Substrate‐Controlled Product Divergence: Conversion of CO₂ into Heterocyclic Products

Abstract

Substituted epoxy alcohols and amines allow substrate-controlled conversion of CO2 into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach results in an unusual scope of CO2-derived products by initial activation of CO2 through either the amine or alcohol unit, thus providing nucleophiles for intramolecular epoxy ring opening under mild reaction conditions. Control experiments support the crucial role of the amine/alcohol fragment in this process with the nucleophile-assisted ring-opening step following an SN i pathway, and a 5-exo-tet cyclization, thus leading to heterocyclic scaffolds.

A One‐Pot Synthesis of N‐Aryl‐2‐Oxazolidinones and Cyclic Urethanes by the Lewis Base Catalyzed Fixation of Carbon Dioxide into Anilines and Bromoalkanes

“…[13] To our delight, the high yield obtained of 3 a (92 % yield) was the general trend observed for several anilines with either electron-donating (Me, tBu, OMe) or -withdrawing (Cl) substituents (3 b-j, 72-92 %), with the notable exception of NO 2 that diminished enough the nucleophilicity to prevent any conversion (3 d). Notably, we also found that the reaction tolerates rather well the presence of a coordinating heteroatom (3 w, 64 %), or severe steric hindrance near the reaction site (3 x, 75 %).…”

“…[12] Alternatively, two reports this year have disclosed the construction of NAOs by fixating simultaneously CO 2 into anilines and epoxides. [13] A contribution by Kleij and co-workers describes the partnership of a Al-based Lewis acid with a source of bromide to effectively catalyze the conversion of epoxy amines into NAOs at room temperature, yet using 10 bar of CO 2 .…”

“…We then sought to investigate the conversion of anilines bearing pharmaceutically important groups that are barely compatible with the drastic conditions used in many of the previous reports. [13] In practice, the reaction accommodated well the presence of groups (Br, I, B(pin)) that may provide a versatile synthetic handle for further transformations on the aniline ring (3 k-m, 55-83 %). Furthermore, the presence of one or two, F or CF 3 groups, in different locations of the aniline ring did not compromise the reaction yields (3 n-u, 57-74 %).…”

Enantioselective Incorporation of CO2: Status and Potential

“…Yu et al 97 reported CuI-catalyzed cyclization of primary amine carbamate salts with aldehydes and aromatic terminal alkynes. In 2015, Kleij and coworkers 98 reported the synthesis of racemic oxazolidinones from epoxy amines (Scheme 21A). A mechanistic investigation with an enantiopure epoxy alcohol showed chirality inversion at the β-carbon, implying that the reaction likely proceeds through an intramolecular attack at the β-carbon.…”

Regioselective Ring‐Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]‐FeIII Triflate Complex

“…The reactionp roceeded with high activity (initial turnover frequency of 1680 h À1 for EtOH) and selectivity( > 95 %) toward the formation of twelve monoalkyl glyceryl ethers (MAGEs) in ar egioselective fashion (84-96 %y ield of the non-symmetric regioisomer). [12][13][14] We have recentlys hown that GLYc an be conveniently obtained as a value-added product from biobasedepichlorohydrin (ECH) productionp lants (EPICEROL process, Solvay), [15] thereby enhancing the environmental sustainability of the entireE CH chain as well as interest towards GLYc onversiont ov aluable chemicals such as polymers, [16] drugs, [17] diols, [18][19][20] solketal, [21,22] and organic carbonates. [1][2][3][4][5][6][7] In particular, since the discoveryo fm anyu seful synthetic strategies that have given access to aw ide variety of chiral epoxides, this reaction has becomeani mportant entry in the toolbox of organic synthesis for obtaining enantiopure molecules.…”