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DOI: 10.1055/s-0035-1560438
Additive-Free Palladium-Catalysed Hydroamination of Piperylene with Morpholine
Publication History
Received: 14 December 2015
Accepted after revision: 12 February 2016
Publication Date:
15 March 2016 (online)
Abstract
In this contribution, the additive-free hydroamination of piperylene, an easily accessible 1,3-diene from naphtha steamcracking, with morpholine is described. This reaction provides an atom economic access to allylic C5 amines in a single step from commercially available and air-stable precursors and ligands. Detailed investigations revealed (DPPB)Pd(CCl3CO2)2 as the most active catalyst. After a 12-hour reaction period, a total yield of 79% allylic amines was obtained in the presence of 0.3 mol% catalyst. Furthermore, a noteworthy influence of the catalyst counter ion and the substrate concentration was discovered.
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Key words
homogeneous catalysis - hydroamination - dienes - amines - additive-free - piperylene - palladiumDue to diminishing resources of fossil feedstocks, several strategies for future sustainable utilisation of raw materials have been developed. On the one hand there is the development of new feedstocks and on the other hand more efficient utilisation of well-known but so far rarely used compounds is revealed. A potential compound is piperylene (1,3-pentadiene, 1), which is easily available from naphtha pyrolysis. It exhibits potential chemical properties; however, so far it is usually hydrogenated to n-pentane and then isomerised to isopentane, which is used as a gasoline additive.[1]
A key factor for sustainability is catalysis, which can lead to decreased energy demand and provide access to new compounds.[2] In this context, direct transition-metal-catalysed hydroamination is a promising reaction, which is 100% atom-economic, offering an answer to growing demand of large-scale production of alkylamines (Scheme [1]).[3]
Today, the industrial production of amines adds up to 400,000 t/y mainly in fine chemical and polymer-additive production.[4] However, hydroamination is one of the ‘top 10 challenges for catalysis’, owing to electronic properties of both olefins and amines, which lead to repulsion of the amine’s free electron pair by the p-electron orbitals of the olefin.[5] To overcome this, high temperatures are favourable, which, however, influence negatively on the reaction entropy.[6] Nevertheless, several homogeneously catalysed hydroaminations of olefins have been reported, in which a broad range of catalysts have been applied. For a comprehensive survey, several reviews have been published.[7] Furthermore, there are some reviews, with a special emphasis on enantioselective hydroamination,[8] base-catalysed hydroaminations,[9] or lanthanides[10] and group 9 metals as catalysts.[11] Recent contributions have expanded the range of feasible catalysts to iron[12] and iridium[13] catalysts. In addition, several contributions with dienes as starting material, which predominantly focus on palladium catalysis have been published.[14] However, there are also other catalysts that have been successfully applied in diene hydroamination.[15] Furthermore, a feasible concept to recycle palladium catalysts by means of thermomorphic solvent systems has been published by our group.[16] The 1,3-dienes mainly used in hydroamination reactions are butadiene, isoprene, and cyclohexadiene. However, piperylene has also been subjected to transition-metal-catalysed hydroamination reactions; indeed, they are rather focused on catalyst design. Beller et al. reported on a reaction with 4-methylphthalimide, which requires addition of stoichiometric amounts of Na2CO3.[17] Furthermore, there are contributions on piperylene hydroamination, which need activation by strong bases such as sodium phenolate[18] or strong acids such as trifluoroacetic acid. In addition, other activators, for example, silver triflate (AgOTf) are frequently required.[19] A complete overview on piperylene hydroamination and other reactions was recently published by our group.[1]
In this contribution, we have used palladium/diphosphine precursors, which are stable to air and moisture and easily accessible by unpretentious methods.[20] The reaction also benefits from the fact that no excess of activator is needed. When using 1,3-dienes in hydroamination reactions there are several possible products, owing to the 1,3-conjugated double bond structure, which allows attack of the nucleophile following a 1,2- and a 1,4-addition pathway. In a side reaction, the formation of telomers can be observed in which two molecules of piperylene react with one molecule morpholine, which gives C10 compounds (Scheme [2])
In this contribution, we have used a piperylene cis/trans-ratio of 3:7 (see experimental). Under chosen conditions the main hydroamination products arise from 1,4-addition, giving the linear allylic amine 2 and the branched product 3. Furthermore, the telomerisation side reaction gives small amounts of telomers, of which the so-called tail-head (th) telomer 4 is the main compound. They are quantified together as ‘telomers’ in the following investigations. Another side reaction is the dimerisation of two molecules of piperylene, however, this occurred only to a limited extent. In this contribution, we have focused on piperylene conversion [X (1)], the formation of the two main products [Y (2)] and [Y (3)] as well as the telomer formation [Y (4)], and selectivity towards hydroamination products [S (HA)].
