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Olefin Reductions Using Hydrazine and Oxygen by Continuous Flow Technology

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Olefin Reductions Using Hydrazine and Oxygen by Continuous Flow Technology HAZARDOUS REACTIONS BARTHOLOMÄUS PIEBER, C. OLIVER KAPPE* *Corresponding author Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010 Graz, Austria Bartholomäus Pieber Oliver Kappe Taming “forbidden“ olefin reductions using hydrazine and oxygen by continuous flow technology KEYWORDS: Flow chemistry, diimide, hydrazine, oxygen, olefin reduction. One of the rare alternative reagents for the reduction of carbon−carbon double bonds is diimide which Abstract can be generated in situ from hydrazine hydrate and oxygen. While this selective method is extremely clean and powerful it is rarely used as the rate-determining oxidation of hydrazine in the absence of a catalyst is relatively slow using conventional batch protocols. A continuous high-temperature/high-pressure methodology dramatically enhances the initial oxidation step, at the same time allowing for a safe and scalable processing of the hazardous reaction mixture. The continuous strategy not only allows the reduction of simple alkenes but can also be applied in semi-synthetic drug manufacturing as shown for the production of the artemisinin precursor dihydroartemisinic acid and a synthetic protocol towards hydrocodone. INTRODUCTION ineffi cient using standard batch conditions (8). Another drawback of this synthetic strategy is the fact that diimide The reduction of unsaturated carbon-carbon bonds is is prone to several undesired side-reactions (Scheme 1). arguably among the most important synthetic transformation On one hand, an over-oxidation process of the unstable N2H2 known. In general, the majority of these reactions are carried intermediate with either O2 or H2O2 - generated during the out by using hydrogen gas and heterogeneous transition initial oxidation - results in the formation of nitrogen and water metal catalysts such as e.g. Pd/C, PtO2, Rh/C or Raney (9). On the other hand, disproportionation of N2H2 leads to Nickel (1). Alternatively, homogeneous transitions metal the formation of hydrazine and nitrogen. Thus, the diimide complexes can be utilized which also accesses asymmetric precursor is usually added in high excess for a quantitative hydrogenation reactions (2). However, in certain cases these consumption of the unsaturated starting material. common strategies are accompanied by severe selectivity problems as several undesired side-reactions such as e.g. hydrogenolysis of protecting groups, reduction of other functionalities, alkene migration or racemization can occur. One of the few alternatives is the use of diimide (N2H2) which has been used as transfer hydrogenation agent in synthetic organic chemistry for more than a century (3). This extremely labile hydrogen donor predominantly reduces unpolarized carbon−carbon double bonds avoiding the above mentioned side-reactions. Diimide is usually prepared in situ by decarboxylation of dipotassium azodicarboxylate or from sulfonylhydrazides via thermal decomposition or a base induced elimination process (3). A more straightforward and Scheme 1. Olefi n reduction by in situ generation of diimide atom economic pathway is the oxidation of hydrazine using, from N2H4 and O2. e.g., H2O2, NaIO4, K3[(FeCN)6] or even molecular oxygen (3). In the latter case several catalytically active species such as Cu (3), or Fe salts (4), guanidine derivatives (5), fl avin-based A key feature of the olefin reduction via in situ generation catalysts (6), or even visible light (7) were studied to enhance of diimide from N2H4 and O2 is the fact that theoretically the reaction rate of the initial oxidation step which is very H2O, N2 and H2O2 are the only byproducts. 38 Chimica Oggi - Chemistry Today - vol. 34(3) May/June 2016 Since the latter is a relatively strong oxidation agent it can and molecular oxygen. Our basic hypothesis was that the be suspectedthat it quantitatively reacts with hydrazine or typical high surface-to-volume areas in a biphasic reaction diimide resulting in negligible amounts in the fi nal reaction mixture in continuous fl ow should dramatically enhance the mixture. It should be kept in mind that H2O2 could also lead oxidation rate of hydrazine hydrate (13, 14). Furthermore, we to selectivity problems by oxidizing other functionalities hypothesize that the additional use of a high-temperature/ of the starting material. A catalyst-free protocol would high-pressure protocol would push the diimide generation to therefore ultimately result in a virtually work-up free transfer its limits offering the possibility for an effi cient and catalyst- hydrogenation process allowing for connecting subsequent free reduction process. The fi rst generation reactor (Scheme 2) downstream processes