A Nickel-Based, Tandem Catalytic Approach to Isoindolinones from Imines, Aryl Iodides, and CO

Abstract

We describe herein a modular nickel-catalyzed synthesis of isoindolinones from imines, aryl iodides, and CO. This reaction is catalyzed by Ni­(1,5-cyclooctadiene)2 in concert with chloride salts and postulated to proceed via a tandem nickel-catalyzed carbonylation to form N-acyl iminium chloride salts, followed by a spontaneous nickel-catalyzed cyclization. A range of aryl iodides and imines have been found to be viable substrates in this reaction, providing a modular route to generate substituted isoindolinones with high atom economy.

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

“…Tandem catalyses are a hot topic in catalytic carbonylation reactions [3][4][5][6][7][8][9][10] when it comes to increasing the efficiency of chemical processes, because it makes merging different reaction steps into a single preparative step possible, reducing waste while saving time and energy [11][12][13]. Transition metal catalyzed tandem catalyses often involve hydroformylation as the initial reaction step to form reactive aldehydes [14], which constitutes a well investigated reaction that is also the subject ongoing research [15][16][17].…”

Tandem C(sp3)−H Arylation/Oxidation and Arylation/Allylic Substitution of Isoindolinones

“…[24] Nonetheless, certain classes of isoindolinones remain difficult to efficiently access. These include isoindolinones with quaternary centers or oxidation adjacent to nitrogen.…”

“…An elegant approach by Kim and coworkers is acylation of N -isopropyl benzamides with a rhodium-based catalyst (Scheme 2A). [24j] More recently Zhao circumvented the need for excess silver oxidant using TBHP in a Pd-catalyzed C–H activation/annulation reaction for the preparation of 3-hydroxyl isoindolinones (Scheme 2B). [24m] The conceptual significance of these works not withstanding, they both have practical drawbacks, including use of 3 equiv of silver and the N –isopropyl group, and excess TBHP and use of hydroxamides as N -protecting groups.…”

“…[24j] More recently Zhao circumvented the need for excess silver oxidant using TBHP in a Pd-catalyzed C–H activation/annulation reaction for the preparation of 3-hydroxyl isoindolinones (Scheme 2B). [24m] The conceptual significance of these works not withstanding, they both have practical drawbacks, including use of 3 equiv of silver and the N –isopropyl group, and excess TBHP and use of hydroxamides as N -protecting groups. Herein, we introduce in situ arylation of isoindolinones adjacent to the nitrogen to provide rapid access to a series of 3-aryl isoindolinones (Scheme 3).…”

Nickel-catalyzed allylic carbonylative coupling of alkyl zinc reagents with tert-butyl isocyanide

“…At the outset of our investigation, we recognized several issues that needed to be addressed in order to develop an effective nickel-catalyzed allylic carbonylation. First, the use of nickel catalysts in carbonylation reactions has been less explored likely due to the strong binding affinity of CO towards nickel [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] . As a rare example, the Skrydstrup group elegantly succeeded the catalytic carbonylation of primary benzylic electrophile using a nickel pincer complex with a CO-gen precursor via the slow addition of Negishi reagent to circumvent the direct Negishi coupling, although the use of allyl electrophiles received limited success with 8% ketone formation 51 .…”