Aluminum Bis(trifluoromethylsulfonyl)amides: New Highly Efficient and Remarkably Versatile Catalysts for C - C Bond Formation Reactions
Andreas Marx, Hisashi Yamamoto*
*Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa,
Nagoya 464-8603, Japan, Email: yamamoto
uchicago.edu
A. Marx, H. Yamamoto, Angew. Chem. Int. Ed., 2000, 39, 178-181.
DOI: 10.1002/(SICI)1521-3773(20000103)39:1<178::AID-ANIE178>3.0.CO;2-W
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Abstract
Aluminum bis(trifluoromethylsulfonyl)amides are highly efficient and versatile promoters for the allylation and pentadienylation of aldehydes, aldol reactions, and aldol cross-coupling of ketones.
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Details
The document discusses the development of new, highly efficient, and versatile catalysts for carbon-carbon bond formation reactions. These catalysts, derived from the superacid bis(trifluoromethylsulfonyl)amine (Tf2NH), exhibit unprecedented efficiency in promoting allylation and other important reactions. The study highlights the limitations of known metal triflates and the successful development of aluminum bis(trifluoromethylsulfonyl)amides, particularly Me2AlNTf2, which catalyzes the addition of allyl trimethylsilane to benzaldehyde with a 93% yield. The catalysts also show excellent performance in the allylation of aromatic and aliphatic aldehydes, pentadienylation, and Mukaiyama aldol reactions. The research further explores the design of tailor-made catalysts for chemoselective aldol reactions, demonstrating the ability of aluminum 2,6-diphenylphenoxides to selectively recognize and activate less-hindered aldehydes. The findings suggest that metal bistriflylamides could be valuable in developing new Lewis acids for important organic transformations, with potential applications in enantioselective processes. The study underscores the correlation between the catalytic ability of these aluminum species and the electronic and steric properties of the ligand sphere.
Key Words
Mukaiyama Aldol Reaction, Sakurai Reaction, aluminum, C-C coupling, Lewis acids, superacidic systems
ID: J06-Y2000-560
