1. Ligand-controlled regiodivergent arylation of aryl(alkyl)alkynes and asymmetric synthesis of axially chiral 9-alkylidene-9,10-dihydroanthracenes.
- Author
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Sun, Chao, Qi, Ting, Rahman, Faiz-Ur, Hayashi, Tamio, and Ming, Jialin
- Subjects
LIGANDS (Chemistry) ,ALKYNES ,ARYLATION ,RHODIUM catalysts ,CATALYSTS ,CARBON - Abstract
Transition metal-catalyzed addition of organometallics to aryl(alkyl)alkynes has been well known to proceed with the regioselectivity in forming a carbon–carbon bond at the alkyl-substituted carbon (β-addition). Herein, the reverse regiochemistry with high selectivity in giving 1,1-diarylalkenes (α-addition) was realized in the reaction of arylboronic acids with aryl(alkyl)alkynes by use of a rhodium catalyst coordinated with a chiral diene ligand, whereas the arylation of the same alkynes proceeded with the usual regioselectivity (β-addition) in the presence of a rhodium/DM-BINAP catalyst. The regioselectivity can be switched by the choice of ligands on the rhodium catalysts. This reverse regioselectivity also enabled the catalytic asymmetric synthesis of phoenix-like axially chiral alkylidene dihydroanthracenes with high enantioselectivity through an α-addition/1,4-migration/cyclization sequence. Transition-metal-catalysed additions of carbon species to aryl(alkyl)alkynes is an established and useful methodology for building towards useful molecular complexity. Here, the authors present rhodium-catalysed regiodivergent additions to aryl(alkyl)alkynes, which allows access to the uncommonly found α-addition products through modulation of the ligand choice. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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