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Canning, Gamman, Jackson and Urquart 73At 673 K the nickel catalysts had low selectivity to MIBK (< 50 %) and asignificant contribution to this loss in selectivity was due to hydrogenation ofMIBK to MIBC. Indeed with the Ni-KOH/silica catalyst the yield of MIBC wasgreater than the yield of MIBK. This behaviour was to be expected as nickel isused industrially to hydrogenate 2-ethyl hexenal, the intermediate in the OXOalcoholprocess to make 2-ethyl hexanol (1), where both alkene and carbonyl arerequired to be hydrogenated. The ratio of MIBK:MIBC at 673 K was 1.4:1 forthe Ni-CsOH catalyst and 0.9:1 for the Ni-KOH catalyst compared to ~10:1 forboth catalysts at 473 K. This change in ratio with temperature is likely to be dueto different activation energies for C=C and C=O hydrogenation.It is noticeable that over the nickel catalysts, isophorone was a majorproduct. The production of isophorone and the small quantities of other byproductsonce again revealed formation of the three intermediate aldol productsof the reaction between MO and acetone. However it is clear that hydrogenationwas not as facile over the nickel catalysts as it was over the palladium catalysts.Hence there was more secondary and tertiary aldol condensation. To furtherinvestigate this a reaction was performed at 573 K using the Ni-KOH/silicacatalyst with nitrogen as the carrier gas rather than hydrogen. The results areshown in Table 1.Table 1. Comparison of selected reaction product yields (%) in N 2 carriercompared to H 2 carrier over Ni-KOH/silica at 573 K.Ni-KOH/SiO 2 MO MIBK MIBC IsophoroneNitrogen 2.1 0 0 1.2Hydrogen 0.1 2.8 0.1 0.2Clearly there is a switch from MO to MIBK when hydrogen was made thecarrier gas. The yield of isophorone dropped as at this temperature thehydrogenation intercepted the MO before it could undergo another aldolcondensation. At 673 K the aldol condensation reaction became kineticallymore competitive with the hydrogenation reaction.Over the temperature range studied the activity was controlled by the basecomponent of the catalyst. The conversion observed with the Ni-KOH catalystwas approximately the same as that observed with the Pd-KOH catalyst; whilethe CsOH catalysts were more active at both temperatures.In conclusion, four catalyst systems, Pd-KOH/silica, Pd-CsOH/silica, Ni-KOH/silica, and Ni-CsOH/silica, have been investigated for the conversion ofacetone to MIBK. Systems highly selective to MIBK have been obtained (Pd-CsOH/silica, 100 % at 473 K). Both the metal and the base affected the productdistributions. The nickel catalysts were generally less selective, with MIBKbeing further hydrogenated to MIBC and isophorone becoming a major productat high temperatures. Over Ni-CsOH/silica, a selectivity of around 30% was
74Synthesis of MIBKobtained for MIBC compared with 99.99%), was pumped via a Gilson HPLC 307 pump at 5 mL hr -1into the carrier gas stream of H 2 (50 cm 3 min -1 ) (BOC high purity) where itentered a heated chamber and was volatilised. The carrier gas and reactant thenentered the reactor containing the catalyst. The reactor was run at 6 bar pressureand at reaction temperatures between 373 and 673 K. Samples were collected ina cooled drop out tank and analyzed by a Thermoquest GC-MS fitted with a CP-Sil 5CB columnReferences1. G. J. Kelly, F. King and M. Kett, Green Chem. 4, 392 (2002).2. K. Schmitt, J. Distedorf, W. Flakus, U.S. Patent 3,953,517 to Veba ChemieAG (1976); J. J. McKetta, and W. A. Cunningham, Encyclopedia ofChemical Processing and Design, Vol. 30, p. 61. Dekker, New York, 1988,p. 61.3. W. K. O’Keefe, M. Jiang, F. T. T. Ng and G. L. Rempel, ChemicalIndustries (CRC), 104, (Catal. Org. React.), 261-266 (2005).4. A. A. Nikolopoulos, G. B. Howe, B. W.-L. Jang, R. Subramanian, J. J.Spivey, D. J. Olsen, T. J. Devon and R. D. Culp, Chemical Industries(Dekker), 82 (Catal. Org. React.), 533 (2001).
