Post on 01-Apr-2015
William Schulz Bechara
Charette Group - Charette Group - LiteratureLiterature Meeting MeetingMay 2May 2ndnd, 2012, 2012
Life of Synthetic COLife of Synthetic CO22, Environmental Impact, , Environmental Impact,
Chemical Synthesis and Industrial ApplicationsChemical Synthesis and Industrial Applications
World's Top Market Value
1) Oil&Gas : 5
2) Telecommunication : 2
3) Eletronics : 4
4) Pharma : 3
5) Food : 2
6) Natural Resources
Exploration : 2
7) Bank : 3
8) Consumer goods &
Retailing : 3
9) Internet :1
3117533162198178248347546
The world still relies heavily today on fossil fuels to cover
about 80% of its energy needs
CO2 – One of the Largest Waste Product
Electricity Without Carbon, Nature News Feature, 14 August 2008, 454.
The world still relies heavily today on fossil fuels to cover
about 80% of its energy needs
Global Warming?
Image from http://berkeleyearth.org/analysis - by Berkeley Earth Surface Temperature Institute. Retrieved 2012-05-02.
Global Warming?
a) Briffa, K. R.; Osborn, T. J.; Schweingruber, F. H.; Harris, I. C.; Jones, P. D.; Shiyatov, S. G.; Vaganov, E. A. J. Geophys. Res. 2001, 106, 2929. b) Esper, J.; Cook, E. R.; Schweingruber, F. H. Science 2002, 295, 5563. c) Jones, P.D.; Briffa, K. R.; Barnett, T. P.; Tett, D. F. B. The Holocene, 1998, 8, 455. d) Mann, M.E., R.S. Bradley and M.K. Hughes, Nature, 1998, 392, 779.; Geophysical Research Letters, 1999, 26, 759. e) Jones, P. D.; Mann, M. E. Reviews of Geophysics, 2004, 42, RG2002 1-42.
Year
CO2 vs Global Warming?
Petit, J. R et al Nature 1999, 399, 429.
CO2 and Global Warming?
a) Petit, J. R et al. Nature 1999, 399, 429. b) Barnola, J.-M.; Raynaud, d.; Korotkevich, Y. S.; Lorius C. Nature, 1987, 329, 408. c) Lorius, C.; Jouzel, J.; Raynaud, D.; Hansen, J.; Le Treut, H. Nature, 1990, 347, 139. d) Martıinez-Garcia, A. et al. Nature 2011, 476, 312. e) Tripati, A. K. et all. Science 2009, 326, 1394. f) Shakun, J. D. et al. Nature 2012, 484, 49.
[...] records suggests a close link between CO2 and climate [...] The role and relative importance of CO2 in producing these climate changes remains unclear [...]
CO2 Emissions Going Up
Aresta, M. Carbon Dioxide as Chemical Feedstock 2010 Wiley, Weinheim.
CO2 Emissions : Natural vs Human (Anthropogenic CO2)
Solomon, S.; Qin, D.; Manning, M. ; Chen, Z.; Marquis, M. ; Averyt, K. B.; Tignor, M.; Miller, H. L. IPCC Fourth Assessment Report: Climate Change, 2007, chap. 7, 515. at http://www.ipcc.ch/publications_and_data/publications_ipcc_fourth_assessment_report_wg1_report_the_physical_science_basis.htm c) Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43.
3.2 GtC/y in 19903.2 GtC/y in 199024 GtC/y in 201024 GtC/y in 2010
Gigatons of C/year Gigatons of C/year
Life of Synthetic CO2
Image from http://www.theurbn.com/2011/06/capturing-time-bp-and-the-future by Hayley Peacock, Capturing Time: BP And The Future, UubanTimes news. Retrieved 2012-05-02.
CO2 Storage / Enhanced Oil recovery
a) Image from http://www.universetoday.com/75740/carbon-capture by Matt Williams, Carbon Capture, Universe Today news. Retrieved 2012-05-02 b) Carbon Capture and Storage (CCS). Global CCS Institute. Retrieved 2012-05-02.
