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 DOI
Katherine Wang, Nattamai Bhuvanesh, John A. Gladysz

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4692 - 4700

Published: Nov. 21, 2023

Abstract Condensations of the title educts R 4 CH=CH(C=O)CH 2 CO Et and 6 CH=CHNO in presence NEt 3 catalyst Λ‐[Co(( S , )‐dpen) ] 3+ 2Cl − B(C F 5 )4 (both 10 mol%, 0 °C; dpen=1,2‐diphenylethylenediamine) afford CHCH(NO )CH(R )CH C(OH)CCO Et, with three contiguous carbon stereocenters, as >99:1 to 85:15 mixtures diastereomers (ten examples). The major are isolated 81–63% yields 97–76% ee. When both aryl groups, additions 1,1,3,3‐tetramethylquanidine/CH CN epimerize CHNO moieties, affording 78:22 67:33 new/old (2 h, RT). Alternatively, epimerization occurs spontaneously over weeks hexanes/isopropanol. These transformations entail two consecutive Michael additions, crystal structures confirm relative absolute product configurations. assignments supported by NMR data solution literature studies similar compounds. Overall, ) affords superior enantio‐ or diastereoselectivities compared those previously reported for reaction.

Language: Английский

Surface science approach to the heterogeneous cycloaddition of CO2 to epoxides catalyzed by site-isolated metal complexes and single atoms: a review DOI Creative Commons
Valerio D’Elia, Arjan W. Kleij

Green Chemical Engineering, Journal Year: 2022, Volume and Issue: 3(3), P. 210 - 227

Published: Feb. 5, 2022

The cycloaddition of CO2 to epoxides afford cyclic organic carbonates is an increasingly relevant non-reductive strategy convert useful products able serve as high-boiling solvents, chemical intermediates, and monomers for the preparation more sustainable polymers. development efficient robust heterogeneous catalysts such transformation is, therefore, crucial can be carried out by several strategies that often require sophisticated and/or expensive networks, linkers, or compounds. A different approach CO2-epoxide coupling applying surface science methodologies graft molecular fragments single atoms on various supports leading well-defined active sites. In this context, organometallic chemistry (SOMC), along with comparable methodologies, a valuable efficient, single-site Lewis acids target reaction metal oxides, whereas, other grafting applied prepare analogous kinds surfaces. Finally, we discuss very recent advances in application atom towards highly epoxides. Overall, show prepared facile hold significant potential future synthesis from CO2.

Language: Английский

Citations

50
Recent Advancements in Metal‐catalysts Design for CO2/Epoxide Reactions DOI
Francesco Della Monica, Carmine Capacchione

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(8)

Published: July 5, 2022

Abstract Carbon dioxide utilization is considered an effective strategy to mitigate the carbon footprint of chemical industry. Among other uses, incorporation into cyclic organic carbonates (COCs) and aliphatic polycarbonates (APCs) has received great attention in field homogeneous catalysis. After few decades research activity, a wide range metal‐based catalytic systems been reported promote this reaction. Nonetheless, better comprehension apparently simple reaction mechanism such transformations reached only recent years. This, turn, allowed for design new guided by clearer mechanistic picture. In review, we present most advancements field, distinguishing between catalysts COCs APCs production classified on bases their ligand structures.

Language: Английский

Citations

21
2-Picolinic acid as a naturally occurring hydrogen bond donor for the preparation of cyclic carbonates from terminal/internal epoxides and CO2 DOI
Ali Rostami,

Amirhossein Ebrahimi,

Mohammed Al-Jassasi

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(23), P. 9069 - 9083

Published: Jan. 1, 2022

Naturally sourced 2-picolinic acid was discovered as an off-the-shelf, non-toxic, and inexpensive HBD catalyst for the cycloaddition of CO 2 to both internal terminal epoxides prepare cyclic carbonates at low loadings.

Language: Английский

Citations

20
Cycloaddition Reactions of Epoxides and CO2 Catalyzed by Bifunctional Rare‐Earth Metal Complexes Bearing Amino‐Bridged Tris(phenolato) Ligands DOI
Yongjie Chen, Yanwei Wang,

Jun Nong

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(14), P. 1571 - 1581

Published: March 15, 2024

Comprehensive Summary Eight zwitterionic rare earth metal complexes stabilized by amino‐bridged tris(phenolato) ligands bearing quaternary ammonium side‐arms were synthesized and characterized. These used as single‐component catalysts for the cycloaddition of CO 2 epoxides, their catalytic activities are obviously higher than those binary analogues. Further studies revealed that halide anions (Cl – , Br I ) influenced activity, lanthanum complex iodide anion showed highest activity this addition reaction. A variety mono‐substituted epoxides converted to cyclic carbonates in good excellent yields (55%—99%) with high selectivity (> 99%) at 30 °C 1 bar whereas internal required both reaction temperatures (60—120 °C) catalyst loading (2 mol%) yields. The was recyclable four times without noticeable loss activity. Based on results kinetic situ IR reactions, a plausible mechanism proposed.

