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Ostgard et al . 207Flat Adsorbtion Edge Adsorption TautomericHOFormHOHOOHHOHOOHOHOOHOOHα - pyranoseMetalMetalHOHOOHHOOOHHOOHHOOHOOHβ - pyranoseMetalMetalHOOHOOHOHOHHOHOOHOOHOHα - furanoseMetalMetalHOHOOHOHOOHHOHOOOHOHOHβ - furanoseMetalMetalFigure 19. The possible adsorbed intermediates for fructose hydrogenation, wherethe more active flat adsorption is better positioned for the metal stabilization of thedeveloping π-bond character between the anomeric carbon and its hydroxyl oxygen.The only flat adsorbed β-pyranose ring that can accommodate the adsorption ofboth the ring oxygen and the hydroxyl oxygen on the anomeric carbon also suffersfrom a 1,3 steric interaction between the methylene hydroxyl group on the C2position and the hydroxyl group on C4 resulting in it being less stable and lesspreferred to the remaining flat adsorbed species. The flat adsorbed α-pyranose ring
208 Fructose Hydrogenationfulfills the requirements of an active intermediate for this mechanism and its lowerconcentration (~2%) is not something that would limit it from making a noticeablecontribution to the product distribution. However this 6-membered ring is morestable and less active than the 5-membered α-furanose and its lower contribution tothe mannitol/sorbitol product mix should have a similar selectivity as the α-furanoseflat adsorbed species. This leaves the α- and β-furanose flat adsorbed species and itis obvious due to the position of the C5 methylene hydroxyl group that the α-furanose ring will approach the surface with far less steric hindrance than the β-furanose ring. Thus a metal, such as Cu, that weakly adsorbs fructose willpreferentially adsorb and hydrogenate the α-furanose over its β counterpart so thatits contribution to the product mix will be far greater than its concentration insolution predicts. It is known that hydrogen dissociation is activated on Cu and nonactivatedon Ni (10, 24, 25) meaning that the Cu surface will contain less hydrogenthan the Ni one at reaction conditions. This could explain why Cu is typically usedunder higher hydrogen pressures (10). This also increases the required residencetime of the active intermediate on the Cu surface as it waits for the relatively sparsesurface hydrogen to react with it and this too favors the α- over the β-furanose ringeven more. Seeing how Cu is less effective than Ni for the dissociation of hydrogen,it could also be less efficacious for the abstraction of the hydrogen atom from thehydroxyl group on the anomeric carbon as needed for the above mentioned preferredreaction intermediate. Once this intermediate is formed, Cu may not be able tostabilize the developing π-bond character as well as Ni, resulting in a higheractivation energy for this hydrogenation in comparison to Ni. During the reaction,the adsorbed hydrogen will add to the bottom of the adsorbed intermediate and thismay result in retention or so-called inversion at the anomeric carbon. This willdepend on how the C2-C3 bond rotates to stabilize the developing π-bond. If theC2-C3 bond of the adsorbed flat species slightly rotates in the direction that pushesthe hydroxyl group on the anomeric carbon away from the ring, there will bestabilization of the forming π-bond with a minimum of strain and energy, and theaddition of hydrogen to the bottom to this species will give a polyol with retention.This rotation will also maintain some degree of bonding between the ring oxygenand anomeric carbon bond so that the adsorbed intermediate can delocalize itselectron density as described above for the preferred reaction intermediate. The C2-C3 bond could also rotate the hydroxyl group towards the ring to stabilize the newlyformed π-bond, however that would not only require more rotation, energy andstrain; it would also break the ring oxygen to anomeric carbon bond and eliminateany stabilization this may bring to the adsorbed intermediate. In agreement with thereaction data and as explained above, Cu clearly favors the hydrogenation of theleast sterically hindered α-furanose with retention at the anomeric carbon to give amannitol-rich product mixture and its less effective stabilization of the developing π-bond is the reason that it has a higher activation energy in comparison to Ni.Because mutarotation (Figure 1) is faster than hydrogenation, it is possible for aless concentrated but more active tautomer to determine the overall selectivity of thereaction (4). This was the case for Cu where the α-furanose was ~6 times moreactive than the more concentrated β-furanose to generate the ~ 2:1 mannitol:sorbitol
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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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Wang et al. 233. Catalytic Hydrogen
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Wang et al. 25The rate expressions
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Wang et al. 27Schiff’s base forma
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Wang et al. 29AcknowledgementsWe gr
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32Halophosphite LigandsIn 1970, Pru
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34Halophosphite LigandsThe ligands,
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36Halophosphite LigandsTable 2 Temp
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38Halophosphite Ligands3. P. W. N.
