Iodine and Lipase Based Green Oxidation Technology Aleksandra Joanna KOTLEWSKA‐MIERNOWSKA Iodine and Lipase Based Green Oxidation Technology PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Delft, op gezag van de Rector Magnificus prof. ir. K. C. A. M. Luyben, voorzitter van het College voor Promoties, in het openbaar te verdedigen op vrijdag 5 november 2010 om 10.00 uur door Aleksandra Joanna KOTLEWSKA‐MIERNOWSKA Master of Science, Engineer in Chemical Technology, Warsaw University of Technology (Polen) geboren te Ciechanów, Polen Dit proefschrift is goedgekeurd door de promotoren: prof. dr. R. A. Sheldon en prof. dr. I. W. C. E. Arends Samenstelling promotiecommissie: Rector Magnifcus, voorzitter Prof. dr. R. A. Sheldon, Technische Universiteit Delft, promotor Prof. dr. I. W. C. E. Arends, Technische Universiteit Delft, promotor Prof. dr. K. R. Seddon, The Queen’s University of Belfast Prof. dr. J. Martens, Carl von Ossietzky University Oldenburg Prof. dr. ir. R. Orru, Vrije Universiteit Amsterdam Dr. U. Hanefeld, Technische Universiteit Delft Dr. M. Ostendorf, MSD Prof. dr. ir. H. van Bekkum, Technische Universiteit Delft ISBN: 978‐90‐816123‐1‐9 The research described in this thesis was supported by ACTS‐IBOS Copyright © 2010 by Aleksandra Joanna KOTLEWSKA‐MIERNOWSKA. All rights reserved. No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the author. Printed in the Netherlands Dla mojego Arka Cover design by Arkadiusz Kotlewski Contents Chapter 1 Introduction to sustainable oxidation chemistry 1 Chapter 2 Hypervalent iodine in organic synthesis 19 Chapter 3 Polymer‐attached iodine(III) reagent in selective oxidations 39 Scope of oxidants Chapter 4 Polymer‐attached iodine(III) reagent in selective oxidations 61 Scope of substrates Chapter 5 Lipase catalyzed in situ generation of hypervalent iodine 91 reagent for selective alcohol oxidation Chapter 6 Epoxidation and Baeyer‐Villiger oxidation using hydrogen 109 peroxide and lipase dissolved in ionic liquids Summary 131 Samenvatting 135 Acknowledgements 139 Curriculum Vitae 143 List of abbreviations ACTS Advanced Catalytic Technologies for Sustainability program. acid carboxylic acid Adogen 464 methyltrialkyl(C8‐C10)ammonium chloride, phase transfer catalyst Asp aspartate ‐ amino acid ARP‐Pt Pt nanoparticles dispersed in amphiphilic polystyrene‐ polyethylene glycol resin BASF The chemical company: Baden Aniline and Soda Factory BAM Fallhammer The BAM Fallhammer test is used to determine the sensitivity of a given solid (including paste‐like and gel‐ type) substances and liquids to drop‐weight impact of known force BA butanoic acid = butyric acid ‐ [BF4] tetrafluoroborate anion BF3OEt Lewis acid, boron trifluoride etherate [BMIm]+ (1‐butyl‐3‐methylimidazolium) cation BTI = PIFA phenyliodine(III) bis(trifluoroacetate) = (bis(trifluoroacetoxyiodo) benzene) = PhI(OCOCF3)2 BV Baeyer‐Villiger CA Octanoic acid= caprylic acid CaLA Candida antarctica lipase A CaLB Candida antarctica lipase B + + [Choline] = [TMEOA] (CH3)3N CH2CH2OH = N,N,N‐trimethylethanolammonium cation cinnamyl alcohol 2(E)‐3‐phenylprop‐2‐en‐1‐ol citral 3,7‐dimethylocta‐2,6‐dienal = lemonal cl. cross‐linked CLEA cross linked enzyme aggregates CTAB cetyl‐trimethyl ammonium bromide conv. conversion DIB = DAIB = BAIB = PIDA iodobenzene diacetate =iodosobenzene diacetate = (diacetoxyiodo)benzene DMP Dess‐Martin Periodane = 1,1,1‐Triacetoxy‐1,1‐dihydro‐ 1,2‐benziodoxol‐3(1H)‐one DMSO dimethylsulfoxide [dbmim] (4‐diacetoxyiodobenzyl)‐3‐methylimidazolium EDG electron donatng groups [emim]+ 1‐ethyl‐3‐methylimidazolium cation + ‐ Et4N Br tetraethylammonium bromide EtOAc ethyl acetate eq. molar equivalent EWG electron withdrawing groups geraniol 2‐trans‐3,7‐dimethyl‐2,6‐octadiëen‐l‐ol Hammett plot relationship (LFER) linear free‐energy relationship relating reaction rates and equilibrium constants for many reactions HBD hydrogen bond donaing H2O2 hydrogen peroxide His histidine – amino acid [HOPMim]+ 1‐(3‐hydroxypropyl)‐3‐methylimidazolium cation ‐ [HCO2] formate anion IBOS The Integration of Biocatalysis and Organic Synthesis – program IBX 2‐iodoxy benzoic acid ILs ionic liquids Janda Jel polytetrahydrofuran cross‐linked polystyrene resins Koser’s reagent hydroxy(tosyloxy)iodobenzene = HTIB ld. Loading lin linear Macroporous polystyrene polystyrene cross linked with bigger spacer Me methyl group = CH3 MeCN = CH3CN acetonitrile m‐CPBA 3‐chloroperoxybenzoic acid Myrcene 7‐Methyl‐3‐methylene‐1,6‐octadiene = β‐myrcene NaOAc sodium acetate ‐ [NO3] nitrate anion Nov. 435 Novozym 435 – CaLB immobilized on polyacrylic resin immobilized NMO 4‐methylmorpholine‐N‐oxide OH alcohol OTf trifluoromethanesulfonate = triflate = CF3SO3‐ OTs tosylate refers to the anion of p‐toluenesulfonic acid ‐ (CH3C6H4SO3 ). phen 1,10-phenanthroline PhICl2 iodobenzene dichloride PhIF2 iodobenzene difluoridee PhIO iodosobenzene (PhIO)n iodosylarenes = iodosylbenzene PhIX2 iodobenzene dihalogen PhI(OAc)2 = ArI(OAc)2 iodobenzene diacetate =iodosobenzene diacetate = (diacetoxyiodo)benzene PIFA phenyliodo‐ bis(trifluoroacetate) PIPO polymer immobilized piperidinyl oxyl = polymer immobilized TEMPO β‐pinene 1S,5S)‐2,6,6‐trimethylbicyclo[3.1.1]hept‐2‐ene or (1S,5S)‐ 6,6‐dimethyl‐2‐methylenebicyclo[3.1.1]heptane PF6 hexafluorophosphate PTC phase transfer catalyst PS‐I iodopolystyrene, polymer‐supported iodosobenzene = iodine (I) PS‐I(III) polymer oxidant PS‐I(OAc)2 = PS(DAIB) = C2 diacetoxyiodobenzene bound to polystyrene resin = derivative polymer‐attached iodosobenzene diacetate PS‐DBIB = C4 derivative polymer supported iodosobenzene dibutanoate PS‐DHIB = C6 derivative polymer supported iodosobenzene dihexanoate PS‐DCIB = C8 derivative polymer supported iodosobenzene dioctanoate pulverization grinding to receive a fine powder ROP ring opening polymerization ROOH organic peroxide e.g. peracetic acid (Ethaneperoxoic acid) salen 2,2'‐Ethylenebis(nitrilomethylidene)diphenol, = N,N'‐ Ethylenebis(salicylimine) TM Select Fluor (F‐TEDA‐BF4) 1‐(chloromethyl)‐4‐fluoro‐1,4‐ diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) Ser serine – amino acid SIBX stabilized 2‐iodoxybenzoic acid + ‐ [TEA] [(HOCH2CH2)3NH = triethanolamine cation TEMPO 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl TFA trifluoroacetic acid TGA thermogravimetric analysis (TGA) TLC thin layer chromatography TMS trimethylsilyl = (CH3)3Si TOF turnover frequency TON turnover number TPAP tetrapropylammonium perruthenate UHP urea‐hydrogen peroxide quant. quantitative CChhaapptteerr 11 Introduction to sustainable oxidation chemistry 1.1 Sustainability in oxidation chemistry 1.1.1 Clean oxidation pathways 1.1.2 Sustainability and fine chemicals 1.1.3 Clean solvent 1.1.4 Recovery and recycling 1.2 Alcohol and alkene oxidation 1.2.1 Alcohol oxidation 1.2.2 Alkene epoxidation 1.3 Lipases 1.4 Scope of the thesis 1.5 References Abstract “Green chemistry efficiently utilizes (preferably renewable) raw materials, eliminates waste and avoids the use of toxic and/or hazardous reagents and solvents in the manufacture and application of chemical products...” P. T. Anastas, 1998 Chapter 1 1.1 Sustainability in oxidation chemistry 1.1.1 Clean oxidation pathways Oxidation is a pivotal transformation in organic chemistry. Usually this is the first step in the conversion of oil‐ and natural gas based feedstock to bulk chemicals. 1,2 As primary oxidant in these processes molecular oxygen is employed in combination with a metal catalyst in order to enhance the rate and selectivity of the reaction. Both heterogeneous and homogeneous catalysts are employed on an industrial scale. Industry makes use of gas phase oxidation for the majority of technologies to produce e.g. styrene, formaldehyde, ethylene oxide, acrylonitrile, acrylic acid or maleic anhydride. Nevertheless, liquid phase oxidation is used to produce compounds such as phenol, acetic acid, propylene oxide, benzoic acid, styrene or vinyl acetate. In general hydrogen peroxide and alkyl hydroperoxides are widely applied to produce epoxides for the bulkd an fine chemicals industry. 3,4 Figure 1.1 (A) Classical route (B) new BASF route to citral 5 The use of catalytic oxidations in bulk chemicals manufacture is common practice but in the fine chemicals industry fewer catalytic methodologies are used. Oxidation reactions are generally performed using stoichiometric amounts of inorganic oxidants such as chromiumVI, 2 Introduction to sustainable oxidation chemistry permanganate, manganese dioxide and periodate, leading to the formation of large quantities of inorganic salts as waste.5 Therefore, there is a pressing need for designing catalytic technologies employing benign oxidants, such as oxygen and hydrogen peroxide, for the production of fine chemicals. One pioneering example is the BASF process for the production of citral (Figure 1.1) via vapour phase oxidation over a silica supported silver catalyst.5 The BASF process uses a silver catalyst to oxidize the intermediate alcohol to the aldehyde. In the chemical process, in contrast, stoichiometric amounts of MnO2 were required. In Table 1.2 a number of single oxygen donors is listed, which can be applied in catalytic oxidations. Table 1.2 Mass percentage active oxygen content of commonly applied oxidants6,7 Oxidant % Active oxygen co-product O2 50 (100) H2O, H2O2 H2O2 47 H2O N2O 36.4 N2