without tedious purifi cation consisted of a mass fl ow controller (MFC) to regulate the procedures. The economic and environmental advantages oxygen stream and a pump delivering a stream of the using these cheap and readily available reagents in an respective olefi n olefi n and hydrazine hydrate in an organic almost waste-free process therefore represent an interesting solvent (16). After mixing of the liquid and gaseous streams, alternative for transition metal catalyzed processes. However, the resulting segmented fl ow pattern entered a heated it has to be pointed out that hydrazine is rather toxic and residence time unit made of perfl uoroalkoxy polymer. The dangerously unstable especially in its anhydrous form. Even reaction mixture was fi nally cooled in a heat exchanger and the less hazardous hydrazine hydrate should not be used depressurized by passing a backpressure regulating unit. without stringent hazard assessments and proper safety precautions. Oxidations using molecular oxygen or air are generally associated with severe safety risks and process challenges since they are exothermic and the heat of the reaction can be diffi cult to dissipate. As the oxidation of hydrazine is relatively slow at ambient conditions a process utilizing elevated temperatures and pressures in organic solvents would be required. To avoid spontaneous ignition of such reactions mixtures, large scale applications in conventional batch reactors have to be carried out below the limiting oxygen concentration (LOC) by mixing the gaseous oxidant with an inert gas as, e.g. N2 to dilute the oxygen/solvent vapour (10). In 1974, a feasibility study for diimide reductions in the syntheses of pharmaceuticals resulted in the utilization Scheme 2. Two feed continuous fl ow set-up for the reduction of of tosylhydrazide as N H precursor as the hydrazine/ oxygen 2 2 olefi ns with N2H2. route “…is hazardous on an industrial scale since mixtures of hydrazine vapor and oxygen are potentially explosive…”(11). An initial study on the catalyst-free reduction of allylbenzene in various alcohols showed that the solvent choice is - in DIIMIDE GENERATION IN CONTINUOUS FLOW particular at elevated temperatures - of crucial importance for enhancing the rate determining oxidation step. Given the Continuous fl ow technology offers the unique possibility to low boiling nature of some potential target molecules n-PrOH address these safety hazards, concurrently working at high (b.p. 97 °C) was the solvent of choice being a compromise temperature/pressure regimes (“Novel Process Windows”) between reaction rate at higher temperatures and the ability feasible for effi cient oxidation protocols (12-14). Exothermic for smooth solvent evaporation. A subsequent, in-depth reactions are easily controlled by the excellent mass and optimization study resulted in a fi nal, totally catalyst-free heat transfer making this technology an ideal tool to harness transfer hydrogenation process at 100-120°C and a system hazardous chemical processes (13, 14). Importantly, the small pressure of 20 bar within 10-30 minutes by using 4-5 equivalents volumes and channel dimensions minimize the possibility hydrazine monohydrate and 8 equivalents of oxygen. Notably, of propagation of an explosion inside the reactor thereby substrates bearing nitro- functionalities, protecting groups and tremendously broadening the possible operation range (15). aryl bromides can be selectively reduced under the applied Another advantage of this enabling technology is that scaling conditions. In most cases evaporation of the solvent and is generally considerably easier for a continuous process than careful drying of the crude material resulted in the desired for a batch process. Flow routes developed and optimized in saturated products in analytical purity (16,17). Only in case the laboratory can often be scaled to production quantities of allyl phenyl sulfi de a non-selective transfer hydrogenation with minimal re-optimization and/or without major changes occurred resulting in signifi cant amounts of oxidation products in the synthetic path (13). Numbering-up of fl ow devices or (sulfoxides and sulfones) of both, the olefi n and its saturated scaling-up of the reactor volume increases the throughput, derivative (18). Moreover it has to be stressed that the use of while the performance of the reactor can be largely aldehydes or ketones as starting materials is troublesome as conserved by keeping certain characteristics of the system these functionalities immediately undergo hydrazine and azine constant (“smart dimensioning”). Alternatively, simply running formation in the presence of hydrazine. a reactor for extended periods of time to generate the desired quantities of pharmaceutical intermediates or fi nal products is often an acceptable strategy. APPLICATION 1: SEMI-SYNTHESIS OF ARTEMISININ
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