CO2 Storage / Enhanced Oil recovery
a) Image from http://www.universetoday.com/75740/carbon-capture by Matt Williams, Carbon Capture, Universe Today news. Retrieved 2012-05-02 b) Carbon Capture and Storage (CCS). Global CCS Institute. Retrieved 2012-05-02.
CO2 Emissions – CCS Project
Image from http://www.metoffice.gov.uk/avoid/files/washington/AVOID_Fennel.pdf - by Dr Paul Fennell, Dr Nick Florin, Grantham Institute for Climate Change, Imperial College Centre for CCS. Professor Nilay Shah and Dr Niall McGlashan, Centre for Process Systems Engineering
Carbon Capture and Storage (CCS) Project
Image from http://www.metoffice.gov.uk/avoid/files/washington/AVOID_Fennel.pdf - pdf presentation from Dr Paul Fennell, Dr Nick Florin, Grantham Institute for Climate Change, Imperial College Centre for CCS. Professor Nilay Shah and Dr Niall McGlashan, Centre for Process Systems Engineering
CCS Project - Operational
Image from http://www.metoffice.gov.uk/avoid/files/washington/AVOID_Fennel.pdf - pdf presentation from Dr Paul Fennell, Dr Nick Florin, Grantham Institute for Climate Change, Imperial College Centre for CCS. Professor Nilay Shah and Dr Niall McGlashan, Centre for Process Systems Engineering
CO2 Scrubbing (Purification)
O2, N2 and other gas
Cold Hot
AminesMgO
M-oxides
CO2, H2O, CO, O2, N2 and other gas
MacDowell, N. et al. Energy Environ. Sci. 2010, 3, 1645.
Recycling CO2
Only 1% of the total CO2 on Earth is currently being used for chemical synthesis :- Chemical inertness,- CO2 capture and storage is expensive.
Recycling CO2 for the production of chemicals not only lower the impact on global climate changes but also provides a grand challenge in exploring new concepts and opportunities for catalytic and industrial development.
a) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. b) Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43. c) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365. c) Gibson, D. H. Chem. Rev. 1996, 96, 2063.
Other
Solvent
Biomass(Energy)
Ligand
Fine chmicals
Bulk chemicals CO2
Other use of CO2
Aresta, M. Carbon Dioxide as Chemical Feedstock 2010 Wiley, Weinheim.
Annual industrial use of CO2 in megatons
3.2GtC/y in 19903.2GtC/y in 199024GtC/y in 201024GtC/y in 2010
Gigatons of C/year Gigatons of C/year
Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43.
Properties of CO2 as Ligand
a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. c) Ma, J.; Sun, N. N.; Zhang, X. L; Zhao, N.; Mao, F. K.; Wie, W.; Sun, Y. H. Catal.Today, 2009, 148, 221. d) Gibson, D. H. Chem. Rev. 1996, 96, 2063.
- Thermodynamically stable- High energy substances required
O
C
O
-
+
-
Weak Lewis Acid
Weak Lewis Base
LnMO
OLnM
O
CO
OCOLnM
Coordination Modes
CO2 Reduction
CO2 + H2
CO
CH4
Hydrocarbons
Higher alcohols
MeOHMeOMe
HCOOH
HCONR2R2NH
a) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. b) Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43. c) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365. c) Gibson, D. H. Chem. Rev. 1996, 96, 2063.
CO2 Reduction
CO2 + H2
CO
CH4
Hydrocarbons
Higher alcohols
MeOHMeOMe
HCOOH
HCONR2R2NH
a) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. b) Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43. c) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365. c) Gibson, D. H. Chem. Rev. 1996, 96, 2063.
“Homogeneous catalysts show satisfactory activity and selectivity, but the recovery and regeneration are problematic. [...] Heterogeneous catalysts are preferable in terms of stability, separation, handling, and reuse, as well as reactor design, which reflects in lower costs for large-scale productions.”