The screening of ligands mainly relies on bidentate ligands, however, also triphenylphosphine has been used for comparison as we he have discovered a crucial influence of the ligand for switching between hydroamination and telomerisation under same reaction conditions (Figure [1]).[16]
Initially, the influence of the anions of the palladium precursors with different ligands was screened. Furthermore, the effect of triphenylphosphine (PPh3) in contrast to diphenylphosphinobutane (DPPB) was investigated. Methanol was chosen as the solvent. For suppression of possible telomerisation, morpholine was used in a two-fold excess. A pressure of 5 bar argon was applied to keep the volatile compounds in solution (Table [1]).
a Reaction conditions: 0.1 mol% precursor LPdX2, M:P (metal/phosphorus ratio) = 1:2; n (piperylene) = 7.5 mmol, n (morpholine) = 15 mmol, T = 100 °C, t = 16 h, 6 mL MeOH, 5 bar argon. X = conversion, Y = yield.
b Linear/branched ratio.
The hydroamination of piperylene with morpholine is heavily dependent on the nature of the precursor anion. Best results were obtained with trichloroacetate using DPPB as the ligand, which provided 63% yield of 1,4-adducts (Table [1], entry 3). In all reactions, the branched isomer 3 was the main compound of the reaction, providing a maximum linear:branched ratio of 1:2.2 (entries 1–3). Although chloride and trifluoroacetate were better leaving groups the reactions led to decreased yields (entries 1 and 2). It seemed that the dissociation behaviour has to be tailor-made only in a narrow range for the desired reaction.
In contrast to bidentate DPPB, the monodentate PPh3 provided only low yields (Table [1], entries 5–8). As expected the main products of all reactions with PPh3 are telomers, which might suggest a nonsufficient stability of the initial complex, which bears two PPh3 ligands, blocking the necessary reaction sites for two molecules of piperylene. However, the telomer yields remained low, which argues for bidentate ligands in further investigations.
First of all, the capability of (DPPB)Pd(CCl3CO2)2 was investigated by varying the precursor concentration (Figure [2]).
The initially applied catalyst concentration of 0.1 mol% provided 63% overall yield of 1,4-adducts. Lowering the amount of catalyst led to the exclusive formation of telomers, which suggests that also small amounts of bidentate ligand dissociated from the metal to provide free coordination sites for two molecules of piperylene. This effect has been observed with all ligands during our investigations, which indicates a general weak coordination of the ligand to the metal. When the amount of precursor was increased, the result was an increasing overall yield of 1,4-adducts, while the yield of telomers slightly decreased. The maximum yield of 80% 1,4-adducts was obtained with 0.3 mol%, which was chosen as a catalyst concentration in the following investigations.
The next influence to be monitored is the nature of ligands. Therefore, we have applied different bidentate ligands in the reaction, which are ordered by their bite angles (Table [2]).[3]
a Reaction conditions: 0.3 mol% precursor (L)Pd(CCl3CO2)2, M:P = 1:2; n (piperylene) = 7.5 mmol, n (morpholine) = 15 mmol, T = 100 °C, t = 16 h, 6 mL MeOH, 5 bar argon. X = conversion; Y = yield.
b Bite angle.
c Linear/branched ratio.
