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Copper‐Catalyzed Enantioselective Difluoromethylation‐Alkynylation of Olefins by Solving the Dilemma between Acidities and Reduction Potentials of Difluoromethylating Agents.
- Source :
-
Angewandte Chemie International Edition . 9/11/2023, Vol. 62 Issue 37, p1-7. 7p. - Publication Year :
- 2023
-
Abstract
- Molecules containing a difluoromethyl group or a propargylic stereocenter are widely used in pharmaceuticals and agrochemicals, and 1,2‐functionalization of olefins is an important method for introducing the two groups into molecules simultaneously. The construction of the propargylic stereocenter with terminal alkynes usually requires bases. However, difluoromethylating agents with high reduction potentials often decompose in the presence of bases because of their acidities, and those with low reduction potentials are stable but difficult to undergo the desired single electron transfer (SET) reduction. Using the linear relationship between reduction potential differences (ΔE) and Hammett substituent constants (σ) of difluoromethyl aryl sulfones, we solved the dilemma between acidities and reduction potentials of difluoromethylating agents. Herein, we report the first enantioselective difluoromethylation‐alkynylation of olefins with difluoromethyl 4‐chlorophenyl sulfone with high enantioselectivity (>90 % ee). We also extended this asymmetric fluoroalkylation‐alkynylation reaction with other fluoroalkyl sulfones, which enabled efficient installation of trifluoromethyl, difluoroalkyl, difluorobenzyl, (benzenesulfonyl)‐difluoromethyl and monofluoromethyl groups into products. [ABSTRACT FROM AUTHOR]
- Subjects :
- *REDUCTION potential
*ALKENES
*DILEMMA
*ACIDITY
*CHARGE exchange
Subjects
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 62
- Issue :
- 37
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 171582864
- Full Text :
- https://doi.org/10.1002/anie.202308816