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

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 3 )−H functionalization of these unactivated substrates has been widely used to directly in...

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Bibliographic Details
Published in:Nature communications 2019-04, Vol.10 (1), p.1774-1774, Article 1774
Main Authors: Li, Fuyuan, Tian, Dong, Fan, Yifan, Lee, Richmond, Lu, Gang, Yin, Yanli, Qiao, Baokun, Zhao, Xiaowei, Xiao, Ziwei, Jiang, Zhiyong
Format: Article
Language:English
Subjects:
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140/131
140/146
140/58
639/638/439/890
639/638/77/883
639/638/77/888
Alcohols
Catalysis
Catalysts
Chemical reactions
Coupling (molecular)
Derivatives
Enantiomers
Gasoline
Humanities and Social Sciences
Ketones
multidisciplinary
Organic chemistry
Phosphoric acid
Raw materials
Science
Science (multidisciplinary)
Substrates
Toluene
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Summary: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 3 )−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 3 )−C(sp 3 ) coupling reactions of activated ketones with toluene and its derivatives by means of chiral acid catalysis. With a La(OTf) 3 /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. Asymmetric transformations involving abundant chemical feedstocks such as toluene and its derivatives are rather rare. Here, the authors report the radical enantioselective C(sp 3 ) −C(sp 3 ) coupling of activated ketones with toluenes by means of chiral acid catalysis to afford enantioenriched tertiary alcohols.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-019-09857-9