The ligand variation reveals a crucial influence of the ligand’s bite angle. The highest yield was obtained with DPPB, which gives 80% overall yield (Table [2], entry 3). Using DPEphos instead, led to 9% yield only, however, the bite angle is only 2° larger than for DPPB (entry 4). In addition, the main reaction with this ligand is the telomerisation reaction, which added up to 16% yield. Further increasing of the bite angle with Xantphos as a ligand, lead to the exclusive formation of telomers (entry 5). Presumably, the bite angle of 111° is too large for sufficient coordination of the ligand to the palladium metal centre, which results in too large distortion of the square-planar geometry, so that the ligand acts only as monodentate. This might favour the simultaneous coordination of two diene molecules. On the other hand, the yield also decreases by lowering the bite angle. Similar results for DPEphos and DPPF have also been reported by Hartwig et al. in the hydroamination of cyclohexadiene.14e For further optimisation, we investigated the influence of the amount of additional ligand on the reaction (Table [3]).
a Reaction conditions: 0.3 mol% (DPPB)Pd(CCl3CO2)2, n (piperylene) = 7.5 mmol, n (morpholine) = 15 mmol, T = 100 °C, t = 16 h, 6 mL MeOH, 5 bar argon. X = conversion; Y = yield; S = selectivity.
b Linear/branched ratio.
The variation of the metal/phosphorus (M:P) ratio revealed that the highest yield of 80% for 1,4-adducts does not need any further addition of a ligand (entry 1). Using a higher ligand surplus resulted in yield decrease from 80 to 74% (entry 4). This might be caused by the in situ formation of the inactive complex (DPPB)2Pd(CCl3CO2)2, which binds two DPPB ligands at the metal centre. This reaction has been described for the reaction of (DPPE)Pd(OAc)2 in methanol in the presence of a ligand excess.[21] Besides, the formation of telomers decreased with higher M:P ratios. Increasing the amount of additional ligand lead to higher selectivities of 1,4-adducts, which increased from 91% (entry 1) with a M:P ratio of 1:2 to >99 (entry 4) at a M:P ratio of 1:10, with no effect on the linear to branched ratio. This follows the expectations, as a high ligand excess effects the coordinative saturation of the metal complex. In further investigations we have used the initial M:P ratio.
a Reaction conditions: 0.3 mol% (DPPB)Pd(CCl3CO2)2, M:P = 1:2; n (piperylene) = 7.5 mmol, n (morpholine) = 15 mmol, T = 100 °C, t = 16 h, 6 mL solvent, 5 bar argon. PC = propylene carbonate; X = conversion; Y = yield.
b Linear/branched ratio.
Besides the different precursor parameters the solvent is usually crucial in homogeneous catalysis. In addition to methanol, the influence of other polar solvents was also investigated. For classification of the solvents the Hansen solubility parameter was used, which refers to the polarity of a solvent (Table [4]).[22]
The highest yield of 1,4-products corresponded to the polarity of the solvent, which was 80% in methanol (Table [4], entry 1). Switching to propylene carbonate (PC) decreased the yield to 5%, however, no telomers were observed. Strongly coordinating DMF totally hindered reaction of piperylene. Obviously the solvent blocked all coordination sites at the palladium complex. Acetonitrile showed similar results as propylene carbonate (entry 4). With toluene, being the least polar solvent during our investigations, a 1,4-adduct yield of 21% can be obtained, but there is also 8% formation of telomers (entry 5). In addition, the excess of branched products increased to 1:6. This suggests that not only polarity of the solvent is responsible for sufficient activity but also the absence of solvents, which can act as a strong binding ligand, such as DMF and acetonitrile.
With an eye on economic production parameters a high space-time-yield and therefore a high piperylene concentration is favourable. Therefore, we have investigated the influence of the substrate concentration. During this the starting substrate ratio remained constant (Figure [3]).
