Chiral acid-catalysed enantioselective C-H functionalization of toluene and its derivatives driven by visible light.

Authors:
Fuyuan Li
Fuyuan Li
Harbin Medical University
China
Dong Tian
Dong Tian
Zhejiang Normal University
China
Yifan Fan
Yifan Fan
Wuhan University
Richmond Lee
Richmond Lee
Henan University
China
Gang Lu
Gang Lu
School of Materials Science and Engineering
Singapore
Yanli Yin
Yanli Yin
Henan University of Technology
China
Baokun Qiao
Baokun Qiao
Henan University
China
Xiaowei Zhao
Xiaowei Zhao
Northeast Normal University
China

Nat Commun 2019 04 16;10(1):1774. Epub 2019 Apr 16.

Key Laboratory of Natural Medicine and Immuno-Engineering of Henan Province, Henan University, 475004, Kaifeng, Henan, China.

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)-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)-C(sp) coupling reactions of activated ketones with toluene and its derivatives by means of chiral acid catalysis. With a La(OTf)/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.

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http://dx.doi.org/10.1038/s41467-019-09857-9DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6467922PMC
April 2019
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