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Augustine, Tanielyan, Marin and Alvez 465Table 1. Effect of ligand and solvent on the hydrogenation of 1 mmole of 6 using 10μmole of Ru(ligand)(S,S)-DPEN at 50°C and 60 psig with 0.25 mmole of KO-tBu.Ligand MeOH/i-PrOH ee (%) r (mmol/min) Conv. (%)(S)-Tol-Binap 30/70 73 0.068 87(R)-Tol-Binap 30/70 -59 0.072 100(R)-P-Phos 30/70 6 0.006 100(R)-Xylyl P-Phos 30/70 7 0.020 100(R)-Binam 60/40 55 0.030 100(R)-Binam 100/0 68 0.020 100(S,S)-Dipamp 30/70 93 0.005 95(R)-Phanephos 30/70 64 0.070 100(R)-Xylyl Phanephos 30/70 86 0.020 96(R)-Xylyl Phanephos 60/40 >99 0.021 100(R)-Xylyl Phanephos 100/0 >99 0.140 100(R)-Xylyl Phanephos EtOH >99 0.039 22different bases used in conjuction with the chiral diamine, DPEN, had on the reactionrate and product ee in the hydrogenations run using the xyl-phanephos ligand. Theoptimized reaction conditions were found to be the use of Ru(Xyl-Phanephos)modified with DPEN as the catalyst and running the reaction in a methanol solutionat 30°C and 60 psig of hydrogen in the presence of potassium t-butoxide. Asubstrate:catalyst ratio of 2500 was routinely used giving the succinimido alcohol, 7,in >98% yield with an ee of > 99%. Increasing the hydrogen pressure to 200 psigsignificantly reduced the reaction time while still maintaining these same ee andconversion values. Hydrogenation of 6 using dichloro [(R)-Xylylphanephos][1S,2S-DPEN]ruthenium(II) gave the S enantiomer of 7 with 99% ee at100% conversion. Using (S)-xylyl phanephos and (1R,2R)-DPEN resulted in theformation of the R enantiomer of 7, again with 99% ee at 100% conversion.Table 2. Effect of the base used on the hydrogenation of 2 mmole of 6 using 2μmole of Ru((R)-Xylyl Phanephos) (S,S)-DPEN at 30°C and 60 psig H 2 .Base (0.25 mmole) ee (%) r (mmol/min) Conv. (%)None >99 0.0004 2KO-t-Bu >99 0.090 100LiO-t-Bu >99 0.069 100K 2 CO 3 - 0 0K 2 CO 3 /12-Cro-4(1:1) a >99 0.016 52K 2 CO 3 /15-Cro-5(1:1) a >99 0.010 68K 2 CO 3 /18-Cro-6(1:1) a >99 0.011 68Li 2 CO 3 /12-Cro-4(1:1) a >99 0.007 50Li 2 CO 3 /15-Cro-5(1:1 ) a >99 0.006 70Li 2 CO 3 /18-Cro-6(1:1) a >99 0.013 64DABCO 0 0.004 0a Carbonates were used in conjunction with crown ethers.
466 Chiral 2-Amino-1-PhenylethanolIt was originally thought that one should be able to remove the succinic acidgroup by treatment of 7 with hydrazine in the same way one is able to produce aprimary amine by treating a phthalimide with hydrazine in the classical Gabrielsynthesis (12). This was not the case, though, since 7 did not react with hydrazine.However, it was found that treatment of 7 with dilute sodium hydroxide readilyhydrolyzed the succinimide to produce the amino alcohol, 1, in 90% yield andhaving a 98 - 99% ee.Experimental SectionAll reagents and ligands were obtained from Aldrich, Acros or Strem and were usedwithout further purification. The methanol, i-propanol and DMF were distilled overcalcium hydride under an argon atmosphere and stored in sealed flasks under argon.The THF was purified by distilled over sodium ketyl under an argon atmosphere andstored in a sealed flask under argon. The (S)-5,5-diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine (3) was purchased from Aldrich as a 1M solution in toluene[(S)-2-methyl-CBS-oxazaborolidine]. All gases used were zero grade. The HPLCanalyses were accomplished using a 250 x 4.6mm Chiracel OJ column withappropriate internal standards.Oxazaborolidine reductions:A 100 mL jacketed reaction flask equipped with an addition port, reflux condenserand a magnetic stir bar was first purged with argon for 10 minutes and then chargedwith a solution of 0.125 mmole of catalyst 3 in 11 mL of THF and 34 mL of a BH 3 -THF solution containing 24 mmole BH 3 , added portionwize over 10 min. Thereaction flask was heated to 65°C and a solution of 6.19g (40 mmole) of phenacylchloride (2) in 7.6 mL of THF was added via syringe pump over three hours at a rateof 0.08 mL/min. After addition was complete, the reaction mixture was stirred for60 min, cooled to ambient and the remaining hydride was decomposed with 5 mL ofdry methanol. The reaction mixture was passed through a short bed of SiO 2 and thesolvent evaporated giving the crude chloro alcohol, 4, in 95% yield with ee = 95%.Five and a half grams of this material was dissolved in 30 mL of methanolfollowed by the addition of 100 mL of 30% aqueous ammonium hydroxide. Theresulting mixture was stirred at room temperature for 2-3 days after which time thelight precipitate which formed was removed by filtration and the methanol onlyremoved by rot-evaporation. To the cold water phase was added 15 g of sodiumchloride and 30% aqueous ammonium hydroxide to pH 12.5. This was extractedtwice with 50 cc portions of ether. The organic phase was dried over magnesiumsulfate and evaporated giving 3.4 g (83%) of the crude amino alcohol, 1, ee = 95%.Catalytic hydrogenationsSuccinimido Ketone, 6: To 17.22 g (0.17 mole) of succinimide in a 1000 mL roundbottomed flask was added 150 mL of THF and the suspension stirred at 65°C untilthe succinimide was dissolved. In a separate 250 mL flask 20.4 g (0.18 mole)potassium t-butoxide was suspended in 120 mL of THF and the suspension sonicatedfor 10 min to give a cloudy solution which was added dropwise to the stirred
