t  ...[more]

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