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Carbon Dioxide and Organometallics pp 199–223Cite as

Ni-Catalyzed Synthesis of Acrylic Acid Derivatives from CO2 and Ethylene

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Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 53))

Abstract

The story of nickelalactones finally ends well. Over three decades after their discovery, catalytic processes have been successfully established to synthesize acrylate derivatives from ethylene and abundantly available carbon dioxide. The performed research during this time in the CO2 utilization via C–C bond formation with olefins is presented within this review. It gives detailed insights starting from the initial milestones in the 1980s up to modern strategies through cleavage auxiliaries. Different approaches are examined from an experimental and theoretical point of view as the choice of cleavage agent and the corresponding ligand is crucial for the reaction control and suppression of undesired pathways. Methylation of the lactone species led to a first successful liberation of methyl acrylate in stoichiometric amounts. These results led to a vast progress in research with auxiliaries afterward. Upon addition of Lewis acids or strong sodium bases, finally the first two different catalytic routes have been established which are discussed in detail.

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Abbreviations

ArF :

3,5-Bis(trifluoromethyl)phenyl

bpy:

2,2′-Bipyridine

BenzP*:

(R,R)-(+)-1,2-Bis(tert-butylmethylposphino)benzene

BTPP:

(tert-Butylimino)tris(pyrrolidino)phosphorane

cdt:

1,5,9-Cyclododecatriene

cod:

1,5-Cyclooctadiene

Cy:

Cyclohexyl

dcpe:

1,2-Bis(dicyclohexylphosphino)ethane

dcpp:

1,3-Bis(dicyclohexylphosphino)propane

dippf:

1,1′-Bis(di-iso-propylphosphanyl)ferrocene

dppb:

1,4-Bis(diphenylphosphino)butane

dppe:

1,2-Bis(diphenylphosphino)ethane

dppf:

1,1′-Bis(diphenylphosphanyl)ferrocene

dppm:

Bis(diphenylphosphino)methane

dppp:

1,3-Bis(diphenylphosphino)propane

dtbpe:

1,2-Bis(di-tert-butylphosphino)ethane

dtbpm:

Bis(di-tert-butylphosphino)methane

dtbpp:

1,3-Bis(di-tert-butylphosphino)propane

DBU:

1,8-Diazabicyclo[5.4.0]undec-7-ene

DFT:

Density functional theory

DIPEA:

N,N-Di-iso-propylethylamine

IR:

Infrared

L:

Ligand

Lac:

2-Oxacyclopentan-3-one

MMA:

Methyl methacrylate

NMR:

Nuclear magnetic resonance

p.a.:

Per year

PAA:

Poly(acrylic acid)

PANa:

Sodium poly(acrylate)

PMMA:

Poly(methyl methacrylate)

rt:

Room temperature

thf:

Tetrahydrofuran

tmeda:

N,N,N′,N′-Tetramethylethylenediamine

TOF:

Turnover frequency

TON:

Turnover number

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  1. Wacker-Lehrstuhl für Makromolekulare Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching bei München, Germany

    Sebastian Kraus & Bernhard Rieger

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  1. Sebastian Kraus
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  2. Bernhard Rieger
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  1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China

    Xiao-Bing Lu

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Kraus, S., Rieger, B. (2015). Ni-Catalyzed Synthesis of Acrylic Acid Derivatives from CO2 and Ethylene. In: Lu, XB. (eds) Carbon Dioxide and Organometallics. Topics in Organometallic Chemistry, vol 53. Springer, Cham. https://doi.org/10.1007/3418_2015_111

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