An octahedral cobalt(<scp>iii</scp>) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO<sub>2</sub> with epoxides under ambient conditions

Emelyanov, Mikhail A.; Stoletova, Nadezhda V.; Lisov, Alexey A.; Medvedev, Michael G.; Smol’yakov, Alexander F.; Maleev, Victor I.; Larionov, Vladimir A.

doi:10.1039/d1qi00464f

Cited by 19 publications

(23 citation statements)

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“…Notably, no kinetic resolution was observed for monosubstituted epoxides in the case of the catalyst Δ( S , S )- 1b I – . We assume that the HBD ability of the Co(III) complexes is responsible for the epoxide activation via weak hydrogen-bonding interactions and that the reaction mechanism is analogous to the mechanism described in our previous reports. , …”

Section: Results and Discussionmentioning

confidence: 48%

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R,R)-1,2-Diphenylethylenediamine

et al. 2021

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Here we report the first synthesis of two diastereomeric cationic octahedral Co(III) complexes based on commercially available (R,R)-1,2-diphenylethylenediamine and salicylaldehyde. Both diastereoisomers with opposite chiralities at the metal center (Λ and Δ configurations) were prepared. The new Co(III) complexes possessed both acidic hydrogen-bond donating (HBD) NH moieties and nucleophilic counteranions and operate as bifunctional chiral catalysts for the challenging kinetic resolution of terminal and disubstituted epoxides by the reaction with CO2 under mild conditions. The highest selectivity factor (s) of 2.8 for the trans-chalcone epoxide was achieved at low catalyst loading (2 mol %) in chlorobenzene, which is the best achieved result currently for this type of substrate.

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Section: Results and Discussionmentioning

confidence: 48%

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R,R)-1,2-Diphenylethylenediamine

et al. 2021

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“…Moreover, the epoxide opening products by water or ethanol were not observed. Thus, the water, ethanol and DMSO molecules are functioning as competitive H‐bond acceptor inhibitors, preventing the epoxide activation by the HBD catalyst Λ( R , R )‐ 2 [15d] …”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…Based on the previous works, [15d,37] we have proposed a reaction mechanism consisting of four steps (Figure 3). Notably, previous investigations showed that attack of an iodide anion at both α‐ [15d,24] and β‐carbons [23] of IM1 are feasible (blue and red arrows in Figure 3), so we consider both these routes. As model reactions we choose CO 2 fixation with each enantiomer of styrene oxide and propylene oxide under catalysis by Δ( S , S )‐ 1 a , Δ( S , S )‐ 1 b , Δ( R , R )‐ 2 and Λ( R , R )‐ 2 .…”

Section: Resultsmentioning

confidence: 99%

“…In our modeling TS1 incorporates only one molecule of catalyst in agreement with the experimentally measured first‐order in it (see Figure 2). In our previous article [15d] we have used translational entropy correction to find out whether the second catalyst molecule can play the role of iodide anion carrier in the initial S N 2 attack. However, that correction relied on a hypothesis that iodide anion has the same reactivity in the solution and in the S complex.…”

Section: Resultsmentioning

confidence: 99%

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Cobalt(III) Complexes as Bifunctional Hydrogen‐Bond Donor Catalysts Featuring Halide Anions for Cyclic Carbonate Synthesis at Ambient Temperature and Pressure: A Mechanistic Insight

et al. 2022

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The metal-templated hydrogen bond donors (HBD) are prospective catalytic systems for the activation of organic molecules in chemical reactions. Here we report the application of the chiral cationic Co(III) complexes based on commercially available (S,S)-1,2-diaminocyclohexane and (R,R)-1,2-diphenylethylendiamine and salicylaldehydes with an iodide counter-anion as bifunctional one-component hydrogen bond donor/nucleophilic catalysts for the conversion of carbon dioxide with epoxides into valuable cyclic carbonates under solvent-and co-catalyst free conditions. We demonstrated that (R,R)-1,2-diphenylethylendiamine based complex Λ(R,R)-2 is superior to (S,S)-1,2-diaminocyclohexane based Δ(S,S)-1 a catalyzing the reaction at ambient conditions (RT and 1 bar CO 2 ). The TON and TOF values of 850 and 35 h À 1 , respectively, were achieved at low catalyst loading (0.1 mol %) at 10 bars of CO 2 and 100 °C. Furthermore, the Co(III) complexes catalyzed the reaction with diluted air/CO 2 mixture (15 vol % of CO 2 ) producing the desired styrene carbonate in up to 75% yield. A plausible catalytic cycle consistent with all experimental observations was proposed based on DFT calculations. The DFT calculations elucidated the difference in the ring opening step in cases of propylene oxide and styrene oxide. In addition, the kinetic resolution of terminal epoxides was observed with selectivity factor (s) of up to 1.6 in case of the complex Λ(R,R)-2.

