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

Abstract

The rhodium-catalyzed reductive cleavage of carbon-cyano bonds is developed using hydrosilane as a mild reducing agent. A wide range of nitriles, including aryl, benzyl, and beta-hydrogen containing alkyl cyanides are applicable to this decyanation reaction. The method can also be applied to organic synthesis; the use of benzyl cyanide as a benzyl anion equivalent and the use of a cyano group as a removable ortho-directing group are demonstrated.

Integrated Palladium‐Catalyzed Arylation of Heavier Group 14 Hydrides

“…Various electronically and structurally diverse aryl iodides were successfully used to produce the corresponding quaternary Group 14 compounds. In particular, a smoother transformation was observed when 4-iodoanisole was used as the first arylating agent, and doubly arylated compounds could be obtained in moderate to good yields by using a second aryl-A C H T U N G T R E N N U N G ating agent (Table 6, entries [1][2][3][4][5][6][7][8][9][10][11][12][15][16][17][18]. The reaction was sensitive to the electronic properties of the first arylating agent.…”

“…[12] Although, satisfactory results were obtained for the preparation of aryltrialkoxysilanes, arylation of trialkylsilane [13] has met with limited success due to the tendency to give a reduced product (Scheme 1a). [14,15] Attention has also been paid to the Pd-catalyzed arylation of trisA C H T U N G T R E N N U N G (2-furyl)germane [16] or hydrogermatrane [8e] with aryl halides. Despite these significant advances, other examples of arylation of hydrogermanes with aryl halides have not been described to date.…”

Characterization of an Anthracene Intermediate in Dynemicin Biosynthesis

“…We further deduced that the singlet could correspond to a lone B ring hydrogen atom, which was supported by chemical shift comparison to the corresponding similarly broadened singlet of anthracene. [18] Finally, we assigned the isolated doublets to either an ortho - or para -disubstituted C ring. With an anthracene core structure proposed, we were left with just one carbon atom from C 15 H 7 IOS unassigned, as well as two of twelve degrees of unsaturation (DoU).…”

Decyanative Cross‐Coupling of Cyanopyrimidines with O‐, S‐, and N‐Nucleophiles: A Route to Alkoxylpyrimidines, Aminopyrimidines and Alkylthiopyrimidines

“…If the cyano group could be employed as the leaving group, Ar–CN would become an alternative substrate to Ar–X for the cross‐coupling reaction , . Since Miller first reported the synthesis of unsymmetrical biaryls via the cross‐coupling of aryl nitriles with Grignard reagents using a phosphine‐based Ni catalyst, continued attention has been paid to decyanative cross‐coupling reactions . Recently, Kalyani described a Ni‐catalyzed cross‐coupling of aryl nitriles with azoles by using the corresponding ligand and BPh 3 at 140 °C (Scheme a) , .…”

“…[7,8] Since Miller first reported the synthesis of unsymmetrical biaryls via the cross-coupling of aryl nitriles with Grignard reagents using a phosphine-based Ni catalyst, [9] continued attention has been paid to decyanative cross-coupling reactions. [10][11][12][13][14][15][16] Recently, Kalyani described a Ni-catalyzed cross-coupling of aryl nitriles with azoles by using the corresponding ligand and BPh 3 at 140°C (Scheme 1a). [17,18] Chatani demonstrated a Rh I -catalyzed silylation reaction of aryl cyanides with hexamethyldisilane involving the cleavage of Ar-CN and Si-Si bonds (Scheme 1b).…”