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Regiodivergent Access to 2- or 3-Substituted Indanones: Catalyst-Controlled Carboacylation via C–C Bond Activation

2020; Chinese Chemical Society; Volume: 3; Issue: 8 Linguagem: Inglês

10.31635/ccschem.020.202000448

2096-5745

Pengcheng P. Shao, Tianyang Yu, Hong Lu, Peng‐Fei Xu, Hao Wei,

Sulfur-Based Synthesis Techniques

Open AccessCCS ChemistryRESEARCH ARTICLE1 Aug 2021Regiodivergent Access to 2- or 3-Substituted Indanones: Catalyst-Controlled Carboacylation via C–C Bond Activation Pengcheng Shao†, Tianyang Yu†, Hong Lu, Peng-Fei Xu and Hao Wei Pengcheng Shao† Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069 , Tianyang Yu† Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069 , Hong Lu Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069 , Peng-Fei Xu State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 and Hao Wei *Corresponding author: E-mail Address: [email protected] Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069 https://doi.org/10.31635/ccschem.020.202000448 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Indanones are ubiquitous in biologically active compounds. Intramolecular hydroacylation of aldehydes and alkenes is an efficient and atom-economic route to indane rings. However, these reactions are limited to the transfer of a hydride to the alkene. The transfer of aryl groups enabling the formation of C–C bonds during the cyclization would be a new method for the synthesis of substituted indanones. This report describes the regiodivergent carboacylation of alkenes with ketones to furnish both 2- and 3-substituted indanones in a regiocontrolled manner. The regioselectivity is controlled by the careful selection of different transition-metal catalysts. Moreover, both transformations show high atom economy and good functional group tolerance, which may have implications for C–C bond cleavage in the preparation of complex cyclic molecules. Download figure Download PowerPoint Introduction Indanone is present in a wide range of biologically active natural products and is associated with many pharmacologically active compounds. The indanone moiety can be used as an intermediate in the synthesis of various medicinal compounds (Figure 1a).1–9 Therefore, the development of synthetic methods toward indanone is in high demand. Transition-metal-catalyzed intramolecular hydroacylation of alkenes with aldehydes is an atom-economic approach to construct the indanone framework (Figure 1b).10–19 This reaction involves activation of a C–H bond and addition of the alkene to an aldehyde to form a new C–C bond. However, this process is strictly limited to the transfer of a hydride to the alkene. The transfer of aryl groups is highly desirable, as it would enable the formation of valuable C–C bonds during the cyclization event. Figure 1 | (a–c) Inspiration for the catalyst-controlled regioselective carboacylation. Download figure Download PowerPoint The insertion of an olefin into a C–C bond, namely the "cut and sew" process, is expected to be a powerful synthetic tool in organic synthesis.20 This method involves the formation of two new C–C bonds across olefins via C–C bond cleavage and enables the rapid construction of complex molecules from simple and readily available feedstock chemicals. Such carboacylation reactions have been extensively demonstrated in strained ring systems.21–26 However, there are only a few known examples of unstrained systems, such as those reported by Douglas and Dong, and the regioselectivity of this reaction remains largely unexplored.27–30 Motivated by the importance of directly forming indane rings, we envisioned using ketones as aldehyde surrogates in catalytic C–C activation.31–37 The reaction is expected to proceed via the chelation-assisted oxidative addition of a transition metal into the C–C bond of ketone 1, followed by olefin migratory insertion.38–48 However, the regioselectivity of this process is a challenge because two distinct regioisomers from migratory insertion are available, namely the 1,2- and 2,1-addition products (Figure 1c). Migratory 1,2-insertion would lead to 3-substituted indanone 2 as the product after reductive elimination of the six-membered metallocycle B. Migratory insertion in the 2,1-sense would produce the five-membered metallocycle C. Subsequent β-hydrogen elimination would give the metal hydride-olefin complex D, which could then undergo hydride re-insertion followed by reductive elimination, to furnish 