Rhodium-Catalyzed Reductive Cleavage of Carbon−Cyano Bonds with Hydrosilane: A Catalytic Protocol for Removal of Cyano Groups

Mamoru Tobisu, Ryo Nakamura, Yusuke Kita and Naoto Chatani

J. Am. Chem. Soc., 2009, 131, 3174–3175

DOI: 10.1021/ja810142v

Summary: Recently, transition metal activation of the C-CN bond has been an area of intense synthetic activity. Much of the previous work has been centered around Ni(0) mediated C-C bond formation. The Chatani group has developed a rhodium-catalyzed hydrosilane mediated reductive cleavage of the C−CN bond. The reaction has a large synthetic scope including decyanation of aryl- and alkyl nitriles. Additionally, the reaction has a very good functional group tolerence and can be performed in the presence of ester, ether, amino and amide groups. This synthetic method was also demonstrated in several examples where a cyano group was present as a removable ortho-directing group (via a C-H functionalization process).

Efficient Boron−Copper Additions to Aryl-Substituted Alkenes Promoted by NHC−Based Catalysts. Enantioselective Cu-Catalyzed Hydroboration Reactions

Yunmi Lee and Amir H. Hoveyda
J. Am. Chem. Soc., 2009, 131, 3160–3161
DOI:10.1021/ja809382c

Summary: This paper describes the development of a Cu-catalyzed formal hydroboration of olefinic substrates (styrene derivatives). The reaction is highly regio and stereoselective affording the organoboron products in moderate to high yield. The reaction utilizes a copper NHC complex (0.5-7.5 mol%) and pinacolatoboron as the boron source. In the asymmetic variant the er's range from 86/14 to 99/1.