The concentration of 1.25 mol·L–1 led to 50% of 1,4-adducts. Lowering the substrate concentration below 1.25 mol·L–1 led to decreasing yields of 1,4-adducts. This might be explained by less collision rates at lower substrate concentrations. Interestingly, the yield of telomers remains nearly stable. Increasing the substrate concentration to 1.50 had only very little influence on the 1,4-adduct yield. On the other hand, a reaction without any solvent provided only very little yield. This might be caused by the coordination of the morpholine, which competes with piperylene for free coordination sites. To get closer insights into the behaviour of the morpholine, the influence of the piperylene/morpholine ratio has been investigated (Table [5]).
a Reaction conditions: 0.3 mol% (DPPB)Pd(CCl3CO2)2, M:P = 1:2; n (piperylene) = 7.5 mmol, morpholine, T = 100 °C, t = 16 h, 6 mL MeOH, 5 bar argon. X = conversion; Y = yield; S = selectivity.
b Linear/branched ratio.
The variation of the substrate ratio reveals that under chosen conditions a two-fold excess of morpholine worked best, as it provided the highest yield of 1,4-adducts of 80%. At an equal amount of morpholine and piperylene the main reaction was telomerisation rather than 1:1 addition. There was no other product beside telomers, however, the yield remained low at 11%, because the bidentate ligand is not the optimal choice for telomerisation reactions. Slightly higher excess of morpholine gives moderate hydroamination yield of 35% (Table [5], entry 2). Increasing the substrate ratio to 1:4 led to decreasing activity of the system, which goes along with the findings in the variation of the substrate concentration, where it was likely that too high amounts of morpholine blocked the catalytic species. Raising the ratio to 1:6 confirmed this trend, as the total yield of 1,4-adducts dropped to 27%.
For overcoming the repulsion between the amine’s free electron pair and the diene structure of piperylene elevated temperatures are favourable. However, this is contrary to the negative reaction entropy. To clarify this problem, we have investigated the influence of the temperature (Figure [4]).
The initially chosen temperature of 100 °C was most suitable for high yields of 1,4-adducts. At lower temperatures of 80 and 90 °C, respectively, the yield decreased. Furthermore, the ratio of 1,4-adducts and telomers was stable. At a temperature higher than 100 °C the yield started to decrease, which was probably caused by the beginning of catalyst deactivation.
In previous investigations, the reaction time has been set to 16 hours. However, efficient reaction design requires an optimised reaction time in regard to the highest possible space-time-yield. Therefore, we have investigated the temporal behaviour of the reaction, not only for shortening the overall reaction time, but also for getting insights into the formation of products. The results are displayed in Figure [5].
After a reaction time of 12 hours, the reaction system provided a 1,4-adduct yield of 79%. At this time, the conversion was 86%, which corresponds to a selectivity of 92%. In the course of the reaction, the branched product 3 is always the main product. Furthermore, the ratio of all products was constant, which intents that there is no subsequent reaction from a kinetically favoured product to a thermodynamically favoured. In addition, the formation of telomers started simultaneously with the formation of 1,4-adducts. Increasing the reaction time did not lead to higher yields. After 20 hours, the yield of 1,4-adducts remained only slightly higher at 81%.
In summary, we have developed an additive-free hydroamination of piperylene with morpholine, which allows high selectivities towards 1,4-adducts with telomerisation as a side reaction. This reaction provides atom economic access to C5 allylic amines in a single step with a maximum yield of 81%, catalysed by easily accessible and stable palladium catalysts.
Both 1H and 13C NMR spectra were recorded in CDCl3 on a Bruker Avance DRX 400 MH spectrometer (Bruker Corp., Billerica, Massachusetts, USA). Gas chromatography (GC) analysis of the reaction solutions was carried out on a Hewlett-Packard gas chromatograph Series 6890 equipped with a HP5 capillary column (coating: 5% diphenyl/95%-dimethoxypolysiloxane; length 30 m; diameter 0.25 mm, thickness 0.25 mm). A flame ionisation detector (FID) connected to an autosampler was used to detect individual components. The qualitative assignment of the chromatographically determined retention times of the individual components was carried out by comparing them to their respective pure substances. The quantitative determinations were achieved using the method of internal standard. The mass spectra were recorded by GC/MS. The mass spectrometer was a Hewlett Packard 5973 with electron energy of 70 eV and a scan range (m/z) of 50–700.