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Catalysis ofOrganic Reactions
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14. Catalyst Manufacture: Laborator
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62. Catalysis of Organic Reactions,
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108. Metal Oxides: Chemistry and Ap
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CRC PressTaylor & Francis Group6000
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xiii14. The Transformation of Light
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xviien Catalisis y Petroquimica (UN
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xix56. Transition Metal Removal fro
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xxiiiChronology of Organic Reaction
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To Zsuzsanna and Tim
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Jones et al. 31. On the Use of Immo
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Jones et al. 5three-phase tests in
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Jones et al. 7In the HKR of rac-epi
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Jones et al. 9term performance char
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Jones et al. 115. A. S. Gruber, D.
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Moses et al. 132. Supported Re Cata
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Moses et al. 15perrhenate, followed
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Moses et al. 17SnCOSnMe 4≡SiOReO
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Moses et al. 19(AlOSi) of the cube.
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Moses et al. 212.510 3 k obs / s -1
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Page 95 and 96: 68Synthesis of MIBKwe examined the
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Page 106 and 107: Ardizzi et al. 79type acidity at th
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Page 137 and 138: 110Oxidation of n-Pentanemethacryli
Page 139 and 140: 112Oxidation of n-PentaneFReqox1ox2
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Page 145 and 146: 118Oxidation of n-PentaneReferences
Page 147 and 148: 120TEMPO Oxidation of Alcoholsthe u
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124TEMPO Oxidation of Alcoholsany d
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126TEMPO Oxidation of Alcoholsconce
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128TEMPO Oxidation of AlcoholsMNT :
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130TEMPO Oxidation of Alcoholsuptak
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132Aminoalcohols to Aminocarboxylic
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142Bromine-Free TEMPO-Based Catalys
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148CO OxidationP25 TiO 2 , respecti
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150CO Oxidation0.02(a)21802110(b)21
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152CO Oxidationcarboxylate species
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Yamauchi 15519. 2006 Murray Raney A
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Yamauchi 157transformation is schem
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Yamauchi 159The X-ray diffraction p
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Yamauchi 161was -0.0009, -0.0032 an
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Yamauchi 163shown in Fig. 12. It wa
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168Nitrobenzene Hydrogenationfurthe
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170Nitrobenzene Hydrogenationhydrog
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172Nitrobenzene HydrogenationThe co
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174Nitrobenzene HydrogenationHence
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176Nitrobenzene Hydrogenation10. G.
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178 Hydrogenation of Dehydrolinaloo
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188Modeling Mass Transfer Hydrogena
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198 Fructose HydrogenationHOHCCH 2O
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200 Fructose HydrogenationTable 1.
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202 Fructose Hydrogenationmmol form
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204 Fructose Hydrogenationthe subst
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206 Fructose Hydrogenationcleave th
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208 Fructose Hydrogenationfulfills
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210 Fructose Hydrogenationis not th
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Disselkamp et al. 21324. Cavitating
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Disselkamp et al. 215column. In a p
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Disselkamp et al. 217selectivity es
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Disselkamp et al. 219hydrogenated (
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Disselkamp et al. 223Scheme 4.cis-2
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Disselkamp et al. 225conventional c
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Ostgard et al. 22725. The Treatment
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Ostgard et al. 229Table 1. The reac
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Ostgard et al. 231metal atoms. Thes
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Ostgard et al. 233In conclusion, th
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Kuusisto, Mikkola and Salmi 23526.
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Kuusisto, Mikkola and Salmi 237100A
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Kuusisto, Mikkola and Salmi 2399. B
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242 1-Phenyl-1-Propyneof cis-β-met
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244 1-Phenyl-1-Propynealkene. When
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Musolino, Apa, Donato and Pietropao
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Gőbölös and Margitfalvi 25329. R
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Gőbölös and Margitfalvi 255maxim
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Gőbölös and Margitfalvi 257Y=421
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Rothenberg et al. 26130. How to Fin
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Rothenberg et al. 263By dividing th
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Rothenberg et al. 265pre-define the
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Rothenberg et al. 267Table 1. Parti
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Rothenberg et al. 269Experimental S
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Angueira and White 27131. Novel Chl
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Angueira and White 273optimizedgeom
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Angueira and White 275F igure 4 - c
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Angueira and White 277Table 1. 27 A
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Angueira and White 279obtained from
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Cao, White, Wang and Frye 28933. Se
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Cao, White, Wang and Frye 291Experi
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294Chiral Ferrocene Ligandsnew Twin
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296Chiral Ferrocene LigandsTable 1.
