Results and Discussion - The Synthesis of Pyrroles via Acceptorless Dehydrogenative Cond

6. The Synthesis of Pyrroles via Acceptorless Dehydrogenative Condensation of

6.2 Results and Discussion

The synthesis of the applied Ir@SiCN catalyst is shown schematically in Fig. 1a. The application of II in the Ir@SiCN catalyst synthesis is based on the solvent compatibility of complex II and the used polysilazane (HTT1800, Clariant Advanced Materials), the high reactivity of II with respect to the crosslinking of the silazane and the possible production of II in a multigram scale. The inexpensive and commercially available polysilazane HTT1800 was added to a THF solution of complex II, wherein an increase in viscosity indicates crosslinking of the polysilazane. Hydrosilylation and dehydrocoupling were identified as the most relevant crosslinking reactions (FT-IR measurements and analysis of the released hydrogen gas via GC). After removal of the solvent, the sample was pyrolyzed under a nitrogen atmosphere at 1100 °C. ICP-OES measurements revealed 18.9 wt% Ir. Powder XRD was carried out to confirm the amorphous nature of the SiCN matrix as well as the presence of metallic iridium nanoparticles (Fig. 1b). The broad reflexes at 2θ values of 40.7°, 47.2° and 69.1° can be assigned to the (111), (200) and (220) reflexes of cubic crystalline iridium. The broadness of the reflexes indicates very small sizes of iridium particles which were calculated to be 1.2 nm.

The existence of an Ir–SiCN nanocomposite was also confirmed by transmission electron spectroscopy (TEM) (Fig. 1a; ESI†). The particles are distributed homogeneously over the whole nitride matrix. An average particle size of 1.3 nm was determined by TEM (Fig. 1c), which is in agreement with the results of the XRD investigation. Analysis by HRTEM also confirmed the existence of crystalline iridium nanoparticles (ESI).

The Synthesis of Pyrroles via Acceptorless Dehydrogenative Condensation of Secondary Alcohols and 1,2-Amino Alcohols Mediated by a Robust and Reusable Catalyst Based on Nanometer-sized Iridium Particles

Fig. 1 a) Synthesis of the Ir@SiCN catalyst. The novel aminopyridinato iridium complex II (for its synthesis, see the ESI) crosslinks the commercially available polysilazane HTT1800 then undergoes pyrolysis under a nitrogen atmosphere at 1100 °C, resulting in Ir@SiCN nanocomposites. The coordinative saturation of the iridium particles by the N atoms of the support material allo ws the formation of homogeneously distributed nanometer -sized Ir particles. b) Powder XRD (red: reflexes of cubic crystalline iridium). c) Particle size distribution. For the HRTEM image, see the ESI.

The reaction of 2-aminobutan-1-ol and 1-phenylethanol was chosen as the model reaction to investigate the optimal reaction parameters. The ratio of amino alcohol to alcohol and the influence of the base were explored first. The highest yield could be obtained by using KO^tBu as a base. At 120 °C (oil bath temperature; 115 °C inside) and with bis(2-methoxylethyl)ether (diglyme) as the solvent, the maximum yield was 73 %. Here, the use of base leads to significant self-condensation of 1-phenylethanol (after oxidation). Hence, the alcohol to base ratio was optimized and the yield could be increased to 96 % (determined by GC) with an iridium loading of 0.33 mol% (or 1.27 wt.%).

Next, we applied other heterogeneous iridium catalysts to underline the need for the novel Ir@SiCN catalyst (Fig. 2). Neither Ir@MIL-101,^[23]Ir/CaCO₃, Ir/Al₂O₃ nor Ir/C was able to catalyze the synthesis of 1a adequately or better using the same amount of active iridium. In contrast to our Ir@SiCN nanocomposite catalyst, the tested commercially available catalysts suffered from a significant activity loss in the second run. The most active commercial

43 catalyst (Ir/C) shows a significant activity loss in the second run (47 % of the conversion of the first run). The activity loss of the other commercial catalysts in the second run is even higher.

Fig. 2 Screening of different heterogeneous iridium catalysts unde r identical conditions using the sa me amount of active Ir. Yields were determined by GC.

With the optimized reaction conditions in hand, the potential of the Ir@SiCN catalyst regarding the substrate scope was investigated. Various amino alcohols were reacted with 1-phenylethanol. The isolated yields were between 93 % (1b) and 86 % (1a,d). It was also possible to introduce an indol group (Table 1, entry 5). Next, the substrate scope with regard to the secondary alcohol was studied. Therefore, 2-amino-1-butanol was used as a constant building block. The catalyst system showed high regioselectivity towards the formation of 2,5-disubstituted pyrroles when aliphatic alcohols like 2-hexanol were used. Only traces of the 2,4-disubstituted pyrrole could be found. The alkylation of a terminal CH3 group is significantly faster than that of a CH₂group at the β-position. Aliphatic alcohols with different lengths (Table 1, entry 8 and 9), branched alcohols (Table 1, entry 7), 1-cyclohexylethanol (Table 1, entry 10) and 1-(1-naphthyl)ethanol (Table 1, entry 11) were applied successfully.

Furthermore, our recyclable catalyst tolerates sulfur-containing functional groups (Table 1, entry 12) and olefin functions (Table 1, entry 13). The C-alkylation step can also take place at a secondary aliphatic carbon atom. As an example, 5-ethyl-3-methyl-2-phenyl-1H-pyrrole (2a) was synthesized in 67 % yield. The application of cyclic alcohols results in bicyclic pyrroles like 2-ethyl-1,5,6,7,8,9-hexahydrocyclohepta[b]pyrrole (2b), which was accessible in 90 % yield. The variation of the amino alcohol yielded bicyclic pyrroles in isolated yields between 75 % (2d) and 81 % (2g). The variation of the alcohol building block resulted in the

generation of smaller (Table 2, entry 8 and 10) and larger (Table 2, entry 9) rings attached to the pyrroles.

Table 1 Synthesis of 2,5 -disubstituted pyrroles from secondary alcohols and 1,2 -amino alcohols^{[ a ]}.

Table 2 Synthesized 2,3,5 -trisubstituted pyrroles^{[ a ]}

Entry Product Yield [%]^[b]

In summary, we presented the efficient synthesis of regioselectively substituted pyrroles starting from secondary alcohols and amino alcohols catalyzed by an Ir nanoparticle catalyst under (relatively) mild conditions. The used SiCN support enables the generation of nanometer-sized Ir particles and the robust nature of that support results in very good reusability of the catalyst under basic conditions. Other Ir nanoparticle catalysts show lower activity and very limited reusability. The Ir@SiCN catalyst, an easy-to-handle and airstable powder, promises versatile applications in sustainable organic synthesis especially if the addition of strong bases is required to mediate the reactions.

Im Dokument Synthesis and Characterization of M@SiCN Catalysts and their Application in the Synthesis of Renewable Products (Seite 53-57)