Mizoroki–Heck Cyclizations of Amide Derivatives for the Introduction of Quaternary Centers

• Published in: Angewandte Chemie International Edition Vol. 56; no. 23; pp. 6567 - 6571
• Main Authors: Medina, Jose M., Moreno, Jesus, Racine, Sophie, Du, Shuaijing, Garg, Neil K.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01-06-2017
• Edition: International ed. in English
• Subjects: Alkenes; amides; Amides - chemistry; Catalysis; Cyclization; Genetic transformation; homogeneous catalysis; Ligands; Mizoroki–Heck reactions; Nickel; Nickel - chemistry; quaternary centers; Stereoselectivity; nickel; amides; quaternary centers; homogeneous catalysis; Mizoroki-Heck reactions
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201703174

We report non‐decarbonylative Mizoroki–Heck reactions of amide derivatives. The transformation relies on the use of nickel catalysis and proceeds using sterically hindered tri‐ and tetrasubstituted olefins to give products containing quaternary centers. The resulting polycyclic or spirocyclic products can be obtained in good yields. Moreover, a diastereoselective variant of this method gives access to an adduct bearing vicinal, highly substituted sp3 stereocenters. These results demonstrate that amide derivatives can be used as building blocks for the assembly of complex scaffolds.
Adding complexity: A non‐decarbonylative Mizoroki–Heck reaction of Boc‐activated amide derivatives is reported. The transformation relies on the use of nickel catalysis and proceeds using sterically hindered tri‐ and tetrasubstituted olefins to give products containing quaternary centers. The results demonstrate that amide derivatives can be used as building blocks for the assembly of complex scaffolds.