Nickel-Catalyzed Diastereoselective Reductive Cross-Coupling of Disubstituted Cycloalkyl Iodides with Aryl Iodides

Abstract

A nickel-catalyzed direct reductive cross-coupling of disubstituted cycloalkyl iodides with aryl iodides was developed. The one-pot reaction, which is simple to operate, was capable of proceeding efficiently in a stereocontrolled manner to afford a variety of cross-coupled products with high diastereoselectivity and wide functional group tolerance.

Ni-Catalyzed Formal Cross-Electrophile Coupling of Alcohols with Aryl Halides

“…The yield for 52 was moderately decreased arising from a sterically more hindered 1,2-diol. The competency of cyclohexane 1,2-diol as exemplified by 53 is noted, as the routine coupling protocols generally require protection/deprotection one of the hydroxyl groups . For 1,2-diol bearing a benzylic hydroxyl group and a primary one as in 1-phenylethane-1,2-diol, the arylation did not generate the appreciable coupling product from either hydroxyl-connected carbon center.…”

“…The competency of cyclohexane 1,2-diol as exemplified by 53 is noted, as the routine coupling protocols generally require protection/deprotection one of the hydroxyl groups. 18 For 1,2diol bearing a benzylic hydroxyl group and a primary one as in 1-phenylethane-1,2-diol, the arylation did not generate the appreciable coupling product from either hydroxyl-connected carbon center. However, a change of TBAB to TBAC primarily resulted in 54, albeit in a low yield, wherein formation of benzyl chloride is necessary for the arylation process (cf.…”

CF3SO2Na-Mediated Five-Component Carbonylation of Triarylboroxines with TMSCF3 and THF/LiOH/NaI to Give Aroyloxyalkyl Iodides

“…Recently, the ring-opening reactions of cyclic ethers are recognized as one of the important transformations in organic synthesis, since (1) the cyclic ethers can be easily obtained from the biomass-derived levulinic acid and furfural, and (2) they can provide an effective approach to the difunctional intermediates, such as the aroyloxyalkyl iodide. Since the aroyloxyalkyl iodide is a versatile reaction center in many frequently used reactions, including cross-coupling, alkylation, addition, reduction, organometallic transformations, halogen exchange reaction, radical precursors, iodine source, etc. Therefore, their synthesis has attracted much attention in organic synthesis.…”

Ni-Catalyzed Remote Radical/Cross-Electrophile Coupling Cascade for Selective C(sp3)–H Arylation

“…Recently, with the further research of chemists, nickel-catalyzed reductive cross-coupling has matured into a relatively complete system to construct the C–C bond . As a novel tool to modify the organic skeleton, this tactic allowed available electrophiles to be coupled, which ordinarily triggers at the preactivated functional groups, such as halogens, OTf, OTs, OAc, NR 2 , NR 3 X, etc . However, without producing an active group in advance, the remote cross-electrophile coupling of inert C­(sp 3 )–H bond remains a significant challenge.…”