2-substituted indanone 3. One solution to this problem is catalyst control. Ideally, each possible product will be selectively formed from the same reactants upon changing the catalyst.49–51 Moreover, it is well established that acyl–metal complexes can undergo reversible CO deinsertion reactions. The competitive decarbonylation is another challenge in developing this process.52–62 Herein, we report a highly selective carboacylation of 2-styryl ketones 1, in which the application of nickel (Ni) and rhodium (Rh) catalysts controls regioselectivity, leading to 2- or 3-substituted indanones, respectively. Experimental Methods General procedure for the Ni-catalyzed carboacylation A 10 mL dried, sealed tube equipped with a stir bar was charged with 1 (0.20 mmol). The tube was capped and transferred into a glovebox. In the glovebox, the tube was charged with Ni(cod)2 (5.5 mg, 0.02 mmol, 10 mol %), PhCl (1.0 mL), and PMe3 (40 μL, 1M in THF, 0.04 mmol, 20 mol %). The tube was capped and removed from the glovebox, and then maintained at 140 °C for 16 h. The reaction mixture was cooled to room temperature, and purified by silica gel flash column chromatography. General procedure for the Rh-catalyzed carboacylation A 10 mL dried, sealed tube equipped with a stir bar was charged with 1 (0.20 mmol) and Rh(cod)2SbF6 (4.4 mg, 0.008 mmol, 4 mol %). The tube was capped and transferred into a glovebox. In the glovebox, the tube was charged with Ph2P(O)H (4.9 mg, 0.024 mmol, 12 mol %) and 1,2-dichloroethane (DCE) (1.5 mL). The tube was capped and removed from the glovebox, and then maintained at 120 °C for 16 h. Subsequently, the reaction mixture was cooled to room temperature, and purified by silica gel flash column chromatography. Results and Discussion Optimization studies We initiated our studies by testing different reaction conditions for the envisioned Ni-catalyzed intramolecular carboacylation, using N-pyrimidinyl indole 1a as the model substrate. After careful optimization of all reaction parameters, 3-indole indanone 2a was obtained in 92% yield using a combination of Ni(cod)2/PMe3 in chlorobenzene (Table 1, Entry 1; see Supporting Information for details). The regioselectivity of 2a was confirmed by single-crystal X-ray analysis. The reaction efficiency was strongly dependent on the nature of the ligand. Other phosphine ligands also promoted this reaction, and the corresponding products were obtained, albeit in lower yields when compared to PMe3 (Entries 2–6). In addition, chlorobenzene as the solvent proved to be superior to dioxane or DCE (Entries 7 and 8). Furthermore, no carboacylation occurred without the Ni catalyst (Entry 9), while the product was obtained in 82% yield with a 5 mol % catalyst loading (Entry 10). Table 1 | Optimization of the Ni-Catalyzed Carboacylation of Indole 1aa Entry Change from Ni "Standard" Conditions Yield (%)b 1 None 92 2 PCy3 instead of PMe3 20 3 PtBu3 instead of PMe3 10 4 PPh3 instead of PMe3 40 5 dppf instead of PMe3 39 6 dppb instead of PMe3 <5 7 Dioxane instead of PhCl 86 8 DCE instead of PhCl 69 9 Without Ni(cod)2 0 10 Ni(cod)2 (5 mol %) and PMe3 (10 mol %) 82 aStandard conditions: 1a (0.1 mmol), Ni(cod)2 (10 mol %), PMe3 (20 mol %), and PhCl (1.0 mL) at 140 °C in sealed tube. bYields were determined by 1H NMR spectroscopy. Subsequently, the Rh-based precatalyst was investigated. Surprisingly, 3-substituted indanone 2a was not obtained when a range of Rh-catalyzed conditions were employed; instead, 2-substituted indanone 3a was isolated. After careful optimization, 3a was ultimately obtained in 88% yield using Rh(cod)2SbF6 and Ph2P(O)H as the metal–ligand combination (Table 2, Entry 1). The Rh catalyst is critical for this transformation, as no product was observed in the absence of Rh(cod)2SbF6 (Entry 2). Other Rh(I) catalysts exhibited lower efficiencies (Entries 3 and 4). Among the various ligands examined, secondary phosphine oxides (SPOs) were critical for facilitating the targeted transformation, and Ph2P(O)H provided the best results (Entries 5–8). Finally, the replacement of DCE with other solvents gave 3a in lower yields (Entries 9 and 10). Table 2 | Optimization of the Rh-Catalyzed Carboacylation of Indole 1aa Entry Change from Rh "Standard" Conditions Yield (%)b 1 None 88 2 Without Rh(cod)2SbF6 0 3 Rh(cod)2NTf2 instead of Rh(cod)2SbF6 67 4 Rh(cod)2BF4 instead of Rh(cod)2SbF6 <5 5 PhiPrP(O)H instead of Ph2P(O)H 55 6 (2-Naphyl)2P(O)H instead of Ph2P(O)H 86 7 PtBu3 instead of Ph2P(O)H <5 8 Ph3P instead of