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40Monolithic Bioreactorstrength for
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42Monolithic BioreactorMenten equat
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Gőbölös et al. 456. Highly Selec
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Gőbölös et al. 47was practically
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Gőbölös et al. 49noteworthy that
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Gőbölös et al. 51Figure 2 NMR sp
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Gőbölös et al. 53internal TMS in
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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Mantilla, Tzompantzi, Torres and G
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68Synthesis of MIBKwe examined the
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70Synthesis of MIBK1412Conversion (
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72Synthesis of MIBK4,4’-dimethyl
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74Synthesis of MIBKobtained for MIB
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Ardizzi et al. 7710. The Control of
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Ardizzi et al. 79type acidity at th
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Ardizzi et al. 81procedure describe
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84Phenol Benzoylationconsecutive Fr
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86Phenol BenzoylationThis does not
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II. Symposium on Catalytic Oxidatio
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92Oxidation with Microchannel Immob
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100 Propylene Partial OxidationThe
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102 Propylene Partial OxidationSiO
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104 Propylene Partial Oxidation0.01
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106 Propylene Partial Oxidation0.02
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108 Propylene Partial OxidationRefe
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110Oxidation of n-Pentanemethacryli
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112Oxidation of n-PentaneFReqox1ox2
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114Oxidation of n-Pentanethe presen
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116Oxidation of n-PentaneIn the mec
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118Oxidation of n-PentaneReferences
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120TEMPO Oxidation of Alcoholsthe u
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122TEMPO Oxidation of AlcoholsThe r
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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
Page 184 and 185: Yamauchi 157transformation is schem
Page 186 and 187: Yamauchi 159The X-ray diffraction p
Page 188 and 189: Yamauchi 161was -0.0009, -0.0032 an
Page 190 and 191: Yamauchi 163shown in Fig. 12. It wa
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Page 195 and 196: 168Nitrobenzene Hydrogenationfurthe
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Page 199 and 200: 172Nitrobenzene HydrogenationThe co
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Page 203 and 204: 176Nitrobenzene Hydrogenation10. G.
Page 205 and 206: 178 Hydrogenation of Dehydrolinaloo
Page 215 and 216: 188Modeling Mass Transfer Hydrogena
Page 225 and 226: 198 Fructose HydrogenationHOHCCH 2O
Page 227 and 228: 200 Fructose HydrogenationTable 1.
Page 229 and 230: 202 Fructose Hydrogenationmmol form
Page 231 and 232: 204 Fructose Hydrogenationthe subst
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Page 240 and 241: Disselkamp et al. 21324. Cavitating
Page 242 and 243: Disselkamp et al. 215column. In a p
Page 244 and 245: Disselkamp et al. 217selectivity es
Page 246 and 247: Disselkamp et al. 219hydrogenated (
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Page 250 and 251: Disselkamp et al. 223Scheme 4.cis-2
Page 252 and 253: Disselkamp et al. 225conventional c
Page 254 and 255: Ostgard et al. 22725. The Treatment
Page 256 and 257: Ostgard et al. 229Table 1. The reac
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Page 260 and 261: Ostgard et al. 233In conclusion, th
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Page 264 and 265: Kuusisto, Mikkola and Salmi 237100A
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Page 269 and 270: 242 1-Phenyl-1-Propyneof cis-β-met
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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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Diez, Di Cosimo and Apesteguia 359A
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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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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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