Reduction Potential
Reduction Potential of CO2 at pH=7CO2 + 1e- → CO2
•- E0 = -1.90 VCO2 + 2H+ 2e- → HCO2H E0 = -0.61 VCO2 + 2H+ 2e- → CO + H2O E0 = -0.53 VCO2 + 4H+ 4e- → H2CO + H2O E0 = -0.48 VCO2 + 6H+ 6e- → CH3OH + H2O E0 = -0.38 VCO2 + 8H+ 8e- → CH4 + 2H2O E0 = -0.24 V
a) Benson, E. E.; Kubiak, C. P.; Sathrum, A. J.; Smieja., J. M. Chem. Soc. Rev. 2009, 38, 89. b) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. c) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
OC
O
2e-
2H
OC
OH
H
or
C O + H2O
2e-
2H
OC
H
H
2e-
2H
HOC
H
HH
2e-
2H
HC
H
HH
1e-O
CO
Reduction of CO2 to CO
Reverse water gas shift (RWGS) is the most promising process :
- Metal : Cu, Cu/SiO2, Cu–Ni/Al2O3, Cu/ZnO, Cu–Zn/Al2O3, Pd/Al2O3, Pt/Al2O3, Pt/CeO2, Ni/CeO2, Rh/SiO2 (from Rh2(OAc)4)
- Temperature : >600 °C
- Cu-based systems remain mostly used.
- Often reduction to CH4 occurs since CO is a better ligand than CO2
a) Xiaoding, X.; Moulijn, J. A. Energy Fuels, 1996, 10, 305. b) Kusama, H.; Bando, K. K.; Okabe, K.; Arakawa, H. Appl. Catal., A 2001, 205, 285. c) Bando, K. K.; Soga, K.; Kunimori, K.; Arakawa, H. Appl.Catal., A 1998, 175, 67. d) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703.
Reduction of CO2 to CO
a) Ernsta, K. H.; Campbell, C. T.; Moretti, G. J. Catal. 1992, 134, 66. b) Fujita, S. I.; Usui, M.; Takezawa, N. J. Catal. 1992, 134, 220. c) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703.
Reduction of CO2 to CO Mechanism with Pt/CeO2
a) Goguet, A.; Meunier, F. C.; Tibiletti, D.; Breen, J. P.; Burch, R. J. Phys. Chem. B 2004, 108, 20240.c) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703.
Photochemical Reduction of CO2 to CO
Takeda, H.; Ishitani, O. Coordination Chemistry Reviews 2010, 254, 346
Sacrificialreducing agent
Sacrificialreducing agent
Photocatalyst(OERS)
GS = Ground State3MLCT = Triplet Metal Ligand Charge Transfer
OERS = One Electron Reduced Species
Photocatalyst(GS)
Photocatalyst
(3MLCT)
h
1 e-
Catalyst(OERS)
Catalyst2-
Catalyst2-
Catalyst(GS)
CO2
2 H+CO + H2O
1 e-
CO2
1st Photochemical Reduction Using Ru Complex
Takeda, H.; Ishitani, O. Coordination Chemistry Reviews 2010, 254, 346
N
N
N
NN
NRuII
OH
N
N
Cl
CC
CReI
O
O
O
OH
NN
Cl
C
CC
ReI
O
O
O
OH
NNCl
CC
CReI
O
O
O
2+
CO2 CO + H2
1 ([Ru(bpy)3]Cl2), CoCl2
h > 400nm MeCN, H2O, NR3 (3 : 1 : 1)
Recent Advances :
Photocatalyst
Reducing catalyst
Reduction of CO2 to CH4 - Sabatier Reaction
Important catalytic process for the production of syngas (CH4 and H2)
a) Lunde, P. J.; Kester, F. L.; Ind. Eng. Chem. Process Des. Dev. 1974, 13, 27. b) Du, G. A.; Lim, S.; Yang, Y. H.; Wang, C.; Pfefferle, L.; Haller, G. L. J. Catal. 2007, 249, 370. c) Park, J. N.; McFarland, E. W.; J. Catal. 2009, 266, 92. d) Chang, F. W.; Kuo, M. S.; Tsay, M. T.; Hsieh, M. C. Appl. Catal., A 2003, 247, 309. e) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703.
