Chiral acid-catalysed enantioselective C-H functionalization of toluene and its derivatives driven by visible light.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 30992448.
- Also identified by DOI 10.1038/s41467-019-09857-9 and PMC identifier 6467922.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Toluene and its derivatives are petroleum-derived raw materials produced from gasoline by catalytic reformation. These abundant chemical feedstocks are commonly used as solvents in organic synthesis. The C(sp<sup>3</sup>)-H functionalization of these unactivated substrates has been widely used to directly introduce benzylic motifs into diverse molecules to furnish important compounds. Despite these advances, progress in asymmetric catalysis remains underdeveloped. Here, we report photoinduced radical-based enantioselective C(sp<sup>3</sup>)-C(sp<sup>3</sup>) coupling reactions of activated ketones with toluene and its derivatives by means of chiral acid catalysis. With a La(OTf)<sub>3</sub>/pybox complex catalyst, a variety of chiral 3-hydroxy-3-benzyl-substituted 2-oxindoles, including many conventionally difficult-to-access variants, are obtained directly from isatins in high yields with good to excellent enantioselectivities. Acenaphthoquinone is also compatible with the use of a chiral phosphoric acid (CPA) catalyst, leading to another series of important enantioenriched tertiary alcohols.