Ruthenium-Catalyzed ortho Alkenylation of Aromatics with Alkenes at

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Ruthenium-Catalyzed ortho Alkenylation of Aromatics with Alkenes at Room Temperature with Hydrogen Evolution Rajendran Manikandan, Padmaja Madasamy, and Masilamani Jeganmohan* Department of Chemistry, Indian Institute of Science Education and Research, Pune 411021, India S Supporting Information *

ABSTRACT: A ruthenium-catalyzed oxidant-free highly regioselective ortho alkenylation of substituted aromatics such as aromatic amides, aromatic ketoximes, and anilides with alkenes in the presence of AgSbF6 and acetic acid in ClCH2CH2Cl at room temperature is described. The alkenylation reaction provides ortho alkenylated aromatics along with evolution of H2 gas. In the reaction, no oxidant was used, and the whole catalytic reaction has occurred without changing the oxidation state of the metal. KEYWORDS: ruthenium catalysis, C−H bond activation, alkenylation, hydrogen evolution, oxidant free, ambient temperature

T

he transition metal-catalyzed ortho alkenylation of substituted aromatics with alkenes via C−H bond activation is one of the powerful methods to synthesize substituted alkenes in a highly regio- and stereoselective manner.1 In 1968, Fujiwara’s group reported a palladiummediated alkenylation of electron-rich aromatics with alkenes via an electrophilic metalation pathway.2a,b In 1993, Murai’s group reported a ruthenium-catalyzed highly regioselective ortho alkylation of electron-deficient aromatic ketones with alkenes via a chelation-assisted oxidative addition pathway.2c Meanwhile, in the chelation-assisted deprotonation pathway, alkenylation can be done at the C−H bond of substituted aromatics with alkenes (Figure 1).1 Initially, palladium

Pd(II), Rh(I) to Rh(III), and Ru(0) to Ru(II)] is required to regenerate the active catalyst. Generally, a stoichiometric amount of inorganic or organic oxidants such as AgOAc, Ag2O, Cu(OAc)2, Fe(OAc)2 PhI(OAc)2, benzoquinone, and K2S2O8 is required to regenerate the active catalyst. Particularly, in most of the reported metal-catalyzed alkenylation reaction, a stoichiometric amount Cu(OAc)2 was used as an oxidant.4,5 Recently, in some metal-catalyzed alkenylation reactions, a catalytic amount of Cu(OAc)2 along with air or oxygen was used.4−7 Meanwhile, in some palladium-catalyzed alkenylation reactions, organic acid along with molecular oxygen was used.8 However, a higher reaction temperature is required to execute the reaction. Due to a higher reaction temperature, in the alkenylation of substituted aromatics with alkenes, the dimerization of alkenes was observed as a side product in most cases.9 Until the current time, in the ruthenium-catalyzed alkenylation reaction, a stoichiometric amount of Cu(OAc)2 or a catalytic amount of Cu(OAc)2 along with air or oxygen oxidant was used.5,6 In addition, in the ruthenium-catalyzed alkenylation reaction, a higher reaction temperature is required. Thus, the development of a convenient protocol for the alkenylation reaction such as alkenylation at room temperature, avoiding oxidants, and suppressing the formation of alkene dimerization is important. In a ruthenium-catalyzed alkenylation reaction, after βhydride elimination, a ruthenium hydride intermediate is formed. It is known that a metal hydride species readily reacts with water or organic acids forming a metal hydroxide or carboxylate species along with hydrogen evolution.10 With this background, we have planned to use acetic acid in the reaction,

Figure 1. ortho Alkenylation of aromatics with alkenes.

complexes are widely used as catalysts in this type of alkenylation reaction.3 Later, the alkenylation reaction has been explored with a rhodium catalyst.4 Recently, a less expensive and easily affordable ruthenium catalyst has gained much attention in this reaction.5 Normally, in the C−H bond functionalization reaction via deprotonation pathway, the oxidation step such as a metal with lower oxidation state into the higher oxidation state [Pd(0) to © XXXX American Chemical Society

Received: October 2, 2015 Revised: December 1, 2015

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ACS Catalysis Table 1. Scope of Aromatic Amides 1b−ma

which could readily react with H−Ru species giving the active Ru-OAc catalyst without using any oxidizing agent. In this manner, the oxidation step such as the oxidation of Ru(0) to Ru(II) can be avoided, and the catalytic reaction can be done without changing the oxidation state of metal. In addition, H2 gas can be produced. Treatment of N-methyl benzamide (1a) with methyl acrylate (2a) (2.0 equiv) in the presence of [{RuCl2(p-cymene)}2] (5.0 mol %), AgSbF6 (20 mol %) and acetic acid (2.0 equiv) in ClCH2CH2Cl (DCE) at room temperature for 24 h gave product 3aa in 81% isolated yield along with H2 gas evolution (Scheme 1). The liberation of H2 gas was confirmed by gas Scheme 1. Ruthenium-Catalyzed ortho Alkenylation of NMethyl Benzamide (1a) with Methyl Acrylate (2a)

