Nickel(0)-Catalyzed Enantioselective Annulations of Alkynes and Arylenoates Enabled by a Chiral NHC Ligand: Efficient Access to Cyclopentenones†
Joachim S. E. Ahlin
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorDr. Pavel A. Donets
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorCorresponding Author
Prof. Dr. Nicolai Cramer
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsaSearch for more papers by this authorJoachim S. E. Ahlin
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorDr. Pavel A. Donets
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorCorresponding Author
Prof. Dr. Nicolai Cramer
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsaSearch for more papers by this authorThis work was supported by the Swiss National Science Foundation (no. 137666). We thank Dr. R. Scopelliti for X-ray crystallographic analysis of compounds 3 la and 6. NHC=N-heterocyclic carbene.
Graphical Abstract
Cyclization: Nickel(0) catalysts with a chiral bulky C1-symmetric N-heterocyclic carbene ligand enabled the efficient asymmetric reductive [3+2] cycloaddition of enoates and alkynes, providing substituted cyclopentenones under mild conditions. The system provided the products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes.
Abstract
Cyclopentenones are versatile structural motifs of natural products as well as reactive synthetic intermediates. The nickel-catalyzed reductive [3+2] cycloaddition of α,β-unsaturated aromatic esters and alkynes constitutes an efficient method for their synthesis. Here, nickel(0) catalysts comprising a chiral bulky C1-symmetric N-heterocyclic carbene ligand were shown to enable an efficient asymmetric synthesis of cyclopentenones from mesityl enoates and internal alkynes under mild conditions. The bulky NHC ligand provided the cyclopentenone products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes.
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