Piperylene was purchased from Haohua Chemical Corporation (Beijing/China) and purified by complexation with CuCl and subsequent distillation, giving an isomer ratio of cis/trans of 30:70.[23] Morpholine was purchased from Acros (Geel, Belgium), purified by redistillation, and stored under argon. All solvents used in this work were purchased from Acros Organics (Geel, Belgium) and were 99% pure or better. Other chemicals were purchased from commercial suppliers and were of the highest purity available. They were used as received without further purification. Selected Pd precursors were obtained from Umicore AG & Co. KG (Hanau, Germany).
All experiments were conducted using a homemade multiplex reactor.[24]
Palladium-Catalysed Hydroamination of Piperylene with Morpholine (Tables 1–5, Figures [2–5])
In each representative experiment, the described amounts (see Tables 1–5 and Figures [2] and 3) of precursor, ligand, and MeOH (6 mL) were transferred into a Schlenk vessel. The mixture was activated in an ultrasonic bath for 2 min followed by the addition of morpholine and further 3 min of ultrasonic activation. Finally, piperylene (1) was added. The mixture was transferred into the evacuated and flame-dried reactor and charged with 5 bar of argon. The reactor was put into an oil bath at chosen temperature. After the reaction time (see also Figures [4] and 5), the reactor was cooled in an ice bath. After cooling, the mixture was analysed by GC (sample composition: 0.025 g dibutyl ether as internal standard, 0.4750 g reaction solution, 0.5000 g i-PrOH as solubility mediator). The main products were identified by comparison with authentic samples in accordance to Kiji et al.[17]
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Palladium-Catalysed Hydroamination of Piperylene with Morpholine; Typical Procedure
Following the above procedure, a typical reaction mixture consisting of Pd(CCl3CO2)2 (9.7 mg, 0.3 mol%), DPPB (9.6 mg, 0.3 mol%), MeOH (6 mL), morpholine (1.3 g, 15 mmol), and piperylene (1; 510 mg, 7.5 mmol) was heated at 100 °C for 16 h. The hydroamination products were removed by distillation (bp 67 °C/1 mbar) and the crude mixture was purified by column chromatography over silica gel (cyclohexane–EtOAc–Et3N, 12:1:0.01) to give products 2 and 3. The telomer 4 was isolated from the sump by column chromatography.
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4-(Pent-2′-enyl)morpholine (2)
Yield: 290.6 mg (25%); colorless liquid.
1H NMR (400.13 MHz, CDCl3/TMS, 25 °C): δ = 0.90 (t, J = 7.5 Hz, 3 H, CH2CH 3), 2.01 (dq, J = 7.4, 5.3 Hz, 2 H, =CHCH 2CH3), 2.38 [br, 4 H, N(CH 2CH2)2O], 2.93 [d, J = 6.8 Hz, 2 H, CH 2N(CH2CH2)2O], 3.70 (t, J = 4.5 Hz, 4 H, N(CH2CH 2)2O), 5.34 (m, 1 H, =CHCH2CH3), 5.52 (m, 1 H, =CHCH2N).
13C {1H} NMR (100.63 MHz, CDCl3/TMS, 25 °C): δ = 15.9 (CH3), 38.7 (CH3 CH2), 63.2 (NCH), 61.4 (CHN), 67.6 (OCH2), 125.3 (CH3CH2 CH=), 139.8 (C=CHCH2N).
MS: m/z (%) = 155 (M+, 15), 126 (11), 110 (33), 100 (23), 96 (28), 87 (100), 86 (47), 82 (10), 69 (32), 68 (38).
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4-(Pent-3′-en-2′-yl)morpholine (3)
Yield: 640 mg (55%); colorless liquid.
