Tandem Functionalization‐Carboxylation Reactions of π‐Systems with CO₂

Abstract

The tandem catalytic functionalization/carboxylation of double as well as triple carbon‐carbon bonds with CO2 represent an emerging research area in synthetic organic methodology. In particular, the combination of mild reaction conditions, stoichiometric acceptor/donorless conditions (visible light photoredox catalysis) and chiral catalysts contributed to a rapid development of this intriguing research area capable of creating chemical diversity/ complexity from readily available unsaturated hydrocarbons and CO2 as a C1‐buinding block. The most recent developments in the field have been collected in the present review article and organized, based on the different sets of π‐systems/intermediates/reactive partners employed (i.e., nickelalactones, organo‐halides) as well as synthetic strategies (i.e., visible‐light photo redox catalysis).

Merging C–C σ-bond activation of cyclobutanones with CO2 fixation via Ni-catalysis

“…8 In particular, the valorization of carbon dioxide via metal-, metal-free, photo- and electrocatalyzed cascade carboxylative processes has rapidly emerged as a valuable route towards molecular complexity. 9–11…”

Theoretical Insights into the Regiodivergence in Ni-Catalyzed [2+2+2] Cycloaddition of Unsymmetric Diynes and CO2

“…Transforming CO 2 into other organic compounds as a feedstock remains challenging, often requiring sluggish reactivity and harsh reaction conditions such as high temperatures and pressure [7][8][9]. Various processes and technologies for activating CO2 are under development in different research fields, and recent decades have witnessed significant contributions from organic chemists in the field of CO 2 chemistry [10][11][12][13][14][15][16]. Although the fixation of CO 2 was initially conducted using stoichiometric organometallic reagents under harsh reaction conditions, several transition metal catalysis methods have emerged as promising approaches for the utilization of CO 2 in recent years.…”

Metal‐Catalyzed Carbonylation Reactions with CO2: An Update

“…[1] Despite the current daily discovery of new methodologies for the fixation/valorization of CO 2 , [2] the seek for an expanded portfolio on sustainable and site-selective carbon dioxide-based transformations is ubiquitous within the chemical community. These can either be realized by enhancing the reactivity of the organic scaffold towards CO 2 capture [3] or by emphasizing the chemical flexibility of the carboxylic carbon.…”