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).

Rhodium-Catalyzed Asymmetric Synthesis of 3,3-Disubstituted 1-Indanones

Ryo Shintani, Keishi Takatsu, Tamio Hayashi

Angewandte Chemie International Edition; 2006, 46, 3537-3737
DOI: 10.1002/anie.200700226

Summary: Chiral indanones that are difficult to obtain by other synthetic methods can be prepared via an enantioselective addition of aryl boronates to aryl alkynyl ketones. The resulting substituted indanones arrive from a tandem Rh-catalyzed C-H functionalization-cyclization sequence. This reaction utilizes a rhodium catalyst system with the asymmetric induction originating from a chiral bisphosphine ligand.

Rhodium-Catalyzed Arylative and Alkenylative Cyclization of 1,5-Enynes Induced by Geminal Carbometalation of Alkynes

Yiyun Chen and Chulbom Lee
J. Am. Chem. Soc., 2006, 128, 15598 -15599
DOI: 10.1021/ja067125+

Summary: A Rh(I)-catalyzed alkyne-boronic acid addition-cyclization has been developed to afford various alkenyl ketone derivatives. The reaction is believed to proceed through a metal vinylidene complex which eventually undergoes an intramolecular conjugate addition to provide the desired cyclized ketone adduct.

10 examples : Reaction Optimization (0-65% yield)
19 examples: Reaction Scope (11-84% yield)
2 examples: Deuterated substrates for mechanistic studies