Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon--trapped in a waste product--and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO₂ and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.

/pdf/using-carbon-dioxide-as-a-building-block-in-organic-4s0h674ulv.pdf

Using carbon dioxide as a building block in organic synthesis

CO2 conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO2 utilization as a measure for global CO2 mitigation. Whereas the latter focuses on reducing the end-of-pipe problem “CO2 emissions” from todays’ industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO2-based chemistry does...

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

A plethora of methods have been developed over the years so that carbon dioxide can be used as a reactant in organic synthesis. Given the abundance of this compound, its utilization in synthetic chemistry, particularly on an industrial scale, is still at a rather low level. In the last 35 years, considerable research has been performed to find catalytic routes to transform CO(2) into carboxylic acids, esters, lactones, and polymers in an economic way. This Review presents an overview of the available homogeneous catalytic routes that use carbon dioxide as a C(1) carbon source for the synthesis of industrial products as well as fine chemicals.

Transformation of Carbon Dioxide with Homogeneous Transition-Metal Catalysts: A Molecular Solution to a Global Challenge?

Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond.

Although known for over 90 years, only in the past two decades has the chemistry of diboron(4) compounds been extensively explored. Many interesting structural features and reaction patterns have emerged, and more importantly, these compounds now feature prominently in both metal-catalyzed and metal-free methodologies for the formation of B–C bonds and other processes.

Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse

to the corresponding methyl ester 2aMe.Byemploying [IPrCuCl] + tBuONa (Table 1, entry 1) or[IMesCuCl] + tBuONa (Table 1, entry 2) as a catalyst,2aMe was obtained in only trace amounts and 49% yield,respectively. In the latter case, a considerable amount (19%yield)ofcis-stilbene(3a)wasobservedasaby-product.When[IPrCuF]

Copper-catalyzed hydrocarboxylation of alkynes using carbon dioxide and hydrosilanes.

https://repository.kulib.kyoto-u.ac.jp/dspace/bitstream/2433/200260/1/j.tet.2015.02.027.pdf

Copper-catalyzed borylative transformations of non-polar carbon–carbon unsaturated compounds employing borylcopper as an active catalyst species

The highly selective copper-catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)-σ-allyl copper species, which was isolated and structurally characterized by single-crystal X-ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3-diene derivatives to afford allylboranes and homoallylboranes.

Highly Selective Copper-Catalyzed Hydroboration of Allenes and 1,3-Dienes

Arylboration of vinylarenes and methyl crotonate with aryl halides and bis(pinacolato)diboron by cooperative Pd/Cu catalysis has been developed, giving 2-boryl-1,1-diarylethanes and an α-aryl-β-boryl ester in a regioselective manner. The reaction is compatible with a variety of functionalities and amenable to be scaled-up to a gram scale with no detriment to the yield. A short synthesis of the biologically active compound CDP840 was performed using the present reaction as a key step.

Arylboration of Alkenes by Cooperative Palladium/Copper Catalysis

Copper-catalyzed highly regio- and stereoselective directed hydroboration of unsymmetrical internal alkynes: controlling regioselectivity by choice of catalytic species.

Kazuhiko Semba

Papers

Copper-catalyzed hydrocarboxylation of alkynes using carbon dioxide and hydrosilanes.

Copper-catalyzed borylative transformations of non-polar carbon–carbon unsaturated compounds employing borylcopper as an active catalyst species

Highly Selective Copper-Catalyzed Hydroboration of Allenes and 1,3-Dienes

Arylboration of Alkenes by Cooperative Palladium/Copper Catalysis

Copper-catalyzed highly regio- and stereoselective directed hydroboration of unsymmetrical internal alkynes: controlling regioselectivity by choice of catalytic species.