Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.
We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2](-) may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Tanvi S
TS
Ratani
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Shoshana
S
Bachman
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Gregory C
GC
Fu
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Jonas C
JC
Peters
D000478:Alkylation; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D055668:Photochemical Processes; D013696:Temperature
D006843:Hydrocarbons, Chlorinated; D009570:Nitriles; D002244:Carbon; D003300:Copper