An unusual endo-selective C-H hydroarylationof norbornene by the Rh(I)-catalyzed reactionof benzamides. Issue 1 (December 2017)

• Record Type: Journal Article
• Authors: Shibata, Kaname; Natsui, Satoko; Tobisu, Mamoru; Fukumoto, Yoshiya; Chatani, Naoto
• Is Part Of: Nature communications. Volume 8:Issue 1(2017)
• Page Start: 1
• Page End: 8
• Publication Date: 2017-12
• Subjects: Biology -- Periodicals; Physical sciences -- Periodicals; 505
• DOI: 10.1038/s41467-017-01531-2
• Languages: English
• ISSNs: 2041-1723

Abstract

Abstract Hydroarylation is an environmentally attractive strategy which incorporates all of the atoms contained in the substrates into the desired products. Almost all the hydroarylations of norbornene reported to date involve anexo -selective reaction. Here we show theendo -selective hydroarylation of norbornene in the Rh(I)-catalyzed reaction of aromatic amides. The addition of sterically bulky carboxylic acids enhances theendo -selectivity of the reaction. The results of deuterium-labeling experiments show that both theortho -carbon and theortho -hydrogen atoms of aromatic amides were attached to the same carbon atom of the norbornane skeleton in the hydroarylation product. These results clearly suggest that hydrometalation or carbometalation, which are commonly accepted mechanisms for the catalytic hydroarylation of C–H bonds, are not involved as the key step in the present reaction, and suggest that the reaction involves a rhodium carbene complex generated from norbornene as the key intermediate. Investigating unusual organometallic pathways may help to efficiently control product selectivity in homogeneous catalysis. Here, the authors report the hydroarylation of aromatic amides with norbornene derivatives and propose the formation of a rhodium-carbene intermediate leading to rarely observedendo -products.