- Thermodynamically favoured.- Metal = Ni, Ru, Rh, Pd, Pt.- Oxide support : SiO2, TiO2, Al2O3, ZrO2, CeO2, MgO, ZrO2, NiO, NiAl2O2.- Temperature : 400 - 700 °C - Dispersion and surface of oxides is important.- Ni is the best catalysts at 400 °C and exhibits excellent catalytic activity and stability yielding CO2 at 76% conversion and a selectivity to CH4 (vs CO and MeOH) of 99%.- Research is being conducted by the National Aeronautics and Space Administration on the application of the reaction using Ce0.72Zr0.28O2 in pace colonization on Mars to convert the Martian CO2 into CH4 and H2O for fuel and astronaut life-support systems.
Potential Bifunctional Model for Pd/MgO Catalysis
a) Park, J. N.; McFarland, E. W. J. Catal. 2009, 266, 92. b) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703.
Synthesis of Hydrocarbons
- Fischer-Tropsch process :
- Metal : Cu, Fe, Co.- Support : Al2O3, Mn, Zr, Zn.- Reaction are limited to small chains, H2O formed suppresses the reaction and they are not cost effective in most cases.
a) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. b) Riedel, T.; Schaub, G.; Jun, K. W.; Lee, K. W. Ind. Eng. Chem. Res. 2001, 40, 1355.
- Gasification of coal, synthesis of syngas :
300,000 barrels of hydrocarbons/year
- Modification to CO2 :
CO2 to MeOH
- Metals : Ag, Au, Pd, Cu- Support (oxides) : Zn, Zr, Ce, Al, Si, V, Ti, Ga, B, Cr. - Temperature : 200-300 °C - Industrial use Cu/ZnO gives 99% selectivity to MeOH (vs CH4) at 260 °C 40 Mt/year for the synthesis of formaldehyde, methyl tert-butyl ether and acetic acid.
a) Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. b) Olah, G. A.; Goeppert, A. Prakash, G. K. S. J. Org. Chem. 2009, 74, 487. c) Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43.
Potential CO2 to MeOH in Industry
82% of conversion
a) Olah, G. A.; Goeppert, A. Prakash, G. K. S. J. Org. Chem. 2009, 74, 487. b) Shulenberger, A. M.; Jonsson, F. R.; Ingolfsson, O.; Tran, K.-C. Process for Producing Liquid Fuel from Carbon Dioxide and Water. US Patent Appl. 2007/0244208A1, 2007. c) Tremblay, J.-F. Chem. Eng. News 2008, 86, 13.d) Image from http:/newenergyandfuel/com/2008/08/29/a-new-leading-process-for-co2-to-methanol – A New Leading Process For CO2 to Methanol, Mitsui Chemicals Inc., New energy and fuel news.
Synthesis of HCOOH
X Y
XY
Richardson, R. D.; Holland, E. J.; Carpenter, B. K. Nature Chem. 2011, 3, 301.
Synthesis of HCOOH from CO2 is still limited.
Synthesis of HCOOH
Richardson, R. D.; Holland, E. J.; Carpenter, B. K. Nature Chem. 2011, 3, 301.
Synthesis of HCOOH
Richardson, R. D.; Holland, E. J.; Carpenter, B. K. Nature Chem. 2011, 3, 301.
Analysis by H NMR :
Combustion Heat of Fuels in Higher Heating Value (HHV)
a) Image from http://en.wikipedia.org/wiki/Heat_of_combustion – Wikipedia - Heat of combustion. b) Olah, G. A.; Goeppert, A. Prakash, G. K. S. J. Org. Chem. 2009, 74, 487.
George A. Olah et al. : [...] Recycling of carbon dioxide [...] however, there is only limited interest in the US [...].
