Photochemistry of alkyl halides. 4. 1-Norbornyl, 1-norbornylmethyl, 1- and 2-adamantyl, and 1-octyl bromides and iodides

Photoinduced, Copper-Catalyzed Carbon–Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature

“…At the same time, we also considered the possibility that the transient formation of an alkyl iodide might open the door to a copper-free cyanation pathway (e.g., eq 6), since homolysis of an alkyl–I bond can occur upon irradiation at 254 nm. 20,21,22,23 …”

“…21 To gain insight into whether a chain process might be operative under our cyanation conditions, we determined the quantum yield for the reaction of cyclohexyl chloride with TBACN. 28 The observed value of 0.030 (.002) does not suggest a chain pathway.…”

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

“…2a,b). Inspired by Kropp's seminal work [25][26][27][28] on the heterolytical cleavage of alkyl C-I bond to form carbocations under ultraviolet irradiation in highly polar solvents, we hypothesized that by harmonizing the rate of C-I bond cleavage (related to the light intensity) and the nucleophilicity of the terminal alkyne, the coupling between alkynes and alkyl iodides can be accomplished directly via radical or carbocation intermedates, in the absence of any transiton metals (Fig. 2c).…”

Synthesis of 1-adamantyl alkyl ethers by intermolecular dehydration of 1-adamantanol with alcohols catalyzed by copper compounds

“…The reaction is performed under irradiation using a low-pressure mercury lamp (λ 254 nm) for 24-48 h under nitrogen atmosphere. [3][4][5][6] Another approach for the synthesis of 1-adamantyl methyl ether in 65-90% yield involves the reactions of 1-chloro-or 1-iodoadamantanes with methanol in the presence of silver perchlorate. 7 The reaction is partially reversible; therefore the precipitated AgCl is immediately filtered off.…”