Nickel‐Catalyzed Reductive Coupling of Chlorosilanes

Abstract

Organosilanes play essential roles in many important research areas. The use of readily available chlorosilanes to catalytically access these compounds is synthetically appealing but remains a long‐standing challenge. Nickel‐catalyzed reductive cross‐coupling reaction has recently emerged as a promising protocol to arrive at this goal. This strategy allows the chlorosilanes to be coupled with various carbon electrophiles under mild conditions. These reactions afford organosilanes with improved molecular diversity, structural complexity, and functional group compatibility. This Concept article summarizes the recent advance on nickel‐catalyzed reductive C−Si couplings of chlorosilanes.

Iron‐Catalyzed Reductive C(aryl)—Si Cross‐Coupling of Diaryl Ethers with Chlorosilanes

“…[ 1‐5 ] Therefore, the development of an efficient strategy to incorporate silicon motifs into organic molecules by forming C(aryl)—Si bonds is of great interest and much importance. Among possible approaches, the catalytic coupling reactions of silicon electrophiles represent a valuable strategy to construct C(aryl)—Si bonds, [ 6‐21 ] because silicon electrophiles like chlorosilanes [ 22‐25 ] are much more abundant and cheaper starting materials than silicon organometallic reagents [ 26‐30 ] and hydrosilanes. [ 31‐33 ] Although various catalysts have been reported for the couplings of silicon electrophiles with carbon nucleophiles, [ 11‐18 ] the reductive cross‐coupling of silicon electrophiles with carbon electrophiles in the formation of C(aryl)—Si bond has remained a great challenge.…”

Cobalt-Catalyzed Cross-Electrophile Coupling of Alkynyl Sulfides with Unactivated Chlorosilanes

“…[7][8][9][10][11][12] However, compared with the well-developed XEC to form C-C bonds, the XEC between carbon electrophile and abundant and economical chlorosilanes to access organosilicon compounds is underdeveloped and highly desirable. [13][14][15] Organosilicon compounds have unique properties that are broadly applicable to synthetic chemistry, medicinal chemistry, materials science and other elds. [16][17][18][19] Very recently, the Shu, Oestreich and other group respectively reported several elegant Ni-catalyzed cross-electrophile protocols to form C-Si bond, in which a variety of aryl/vinyl/alkyl electrophiles underwent a highly e cient coupling with activated chlorosilanes (R = vinyl, H, Fig.…”

From Quaternary Carbon to Tertiary C(sp3)–Si and C(sp3)–Ge Bonds: Decyanative Coupling of Malononitriles with Chlorosilanes and Chlorogermanes Enabled by Ni/Ti Dual Catalysis

“…Dichlorosilane serves as a more abundant organosilicon source compared to monochlorosilane, making the development of their coupling methods significant. 54 The reaction with dichlorodimethylsilane yielded the monochlorosilane product, which was further converted to silanol 3av upon aqueous workup (Scheme 2c). Dichlorosilanes such as 1,1-dichlorosilinane (3aw), dichlorodiethylsilane (3ax), 1,2-dichlorotetramethyldisilane (3ay), and dichloro(3-chloropropyl)methylsilane (3az) afforded the corresponding silanols in 33−37% yields.…”

“…One of the most notable features of this reaction is the tolerance of dichlorosilanes and chlorohydrosilanes. Dichlorosilane serves as a more abundant organosilicon source compared to monochlorosilane, making the development of their coupling methods significant . The reaction with dichlorodimethylsilane yielded the monochlorosilane product, which was further converted to silanol 3av upon aqueous workup (Scheme c).…”