CO2 in Organic Chemistry
Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
CO2
R-M
R-CO2H
RNHRHN OH
O
ROH
RO OH
O
CO2H
2 RO
O
RR
O
O O
O
R=Alk,Ar,vinyl
O
O
On
Polymers
Industrial Synthesis of Salicylic Acid
a) Xiaoding, X.; Moulijn, J. A. Energy Fuels, 1996, 10, 305. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
ONa OH
CO2Na
OH
CO2H
CO2 5-7 bar
125 °C
H2SO4
90%
ONa OH
CO2Na
OH
CO2H
CO2
125 °C
H2SO4
50%
Urea Synthesis and Derivatives
a) Xiaoding, X.; Moulijn, J. A. Energy Fuels, 1996, 10, 305. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
Mesoporous silica
Reaction of CO2 with Organometallic Reagents
R
RLnM
O
R
CO2LnM
R
O
R
R
LnMO
R
CO2LnM
R
O
XLnMCO2
LnM O X
OX = H, C, O, ...
a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
Dialkyl Carbonate Synthesis
Cl Cl
O2 ROH
RO OR
O+ 2 HCl+
2 ROHRO OR
O++ CO2 H2O
With Phosgene :
With CO2 :
Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
Dimethyl Carbonate Synthesis
2 MeOHMeO OMe
O++ CO2 H2O
(300 bar)
Bu2Sn(OMe)2
180 °C, 70 hMol sieves
50% conversionfrom MeOH
Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
2 MeOHMeO OMe
O++ CO2
(300 bar)
Bu2Sn(OMe)2 (2 mol%)EtNH3(OTf) (0.02 mol%)
180 °C, 70 h
OMeMeO
MeMe+
O
MeMe+ 2 MeOH
0.25 g / h / 20 mL of rx
Recycle
- H2O
Dimethyl Carbonate Synthesis from Epoxides
O
MeO OMe
O++ CO2
Catalyst+ MeOH OHHO
a) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365. b) Bhanage, B. M.; Fujita, S.; Ikushima, Y.; Torii, K.; Arai, M. Green Chem. 2003, 5, 71
OO
O
via
Polymerization
2.0 MPa
Catalyst / cocatalyst / epichlorohydrin1/1/1000 (molar ratio)
Wu, G.-P.; Wei, S.-H.; Ren, W.-M.; Lu, X.-B.; Xu, T.-Q.; Darensbourg, D. J. J. Am. Chem. Soc., 2011, 133, 15191.
C-C Bond Formation
Wu, G.-P.; Wei, S.-H.; Ren, W.-M.; Lu, X.-B.; Xu, T.-Q.; Darensbourg, D. J. J. Am. Chem. Soc., 2011, 133, 15191.
Synthesis of a Cyclic Carbonate from an Oxirane
+ CO2
Bu3SnI2OO O
O
n
98%
O O
O
+ CO2O
100 %
Bu3SnI2
HMPA
a) Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43. b) Baba, A.; Kashiwagi, H.; Matsuda, H. Organometallics 1987, 6, 137. c) Tian, J. S.; Wang, J. Q.; Chen, J. Y.; Fan, J. G.; Cai, F.; He, L. N. Appl. Catal., A 2006, 301, 215.
Reaction of CO2 with Organometallic Reagents
R
RLnM
O
R
CO2LnM
R
O
R
R
LnMO
R
CO2LnM
R
O
XLnMCO2
LnM O X
OX = H, C, O, ...
a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
Possible Catalytic Synthesis of Acrylic Acid
“-H elimination is not favored for steric reasons: the rigid five membered ring does not allow the -H atoms to come close to the nickel center.”
a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365. c) Bruckmeier, C.; Lehenmeier, M. W.; Reichhardt, R.; Vagin, S. ; Rieger, B. Organometallics 2010, 29, 2199.