Ph2P(O)H <5 9 Dioxane instead of DCE 14 10 Toluene instead of DCE 40 aStandard conditions: 1a (0.1 mmol), Rh(cod)2SbF6 (4 mol %), Ph2P(O)H (12 mol %), and DCE (1.5 mL) at 120 °C in sealed tube. bYields were determined by 1H NMR spectroscopy. Scope of the reaction With the optimized conditions in hand, the substrate scope of the Ni-catalytic system was examined (Scheme 1). Electron-donating and electron-withdrawing substituents at the 3-, 4-, 5-, and 6-positions were compatible with the reaction conditions. Common functional groups such as aryl fluoride ( 2c, 2e, and 2k), chloride ( 2d and 2f), ether ( 2h), ester ( 2i), and nitro ( 2j) were unaffected by the reaction conditions. It is encouraging to note that substrates bearing substituents with different steric and electronic properties on the aryl ring of styrene, including methoxy ( 2m and 2o), fluoro ( 2n and 2q), and chloro ( 2p) groups, all provided good yields of the desired products. Furthermore, several simple diaryl ketones were also subjected to this Ni-catalyzed reaction and reacted as expected to form the corresponding products in good yields ( 2r– 2u). Under these Ni-catalyzed conditions, toluene as solvent instead of PhCl gave better yields. The regioisomers, 2-substituted indanones 3, were not obtained in any of these reactions. Scheme 1 | . Substrate scope. aToluene as solvent and reaction performed at 160 °C. bDioxane as solvent and reaction performed at 160 °C. Download figure Download PowerPoint Further studies revealed that the Rh-catalytic system could be successfully extended to various diaryl ketones, giving 2-substituted indanones 3 in high yields and selectivity (Scheme 1). Initially, we examined the effect of the indole-ring substituent on the reaction. The introduction of various electron-donating and electron-withdrawing groups at the 3-, 4-, 5-, and 6-positions of the indole ring was fully tolerated, and the corresponding 2-substituted indanones were isolated in consistently good to high yields ( 3b– 3k). With respect to the alkene component, styrene derivatives bearing electron-donating ( 3m and 3o) and electron-withdrawing substituents ( 3n, 3p, and 3q) worked well. Moreover, pyridylbenzene and pyrazolylbenzene also proved to be competent substrates, affording the desired products in modest to good yields ( 3r– 3u). Branched olefins were also studied. More specifically, using our standard Ni-based catalyst system, substrates tethered with a 1,1-disubstituted alkene ( 1v) and a 1,2-disubstituted alkene ( 1w) gave the corresponding products, namely 2,2-disubstituted indanone 2v and 2,3-disubstituted indanone 2w, in yields of 54% and 89%. However, Rh catalysis was unsuccessful in the attempted carboacylations of 1v and 1w, and no indanone products were detected in these reactions. Mechanistic studies To obtain mechanistic insights, we first performed experiments in which a 1∶1 mixture of substrates 1d and 1l was subjected to the optimized Ni- and Rh-catalytic conditions (Scheme 2a). After the reaction, we isolated products 2d and 2l from the Ni-catalyzed process, and products 3d and 3l from the Rh-catalyzed process, which indicates that the reactions occur intramolecularly. Scheme 2 | (a–c) Mechanistic exploration. Download figure Download PowerPoint Furthermore, a series of deuterium labeling experiments were conducted (Scheme 2b). Initially, a deuterium-labeling experiment using d- 1r-1 under Ni-catalytic conditions gave 94% deuterium incorporation at the b carbon in the product d- 2r-1. When d- 1r-2 was used as the substrate for Ni catalysis, deuterium was retained at the a carbon. These results are consistent with the proposed 1,2-migratory insertion pathway. Subsequently, substrate d- 1r-1 was treated under the standard reaction conditions for Rh catalysis, and 74% deuterium incorporation was observed at the b carbon of product d- 3r-1. When d- 1r-2 was used as the substrate, one of the deuterium atoms on the a carbon was transferred to the b carbon in product d- 3r-2.a These experiments support the proposed 2,1-migratory insertion mechanism. The byproducts formed during a catalytic reaction often provide useful information regarding the reaction mechanism and possible intermediates. Thus, 1a was subjected to Rh-catalyzed conditions using PhiPrP(O)H as a ligand. While the desired 3a was furnished, two major byproducts, dimer 4a and alkene 4a′, were also isolated and characterized (Scheme 2c). Furthermore, the reaction performed in the absence of the ligand gave