Selective Three-Component Reductive Alkylalkenylation of Unbiased Alkenes via Carbonyl-Directed Nickel Catalysis

Abstract

A Ni-catalyzed enantioselective reductive three-component alkylalkenylation of β,γ-alkenyl ketones with cis-alkenyl iodides and fluoroalkyl iodides in the presence of Mn is reported. By leveraging five-membered nickellacycles stabilized by pendant ketone group and chiral bis­(oxazoline) (BiOx) ligand, this three-component protocol allows efficient access to enantioenriched β-alkenyl ketones from simple starting materials. Ni-catalyzed three-component alkylalkenylation of diverse electronically unbiased alkenes beyond β,γ-alkenyl ketones that enables regioselective construction of two C­(sp3)–C­(sp3) and C­(sp3)–(sp2) bonds in one single operation is also demonstrated.

Nickel‐Catalyzed Markovnikov‐Selective Hydrodifluoromethylation of Alkynes Using BrCF2H

“…Switching the dtbbpy ligand to PPh 3 or PCy 3 gave no formation of product 2, indicating the critical effect of the bidentate nitrogen ligand (entries 10,11). Replacing (EtO) 2 MeSiH with other silanes such as Ph 2 SiH 2 , (EtO) 3 SiH, and (Me 2 SiH) 2 O led to decreased yields with varied levels (entries [12][13][14]. According to Hu's report, [15] the use of (EtO) 2 MeSiH could be beneficial to facilitate the formation and insertion of nickel hydride.…”

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

“…More recently, the same group employed a similar strategy for the enanatioslective arylfluoroalkylation of allyl esters (mostly indole‐3‐carboxylates) with fluoroalkyl iodides and (hetero)aryl bromides with excellent yields and high enantioselectivity (over 89:11 er) [192] . Later on, they adopted the same concept for highly enantioselective fluoroalkylation‐alkenylation of β,γ‐alkenyl ketones with cis ‐alkenyl iodides, benefiting from the stabilization of the nickellacycle intermediate by pendant carbonyl [193] …”

Copper-Catalyzed Hydroxyperfluoroalkylation of Unactivated Alkenes: Access to β-Perfluoroalkyl Alcohols

“…Based on the above-mentioned mechanistic studies and previous reports, ,, a plausible mechanism is illustrated in Scheme . Initially, copper salt LCuX was converted to LCu-Bpin intermediate A in the presence of B 2 pin 2 and Cs 2 CO 3 .…”