1H NMR (400.13 MHz, CDCl3/TMS, 25 °C): δ = 1.07 (d, J = 6.6 Hz, 3 H, NCHCH 3), 1.62 (dd, J = 6.6, 4.3 Hz, 3 H, CH=CHCH 3), 2.36–2.48 [br, 4 H, N(CH 2CH2)2O], 2.76–2.69 (m, 1 H, NCH), 3.64 [t, J = 4.5 Hz, 4 H, N(CH2CH 2)2O], 5.41 [mc, (5.50–5.27), 2 H, CH=CH].
13C {1H} NMR (100.63 MHz, CDCl3/TMS, 25 °C): δ = 18.2 (2 C, CH3), 50.9 (2 C, NCH2), 63.2 (NCH), 67.6 (2 C, OCH2), 127.4 (CH3 CH=), 133.4 (C=CHCH).
MS: m/z (%) = 155 (M+, 8), 141 (10), 140 (100), 114 (14), 110 (6), 87 (3), 86 (6), 82 (5), 70 (5), 69 (24), 68 (5), 67 (4) 58 (4), 57 (5), 56 (21), 55 (11).
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4-(6′-Methylnona-3′,8′-dien-2′-yl)morpholine (4)
Yield: 132.7 mg (8%); slightly yellow liquid.
1H NMR (500.13 MHz, CDCl3/TMS, 25 °C): δ = 0.81 (d, J = 6.7 Hz, 3 H, CHCH 3), 1.05 (d, J = 6.7 Hz, 3 H, NCHCH 3), 1.47–1.58 (m, 1 H, CHCH3), 1.77–1.85 (m, 2 H, CHCH 2CH=CH), 1.93–2.04 (m, 2 H, CH2=CHCH 2CH), 2.39 (br, 4 H, NCH2), 2.72–2.78 (m 1 H, CHN), 3.64 (t, J = 4.6 Hz, 4 H, OCH2), 4.93 (d, J = 15.1 Hz, 2 H, CH 2=CH), 5.26–5.31 (m, 1 H, CH=CH), 5.39–5.47 (m, 1 H, CH=CH), 5.69–5.73 (m, 1 H, CH2=CH).
13C {1H} NMR (125.77 MHz, CDCl3/TMS, 25 °C): δ = 17.7 (CH3), 18.9 (CH3), 32.8 [CH(CH3)], 38.9 (CH2CH=CH), 40.6 (CH2=CHCH2), 50.4 (2 C, NCH2), 62.7 [CH(CH3)N], 67.1 (CH2O), 115.6 (CH2=CH), 130.6 [CH=C(CH3)N], 133.1 (CH=CH2), 137.3 (CH2=CH).
MS: m/z (%) = 223 (M+, 1), 209 (17), 208 (100), 166 (20), 140 (9), 86 (16).
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Acknowledgment
The authors would like to thank Umicore AG & Co. KG for donation of palladium precursors.
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- 2 IEA, Dechema, ICCA, Technology Roadmap Energy and GHG Reductions in the Chemical Industry via Catalytic Processes. Dechema; Frankfurt: 2013
- 3 Behr A, Neubert P. Applied Homogeneous Catalysis . Wiley-VCH; Weinheim: 2012
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- 5 Haggin J. Chem. Eng. News 1993; 71 (22) (22) 23
- 6 Steinborn D, Taube R. Z. Chem. 1986; 26: 349
- 7a Huang L, Arndt M, Gooßen K, Heydt H, Gooßen LJ. Chem. Rev. 2015; 115: 2596
- 7b Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem. Rev. 2008; 108: 3795
- 7c Müller TE, Beller M. Chem. Rev. 1998; 98: 675
- 7d Nobis M, Drießen-Hölscher B. Angew. Chem. Int. Ed. 2001; 40: 3983 ; Angew. Chem. 2001, 113: 4105
- 7e Hartwig JF. Pure Appl. Chem. 2004; 76: 507
- 8a Hii KK. Pure Appl. Chem. 2006; 78: 341
- 8b Hultzsch KC. Org. Biomol. Chem. 2005; 3: 1819
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