the side product 4a in 67% yield, as confirmed by X-ray crystallography ( 4d). The presence of these two side products supports Rh-hydride D as a possible intermediate. The decarbonylation of intermediate D and reductive elimination should then result in the formation of compound 4a′, while the decarbonylation of intermediate D followed by insertion of the tethered alkene would lead to intermediate G, which can bind with another molecule of 1a. The second insertion forms the intermediate H, which can undergo β-H elimination followed by reductive elimination to furnish 4a. Based on the experimental results, a plausible mechanism was proposed, as outlined in Scheme 3. Following coordination of the transition-metal catalyst to 1a to form 1-INT-A and 2-INT-A, oxidative addition of the C–C bond to the metal center is likely to form the acyl-M-indole complexes 1-INT-B and 2-INT-B. At this stage, the mechanism of this reaction may diverge depending on the regioselectivity for migratory insertion. Ni catalysis enables the 1,2-insertion pathway, leading to intermediate 1-INT-C. Subsequent reductive elimination from 1-INT-C affords 2a. Alternatively, Rh catalysis results in intermediate 2-INT-C, which would be formed by a 2,1-insertion of 2-INT-B. Subsequent β-hydrogen elimination would lead to intermediate 2-INT-D, which upon hydride re-insertion followed by reductive elimination, leads to 3a. Scheme 3 | Proposed mechanism. Download figure Download PowerPoint Synthetic utility To demonstrate the practicability of this method, gram-scale reactions were carried out. Thus, on a 1 g scale, the desired indanones 2a and 3a were isolated in 82% and 80% yields, respectively (Scheme 4). Simple transformations of the 3-substituted indanone 2a were conveniently derivatized. For instance, conjugated inden-1-one 5a was prepared in a good yield through dehydrogenation. Reduction of 2a with NaBH4 afforded the secondary alcohol 6a, which was converted to indene 7a in the presence of TsOH. Upon treatment of 6a with NaOEt, the corresponding N–H indole 8a was obtained in a moderate yield. Notably, directing group migration took place under basic conditions, leading to enol butyrate 9a. Furthermore, 2-substituted indanone 3a was conveniently derivatized. Enolate alkylation afforded α-disubstituted indanones 10a and 11a, and indanone 3a was converted to the corresponding N–H indole 13a in a single step. Finally, the directing group migrated from the indole ring to the α-position of the indanone scaffold under basic conditions. Scheme 4 | Synthetic utility. Download figure Download PowerPoint Conclusion A new approach for the catalyst controlled and regioselective preparation of substituted indanones has been developed. The switch in selectivity was attributed to the careful choice of different transition-metal catalysts, which notably converted the same substrates to either 2- or 3-substituted indanones. The reaction is atom economical with a high efficiency and selectivity over a wide range of substrates. We believe that this unique catalyst-controlled regioselective transformation should not only aid in understanding the behaviors of different transition-metal catalysts in C–C bond cleavage, but will also open opportunities for preparing new C–C activation systems for the rapid construction of useful products. Detailed mechanistic study (experimental and computational) and efforts to expanding new reactivity of ketones are ongoing in our laboratories. Footnotes a The H/D scrambling at the a carbon was probably due to the exchange of deuterium and hydrogen in the reaction system. Supporting Information Supporting Information is available. Conflict of Interest There is no conflict of interest to report. Funding Information Financial support for this study was provided by the National Natural Science Foundation of China (nos. 21632003, 21901202, and 21971205) and the Natural Science Basic Research Program of Shaanxi (no. 2020JQ-576). Acknowledgments The authors wish to thank Prof. Guangbin Dong for insightful discussions. References 1. Patil S. A.; Patil R.; Patil S. A.Recent Developments in Biological Activities of Indanones.Eur. J. Med. Chem.2017, 138, 182–198. Google Scholar 2. Kerr D. J.; Hamel E.; Jung M. K.; Flynn B. L.The Concise Synthesis of Chalcone, Indanone and Indenone Analogues of Combretastatin A4.Bioorg. Med. Chem.2007, 15, 3290–3298. Google Scholar 3. Gu X. H.; Yu H.; Jacobson A. E.; Rothman R. B.; Dersch C. 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