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Catalysis ofOrganic Reactions
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14. Catalyst Manufacture: Laborator
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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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xxiiiChronology of Organic Reaction
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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. 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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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. 47was practically
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Gőbölös et al. 49noteworthy that
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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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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84Phenol Benzoylationconsecutive Fr
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86Phenol BenzoylationThis does not
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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
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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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176Nitrobenzene Hydrogenation10. G.
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178 Hydrogenation of Dehydrolinaloo
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188Modeling Mass Transfer Hydrogena
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200 Fructose HydrogenationTable 1.
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204 Fructose Hydrogenationthe subst
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206 Fructose Hydrogenationcleave th
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210 Fructose Hydrogenationis not th
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Kuusisto, Mikkola and Salmi 237100A
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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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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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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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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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382 Polyurethane from Natural Oilfr
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406“Green” Catalysts for Biodie
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Page 455 and 456: Marincean et al. 429Experimental Se
Page 457 and 458: Marincean et al. 431neutralize all
Page 459 and 460: Marincean et al. 433suggesting that
Page 461 and 462: Marincean et al. 435increasing from
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Page 466 and 467: Kocal 439description of the four st
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Page 475 and 476: 448Propylene Oxidation to POSupercr
Page 477 and 478: 450Propylene Oxidation to POTable 1
Page 479 and 480: 452Propylene Oxidation to PO
Page 482 and 483: Riermeier et al. 45550. catASium ®
Page 484 and 485: Riermeier et al. 457It is interesti
Page 486 and 487: Riermeier et al. 459Reaction of the
Page 488: Riermeier et al. 461References1. I.
Page 491: 464 Chiral 2-Amino-1-Phenylethanolp
Page 495 and 496: 468 Chiral 2-Amino-1-Phenylethanola
Page 497 and 498: 470 t-Butanol DehydrationResults an
Page 499 and 500: 472 t-Butanol Dehydrationcomprises
Page 502 and 503: Pohlmann et al 47553. Leaching Resi
Page 504 and 505: Pohlmann et al 477this study. In th
Page 506: Pohlmann et al 479Experimental Sect
Page 509 and 510: 482 Reductive AlkylationSince the p
Page 511 and 512: 484 Reductive AlkylationTable 2. Re
Page 514 and 515: Wolf, Seebald and Tacke 48755. Acce
Page 516 and 517: Wolf, Seebald and Tacke 489100Norma
Page 518 and 519: Wolf, Seebald and Tacke 4911,88Figu
Page 520 and 521: Woods et al. 49356. Transition Meta
Page 522 and 523: Woods et al. 495Effect of oxidation
Page 524 and 525: Woods et al. 497
Page 526: Woods et al. 499removed the samples
Page 529 and 530: 502 Electroreductive Catalytic Ullm
Page 531 and 532: 504 Electroreductive Catalytic Ullm
Page 534 and 535: Catalysis of Organic Reactions 507A
Page 536 and 537: Catalysis of Organic Reactions 509K
Page 538: Catalysis of Organic Reactions 511T
Page 541 and 542: 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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