Transition-Metal Catalyzed C-H Bond Olefination Reactions

Transition metal-catalyzed oxidative C-H bond olefination (usually called Fujiwara-Moritani reaction) has been developed to be one of the most important C-C bond-forming processes. Compared with traditional Heck reaction, Fujiwara-Moritani reaction has many advantages, such as simplicity of starting material, high atom economy, friendly to the environment, etc. But most reports about this reaction were catalyzed by palladium in the earliest reports. Relatively speaking, reactions of this type catalyzed by Rh(â…¢) and Ru(â…¡) were rarely reported. This paper focused on the Fujiwara-Moritani reaction catalyzed by Rh(â…¢) and Ru(â…¡). The main contents are as follows:We succeeded to achieve the ortho-alkenylation of phenol carbamtes using two different paths. One way was the Ru(â…¡)-catalyzed oxidation coupling between phenol carbamates and alkenes, the other is Rh(â…¢)-catalyzed hydroarylation of alkyne with phenol carbamates. Both reactions were highly regionselctive and stereoselctive. And the reaction used N, N-dimethylcarbamoyl as the directing group, which could be easily removed, giving the ortho alkenyl phenol products.We have developed the Rh-and Ru-catalyzed C2alkenylation of indoles compounds using N,N-dimethylcarbamoyl as the directing group. The two catalytic systems demonstrated high catalytic efficiency, wide olefin substrates scope, and excellent regionselctivity and stereoselectivity. Besides, we can successfully expand our methodology to pyrroles.We furnished the olefination of N-methoxybenzamides using the Ru(â…¡) as the catalyst. And by using CONH(OMe) as the oxidizing directing group, the reaction could performed in a mild reaction condition without the additional oxidant. Interestingly, depending on the kind of different alkenes, the reaction gave two types of products.