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Enantioselective Syntheses of Multiply Functionalized Six‐Membered Carbocycles from Nitroalkenes and γ,δ‐Unsaturated ß‐Ketoesters using Chiral Catalysts Derived from Cobalt(III) and 1,2‐Diphenylethylenediamine

Wang,

Bhuvanesh,

Gladysz

2023

Adv Synth Catal

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Condensations of the title educts R4CH=CH(C=O)CH2CO2Et and R6CH=CHNO2 in the presence of NEt3 and the catalyst Λ‐[Co((S,S)‐dpen)3]3+2Cl−B(C6F5)4− (both 10 mol%, 0 °C; dpen=1,2‐diphenylethylenediamine) afford R6CHCH(NO2)CH(R4)CH2C(OH)CCO2Et, with three contiguous carbon stereocenters, as >99:1 to 85:15 mixtures of diastereomers (ten examples). The major diastereomers are isolated in 81–63% yields and 97–76% ee. When R4 and R6 are both aryl groups, additions of 1,1,3,3‐tetramethylquanidine/CH3CN epimerize the CHNO2 moieties, affording 78:22 to 67:33 mixtures of the new/old diastereomers (2 h, RT). Alternatively, epimerization to >99:1 mixtures occurs spontaneously over 4 weeks in hexanes/isopropanol. These transformations entail two consecutive Michael additions, and two crystal structures confirm the relative and absolute product configurations. These assignments are supported by NMR data in solution and literature studies of similar compounds. Overall, catalyst Λ‐[Co((S,S)‐dpen)3]3+2Cl−B(C6F5)4− affords superior yields and enantio‐ or diastereoselectivities compared to those previously reported for the title reaction.

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An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO₂ with epoxides under ambient conditions

Abstract: Hydrogen bond donors (HBD) are a sustainable privileged class of catalysts which are broadly used for the activation of compounds in synthetic chemistry. Among them, the metal-templated HBD complexes present...

Cited by 19 publications

References 106 publications

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R,R)-1,2-Diphenylethylenediamine

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R,R)-1,2-Diphenylethylenediamine

Cobalt(III) Complexes as Bifunctional Hydrogen‐Bond Donor Catalysts Featuring Halide Anions for Cyclic Carbonate Synthesis at Ambient Temperature and Pressure: A Mechanistic Insight

Enantioselective Syntheses of Multiply Functionalized Six‐Membered Carbocycles from Nitroalkenes and γ,δ‐Unsaturated ß‐Ketoesters using Chiral Catalysts Derived from Cobalt(III) and 1,2‐Diphenylethylenediamine

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An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO2 with epoxides under ambient conditions

Abstract: Hydrogen bond donors (HBD) are a sustainable privileged class of catalysts which are broadly used for the activation of compounds in synthetic chemistry. Among them, the metal-templated HBD complexes present...

Cited by 19 publications

References 106 publications

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R,R)-1,2-Diphenylethylenediamine

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R,R)-1,2-Diphenylethylenediamine

Cobalt(III) Complexes as Bifunctional Hydrogen‐Bond Donor Catalysts Featuring Halide Anions for Cyclic Carbonate Synthesis at Ambient Temperature and Pressure: A Mechanistic Insight

Enantioselective Syntheses of Multiply Functionalized Six‐Membered Carbocycles from Nitroalkenes and γ,δ‐Unsaturated ß‐Ketoesters using Chiral Catalysts Derived from Cobalt(III) and 1,2‐Diphenylethylenediamine

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An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO₂ with epoxides under ambient conditions