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298Chiral Ferrocene Ligandsprevents
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300Chiral Ferrocene LigandsConclusi
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302Chiral Ferrocene Ligandsextracte
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304 Catalyst Library DesignIn gas p
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306 Catalyst Library Designd−(b 0
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308 Catalyst Library DesignBasic Pr
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310 Catalyst Library DesignD in com
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312 Catalyst Library DesignCatalyst
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314 Catalyst Library Design27. S. H
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316 Dendrimer TemplatesWe are devel
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318 Dendrimer TemplatesThe differen
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320 Dendrimer TemplatesWe encounter
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322 Dendrimer TemplatesThe 100 cm -
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328Rearrangement of 3,4-Epoxy-1-But
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3382,5-Dimethyl-2,4-Hexadieneharves
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3422,5-Dimethyl-2,4-Hexadiene10086Y
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348Heteropoly AcidsSOOO O+ +OS1 2 3
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350Heteropoly AcidsTable 3. Acylati
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352Heteropoly AcidsSiO 2 is the bes
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Diez, Di Cosimo and Apesteguia 3554
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Diez, Di Cosimo and Apesteguia 357T
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378 Polyurethane from Natural OilMe
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380 Polyurethane from Natural Oilco
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382 Polyurethane from Natural Oilfr
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384 Polyurethane from Natural OilTh
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386 Carbonylation of Chloropinacolo
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396 Recycling Homogeneous Catalysts
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406“Green” Catalysts for Biodie
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416 Production of BiodieselTable 1.
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418 Production of Biodieselto a mas
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420 Production of BiodieselEthyl st
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422 Production of Biodiesel10080Sel
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424 Production of Biodieselproduct
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Marincean et al. 42747. Glycerol Hy
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Marincean et al. 429Experimental Se
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Marincean et al. 431neutralize all
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Marincean et al. 433suggesting that
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Kocal 43748. Developing Sustainable
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Kocal 439description of the four st
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Kocal 441metallurgy in parts of the
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Kocal 443that capital investment co
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Kocal 4455. J.J. Siirola, An Indust
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448Propylene Oxidation to POSupercr
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450Propylene Oxidation to POTable 1
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452Propylene Oxidation to PO
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Riermeier et al. 45550. catASium ®
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Riermeier et al. 457It is interesti
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Riermeier et al. 459Reaction of the
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Riermeier et al. 461References1. I.
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464 Chiral 2-Amino-1-Phenylethanolp
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466 Chiral 2-Amino-1-PhenylethanolI
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468 Chiral 2-Amino-1-Phenylethanola
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470 t-Butanol DehydrationResults an
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472 t-Butanol Dehydrationcomprises
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Pohlmann et al 47553. Leaching Resi
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Pohlmann et al 477this study. In th
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Pohlmann et al 479Experimental Sect
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482 Reductive AlkylationSince the p
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484 Reductive AlkylationTable 2. Re
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Wolf, Seebald and Tacke 48755. Acce
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Wolf, Seebald and Tacke 489100Norma
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Wolf, Seebald and Tacke 4911,88Figu
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Woods et al. 49356. Transition Meta
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Woods et al. 495Effect of oxidation
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Woods et al. 497
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Woods et al. 499removed the samples
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502 Electroreductive Catalytic Ullm
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504 Electroreductive Catalytic Ullm
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Catalysis of Organic Reactions 507A
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Catalysis of Organic Reactions 509K
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Catalysis of Organic Reactions 511T
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514 Keyword Indexcarboncarbon dioxi
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516 Keyword Indexethanolamine 16 13
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518 Keyword IndexNi, activated 25 2
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520 Keyword Indexsuccinimido ketone
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