No Catalysis Possible
a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
Catalysis with MeI
a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
<56%
MeI decomposes the Ni complex
Ni-Catalyzed Stereoselective Ring-Closing Carboxylation
a) Takimoto, M.; Nakamura, Y.; Kimura, K.; Mori, M. J. Am. Chem. Soc. 2004, 126, 5956. a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
TsNPh
H
H
CO2Me
TsNEt
H
H
CO2Me
81%95% ee
57%94% ee
TsN
H
H
CO2Me
13%94% ee
H
H
CO2Me
100%94% ee
MeO2C
MeO2C
H
H
CO2Me
90%94% ee
O
OO
H
H
CO2Me
95%95% ee
BnO
BnO
Ni-Catalyzed Stereoselective Ring-Closing Carboxylation
L : Phosphine ligandZnEt2 : Transmetalation & reduction of Ni
-H elimination
Reductive elimination
Bisallyl species
a) Takimoto, M.; Nakamura, Y.; Kimura, K.; Mori, M. J. Am. Chem. Soc. 2004, 126, 5956. a) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. b) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
Coupling of CO2 and Alkynes
a) Inoue, Y.; Itoh, Y.; Hashimoto, H. Chem. Lett. 1977, 85. b) Cokoja, M et al.. Angew. Chem. Int. Ed. 2011, 50, 8510. c) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
+ +
<10%
Ni- Catalyzed Organozinc Coupling with CO2
R Zn X
1. [Ni(PCy3)2]2(N2)PhMe, 0 °C, 1 atm CO2, THF
2. 1 M HClR CO2H
Yeung, C. S.; Dong, V. M. J. Am. Chem. Soc. 2008, 130, 7826.
Reaction Mechanism
Yeung, C. S.; Dong, V. M. J. Am. Chem. Soc. 2008, 130, 7826.
NiO
O
Cy3P
Cy3P (II)
NiRCy3P
Cy3P (II)
O
O
ZnBr(Cy3)P2Ni(0)
R Zn BrCO2
RO
O ZnBrR
O
OH
H+
Transmetallation
ReductiveElimination
OxidativeCycloaddition
Au Catalyzed Carboxylation of C-H Bonds
Boogaerts, I. I. F.; Nolan, S. P. J. Am. Chem. Soc. 2010, 132, 8858.
Au Catalyzed Carboxylation of C-H Bonds
Boogaerts, I. I. F.; Nolan, S. P. J. Am. Chem. Soc. 2010, 132, 8858.
Au Catalyzed Carboxylation of C-H Bonds Mechanism
a) Boogaerts, I. I. F.; Nolan, S. P. J. Am. Chem. Soc. 2010, 132, 8858. b) Lckermann, L. Angew. Chem. Int. Ed. 2011, 50, 3842.
Also done with Cu(IPr)Ot-Bu
Biomass Synthesis
Algae + CO2 + H2O + h
=
O2 + Biomass (Biofuel)
=
CO2RWE's Algae Project, The Niederaussem Coal Innovation Centre, http://www.rwe.com/web/cms/en/213188/rwe-power-ag/innovations/coal-innovation-centre/rwes-algae-project/
Conclusion
A lot of work has been done for CO2 recycling and still a lot of work will have to be done to lower CO2 emissions.
- Elucidate mechanisms- Find more cost-effective methods- Incorporate renewable source of energy. ex. solar, etc. - Perform cyclic reactions where CO2 is formed and reduced in one reactor providing clean energy.
Fuels
Reduction Combustion EnergyRenewable
Energy
- Why not directly invest in renewable energy???
Consolidating Phase for the Pharma
What's Really Driving The Pharma M&A Frenzy, Forbes, http://www.forbes.com/sites/davidmaris/2012/04/27/pharma-feeding-frenzy/
- AstraZeneca announced it is buying Ardea for $1 billion.- Watson Pharmaceuticals announced it is buying Actavis for $5.6 billion.- J&J stated being days away from closing on its $21 billion acquisition of Synthes.- Glaxo got rebuffed from Human Genome Sciences in a $2.6 billion bid.- Pfizer announced the $12 billion divestiture of its infant nutritional business to Nestlé.
Why?- Blockbusters going off patent- Fewer drug approvals
Consequences : - Buy companies with solid pipelines that will deliver growth- Layoff- More partnerships to save $ : ex. Merck : 75 partnerships, Lilly : > 100 partnerships, etc
One biotech CEO who had sold his first company for several hundred million dollars, who is now on his second, put it this way to me:
“Large pharma can’t develop drugs any more. They are too slow. They make decisions for political reasons. Their hurdles are too high. They have to keep buying companies like us just to stay innovative.”