Reductive Functionalization Of CO2 Research Articles

Reductive functionalization of CO2 under mild reaction conditions for the catalytic synthesis of N-formamides by Mannich base based Cobalt (III) complex

Reductive functionalization of carbon dioxide is an important approach which not only reduces CO2 concentration but also functionalized it for the formation of value added chemicals. In this perspective, a hexadentate mononuclear cobalt (III) complex [CoIIIL] of Mannich base ligand (H4L) was synthesized and structurally characterized by single crystal X-ray diffraction. The electronic spectra of the complex showed two bands at 448 and 561 nm corresponds to the LMCT and d-d transitions respectively. The derived inexpensive [CoIIIL] complex was very much effective as catalyst in carbon dioxide functionalization reaction. The catalytic synthesis of mono selective N-formamide product from amines was produced through diagonal transformation of carbon dioxide in presence of polymethylhydrosiloxane (PMHS) as reducing agent and [CoIIIL] complex as catalyst. The effects of various reaction parameters were examined. Broad range of substrates (aromatic as well as aliphatic amines) smoothly produced good percentage of respective N-formamides product (72–94%) under mild reaction condition utilizing 1 atmospheric CO2. The high TON (1540–2000) and TOF value (192.5–400.0 h−1) for the catalytic reactions strongly depicted the productive nature of the [CoIII(L)] catalyst. The probable mechanestics studies clearly reveals that the [CoIIIL] complex activated the Si−H bond of PMHS to react with carbon dioxide in order to form the silyl formates intermediate for activation of N–H bonds in amines, thus leading to the excellent performance of the catalytic reaction.

Catalytic reduction and reductive functionalisation of carbon dioxide with waste silicon from solar panel as the reducing agent

Waste silicon wafer recovered from the solar panel production process acted as a reducing agent for reduction and reductive functionalization of CO2 with fluoride catalyst.

Iron-Mediated C–C Bond Formation via Reductive Coupling with Carbon Dioxide

Carbon dioxide functionalization is a potentially transformative method to enhance the sustainability of carbon-based commercial chemicals. The reductive functionalization of CO2 via C–C bond formi...

Porous Organic Polymers with Built-in N-Heterocyclic Carbenes: Selective and Efficient Heterogeneous Catalyst for the Reductive N-Formylation of Amines with CO2.

A series of porous organic polymers (POPs) based on N-heterocyclic carbene (NHC) building blocks has been prepared through an octacarbonyldicobalt complex [Co2 (CO)8 ]-catalyzed trimerization of terminal alkyne groups. By changing the monomer ratio in the copolymerization, cross-linked POPs with tunable surface areas of 485-731 m2 g-1 and pore volumes of 0.31-0.51 cm3 g-1 were easily prepared. Compared with the analogues homogeneous NHC (SIPr) catalysts, the POPs exhibited an enhanced catalytic activity and high selectivity in the reductive functionalization of CO2 with amines. The extraordinary performance of the sample could be attributed to the combination of the gas enrichment (or storage) effect, enhanced in-pore concentrations of other substrates, and advantageous micropore structures of the porous polymers. Meanwhile, these catalysts can easily be separated and recycled from the reaction systems with only a slight loss of activity. This excellent catalytic performance and facile recycling of heterogeneous catalysts make them very attractive. These NHC-containing POPs may provide a new platform for catalytic transformations of CO2 .

Transition-Metal-Free Reductive Deoxygenative Olefination with CO2.

A new transition-metal-free reductive deoxygenative olefination of phosphorus ylides with CO2, an abundant and sustainable C1 chemical feedstock, is described. This catalytic CO2 fixation afforded β-unsubstituted acrylates and vinyl ketones in good yields with broad scope and good functional group tolerance under mild reaction conditions. Cost-effective and easily handled polymethylhydrosiloxane was used as a reductant. Bis(silyl)acetal was proved to be the key intermediate in this reductive functionalization of CO2.

Reductive CO2 Fixation via Tandem C-C and C-N Bond Formation: Synthesis of Spiro-indolepyrrolidines.

We describe herein a tandem C-C and C-N bond-forming reaction in the reductive functionalization of CO2, an abundant and cheap C1 chemical feedstock. This catalytic metal-free CO2 fixation afforded spiro-indolepyrrolidines by dearomatization of tryptamine derivatives with broad scope and good functional group tolerance under mild conditions.

ChemInform Abstract: Boron‐Mediated Activation of Carbon Dioxide

AbstractReview: 103 refs.

Carbon dioxide reduction to methylamines under metal-free conditions.

The first metal-free catalysts are reported for the methylation of amines with carbon dioxide. Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new methodology enables the methylation of N-H bonds in a wide variety of amines, including secondary amines, with increased chemoselectivity.

Carbon Dioxide Reduction to Methylamines under Metal‐Free Conditions

AbstractThe first metal‐free catalysts are reported for the methylation of amines with carbon dioxide. Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new methodology enables the methylation of NH bonds in a wide variety of amines, including secondary amines, with increased chemoselectivity.

Complete Catalytic Deoxygenation of CO2 into Formamidine Derivatives

C1, seen them all: A catalytic transformation that uses CO2 as an oxygen-free C1 building block is presented. The reductive functionalization of CO2 is promoted by N-heterocyclic carbenes or guanidines as organocatalysts in the presence of amines and hydrosilanes. This diagonal strategy selectively affords benzimidazoles, quinazolinones, 3,4-dihydroquinazolines, formamidines, and their derivatives, directly from CO2 under mild conditions. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.