Language: Английский

Citations

4
Iron(III) Complexes with Pyridine Group Coordination and Dissociation Reversible Equilibrium: Cooperative Activation of CO2 and Epoxides into Cyclic Carbonates DOI
Yongbo Zhou,

Fei Chen,

Zhi‐Hong Du

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(35), P. 16491 - 16506

Published: Aug. 20, 2024

Herein, a series of [ONSN]-type iron(III) complexes were synthesized. A binary catalytic system in combination with iron and tetrabutylammonium bromide (TBAB) exhibited high activity for the synthesis cyclic carbonates from CO

Language: Английский

Citations

4
Cycloaddition of di-substituted epoxides and CO2under ambient conditions catalysed by rare-earth poly(phenolate) complexes DOI

Yuting Qing,

Tiantian Liu, Bei Zhao

et al.

Inorganic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(12), P. 2969 - 2979

Published: Jan. 1, 2022

Lanthanum complex 1/TBAI is the first catalyst to achieve cycloaddition of 1,2-disubstituted epoxides with 1 bar CO 2 at room temperature. A DFT study discloses that poly(phenolato) ligand plays a key role in product dissociation step.

Language: Английский

Citations

16
Post-Modification of Octahedral Chiral-at-Metal Cobalt(III) Complexes by Suzuki–Miyaura Cross-Coupling and Evaluation of Their Catalytic Activity DOI
Olga V. Khromova, Mikhail A. Emelyanov,

Nadezhda V. Stoletova

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(18), P. 2505 - 2513

Published: Jan. 19, 2023

A family of well-defined Λ- and Δ-configured octahedral cationic chiral-at-cobalt catalysts were expanded through a straightforward postcomplexation the bromine-functionalized Co(III) complexes based on (R,R)-1,2-cyclohexanediamine (S,S)-1,2-diphenylethylenediamine by Suzuki–Miyaura cross-coupling reaction (CCR) with arylboronic acids. The corresponding modified isolated standard silica column chromatography up to 65% yields. Indeed, it is first example direct modification ligand sphere chiral CCR. It was observed for time that metal center epimerized during process at transmetalation stage palladium catalyst in case minor diastereomers (Δ(R,R)-1 Λ(S,S)-2). Next, efficacies obtained metal-templated 1–4 evaluated benchmark asymmetric reactions order compare their catalytic activity. Chiral have been examined as hydrogen bond donor (HBD) such important epoxidation chalcone fixation CO2 into valuable cyclic carbonates.

Language: Английский

Citations

8
Porous polymer beads with grafted poly(tertiary amine) as catalysts for fixation of carbon dioxide into propylene carbonate DOI

Weiwei Niu,

Zhiyi Yin,

Dong Chen

et al.

Polymer Bulletin, Journal Year: 2024, Volume and Issue: 81(13), P. 12089 - 12103

Published: May 6, 2024

Language: Английский

Citations

2
Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 DOI Creative Commons
Mikhail A. Emelyanov,

Alexander V. Bachinskiy,

Yana V. Derkach

et al.

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: 12, P. 100115 - 100115

Published: Nov. 28, 2024

Language: Английский

Citations

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

Nadezhda V. Stoletova,

Alexander F. Smol’yakov

et al.

Inorganic Chemistry, Journal Year: 2021, Volume and Issue: 60(18), P. 13960 - 13967

Published: Aug. 27, 2021

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 metal center (Λ Δ configurations) were prepared. The new possessed both acidic hydrogen-bond donating (HBD) NH moieties nucleophilic counteranions operate as bifunctional chiral catalysts for challenging kinetic resolution terminal disubstituted epoxides by reaction CO2 under mild conditions. highest selectivity factor (s) 2.8 trans-chalcone epoxide was achieved low catalyst loading (2 mol %) in chlorobenzene, which is best result currently this type substrate.

Language: Английский

Citations

15