Iron-Catalyzed C-C Bond Cleavage of Oximes for Direct Coupling of Benzothiazole in Water.

An Fe-catalyzed coupling reaction between oxime ester and benzothiazole is described, which involves C-C bond cleavage of oxime ester via a single-electron transfer process. This iron catalytic system performed in water under mild reaction conditions offers a streamlined strategy to the construction of alkyl nitrile substituted benzothiazole derivatives. Application of this strategy for the synthesis of some key important compounds including 4-heterocyclic-3-arylbutanoic acid is also reported.

Transition metal-catalyzed arylation of unstrained C-C single bonds.

Carbon-carbon bond activation is one of the most challenging and important research areas in organic chemistry. Selective C-C bond activation of unstrained substrates is difficult to achieve owing to its inert nature and competitive side reactions, but the ubiquitous presence of C-C bonds in organic molecules makes this transformation attractive and of vital importance. Moreover, transition metal-catalyzed arylation of unstrained C-C single bonds can realize the cleavage of old C-C bonds and introduce important aryl groups into the carbon chain to construct new C-C bonds at the same time, providing a powerful and straightforward method to reconstruct the skeleton of the molecules. In recent years, considerable progress has been made in the area of direct arylation of C-C bonds, and ß-C elimination or oxidative addition strategies play key roles in these transformations. This review summarizes recent achievements of transition metal-catalyzed arylation of unstrained C-C bonds, demonstrated by various kinds of substrates including alcohol, nitrile and carbonyl compounds, and each example is detailed by its corresponding mechanism, catalytic system and scope of the substrate.

Selective Activation of Unstrained C(O)-C Bond in Ketone Suzuki-Miyaura Coupling Reaction Enabled by Hydride-Transfer Strategy.

A Rh(I)-catalyzed ketone Suzuki-Miyaura coupling reaction of benzylacetone with arylboronic acid is developed. Selective C(O)-C bond activation, which employs aminopyridine as a temporary directing group and ethyl vinyl ketone as a hydride acceptor, occurs on the alkyl chain containing a ß-position hydrogen. A series of acetophenone products were obtained in yields up to 75%.