Transition Metal-Catalyzed Hydrogenations

Forbes, Aaron; Verdolino, Vincenzo; Helquist, Paul; Wiest, Olaf

doi:10.1007/978-3-642-25258-7_4

Cited by 2 publications

(1 citation statement)

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“…Interestingly, from a mechanistic point of view, metal-catalyzed hydrogenation and hydrocarboxylation of alkenes show similarities (assuming an inner-sphere mechanism): initially the alkene inserts into a metal–hydride bond to form a metal–alkyl intermediate (Scheme ). ,− The nucleophilic alkyl can then react with an electrophile, which would be a proton in hydrogenation and a CO 2 molecule in hydrocarboxylation reactions. However, H + and CO 2 have different electrophilicities, and their modes of interaction with the metal at the bond formation step may differ substantially.…”

Section: Summary Of Status and Future Outlookmentioning

confidence: 99%

Enantioselective Incorporation of CO₂: Status and Potential

et al. 2017

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CO2 is a promising and sustainable carbon feedstock for organic synthesis. New catalytic protocols for efficient incorporation of CO2 into organic molecules are continuously reported. However, little progress has been made in the enantioselective conversion of CO2 to form enantioenriched molecules. In order to allow CO2 to become a versatile carbon source in academia, and in the fine chemical and pharmaceutical industries, the development of enantioselective approaches is essential. Here we discuss general strategies for CO2 activation and for generation of enantioenriched molecules, alongside selected examples of reactions involving asymmetric incorporation of CO2. Main product classes considered are carboxylic acids and derivatives (C-2 CO2 bonds), and carbonates, carbamates, and polycarbonates (C-OCO bonds). Similarities to asymmetric hydrogenation are discussed, and some strategies for developing novel enantioselective CO2 reactions are outlined.

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Section: Summary Of Status and Future Outlookmentioning

confidence: 99%

Enantioselective Incorporation of CO₂: Status and Potential

et al. 2017

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Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

Hopmann

2015

Int J of Quantum Chemistry

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Asymmetric catalysis is essential for the synthesis of chiral compounds such as pharmaceuticals, agrochemicals, fragrances, and flavors. For rational improvement of asymmetric reactions, detailed mechanistic insights are required. The usefulness of quantum mechanical studies for understanding the stereocontrol of asymmetric reactions was first demonstrated around 40 years ago, with impressive developments since then: from single-point Hartree-Fock/STO-3G calculations on small organic molecules (1970s), to the first full reaction pathway involving a metal-complex (1980s), to the beginning of the density functional theory-area, albeit typically involving truncated models (1990s), to current state-of-the-art calculations reporting free energies of complete organometallic systems, including solvent and dispersion corrections. The combined studies show that the stereocontrol in asymmetric reactions largely is exerted by nonbonding interactions, including CH/p attraction and repulsive forces. The ability to rationalize experimental results opens up for the possibility to predict enantioselectivities or to design novel catalysts on basis of in silico results.

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Transition Metal-Catalyzed Hydrogenations

Cited by 2 publications

References 145 publications

Enantioselective Incorporation of CO₂: Status and Potential

Enantioselective Incorporation of CO₂: Status and Potential

Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

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Transition Metal-Catalyzed Hydrogenations

Cited by 2 publications

References 145 publications

Enantioselective Incorporation of CO2: Status and Potential

Enantioselective Incorporation of CO2: Status and Potential

Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

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Enantioselective Incorporation of CO₂: Status and Potential

Enantioselective Incorporation of CO₂: Status and Potential