chromatograph with a TCD detector. In the reaction, no methyl acrylate (2a) dimerization product and reduced product of 2a such as methyl propionate (Et-CO2Me) was observed. The alkenylation reaction was also examined with 1.0 equiv of methyl acrylate (2a). However, product 3aa was observed only in 62% yield. It is important to note that in the present reaction, ortho alkenylation of benzamides followed by intramolecular aza-Michael cyclization providing cyclic lactams was not observed.5d The alkenylation reaction was also examined with other solvents such as 1,4-dioxane, THF, DME, methanol, toluene, CH3CN, DMSO, DMF, and water instead of DCE. THF, DME and 1,4-dioxane were partially effective, providing product 3aa in 52%, 54%, and 40% isolated yields, respectively. Remaining solvents were not effective. Further, the alkenylation reaction was examined with other organic acids such as pivalic acid, 2,6-dimethylbenzoic acid, 1-adamantanecarboxylic acid, and benzoic acid instead of acetic acid. These acids were partially effective, yielding product 3aa in 69%, 64%, 61%, and 38% yields, respectively. The catalytic reaction was also tested with other additives such as AgBF4, AgOTf, KPF6, and CuBF4 instead of AgSbF6. AgBF4 and AgOTf were partially effective, providing product 3aa in 52% and 64% yields, respectively. KPF6 and CuBF4 were not effective. It is important to note that no product 3aa was observed without additive AgSbF6. Under the optimized reaction conditions, the alkenylation reaction of 1a was tried in a gram scale with 2a. The reaction worked nicely and providing product 3aa in 79% isolated yield. The scope of the alkenylation reaction was examined with various substituted aromatic amides 1b−m (Table 1). The alkenylation reaction was compatible with various sensitive functional groups such as F-, Cl-, Br-, I-, CF3-, and NO2substituted aromatic amides. The reaction of electron-donating groups such as Me- and OMe-substituted benzamides 1b−c with 2a provided ortho alkenylated benzamides 3ba and 3ca in 78% and 46% yields, respectively (Table 1, entries 1 and 2). Halogen groups such as F-, Cl-, Br-, and I-substituted benzamides 1d−g provided ortho alkenylated aromatic amides 3da-ga in 71%, 64%, 61%, and 55% yields, respectively (entries 3−6). Less-reactive electron-withdrawing groups such as NO2-

a

All reactions were carried out using substituted amides 1b−m (100 mg), methyl acrylate (2a) (2.0 equiv), [{RuCl2(p-cymene)}2] (0.05 equiv), AgSbF6 (0.20 equiv), AcOH (2.0 equiv) in 1,2-dichloroethane (3.0 mL) at room temperature for 24 h. bIsolated yield. cAcOH (4.0 equiv) was used.

and CF3-substituted benzamides 1h−i also efficiently participated in the reaction, giving alkene derivatives 3ha and 3ia in 53% and 69% yields, respectively (entries 7−8). ortho-Methyl benzamide (1j) was also effectively involved in the reaction, giving product 3ja in 70% yield (entry 9). Next, the alkenylation reaction was tested with unsymmetrical aromatic amides 1k−m (entries 10−12). meta-Chloro benzamide (1k) and 2-naphthyl benzamide (1l) underwent alkenylation at the less-hindered C−H bond with 2a, providing alkene derivatives 3ka and 3la in 68% and 78% yields, respectively. In contrast, in the reaction of 1m with 2a, an alkenylation takes place at a hindered C6−H of 1m, yielding product 3ma in 62% yield. Due to the dual coordination of an ether O atom and carbonyl oxygen atom of amide 1m, alkenylation takes place selectively at the hindered C−H bond. The alkenylation reaction was examined with N-substituted aromatic amides 1n−q with 2a or 2b (Scheme 2). N-Benzyland N-OMe-substituted benzamides 1n−p efficiently reacted with 2a or 2b, giving the corresponding alkene derivatives 3na, 3oa and 3pb in 51%, 86% and 88% yields, respectively. In the reaction of 1o−p with 2, OMe moiety of the amide group was 231

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ACS Catalysis Scheme 2. Scope of N-Substituted Benzamides

respectively (entries 1−3). 2-Phenoxyethyl acrylate (2f) was also nicely involved in the reaction, yielding an alkene derivative 3af in 61% yield (entry 4). n-Butyl (2b), tert-butyl (2g), and cyclohexyl (2h) acrylates reacted with 1o, providing ortho alkenylated benzamides 3ob−oh in 91%, 88%, and 90% yields, respectively (entries 5−7). Phenyl vinyl sulphone (2i) also participated in the reaction, providing product 3ai in 61% yield (entry 8). However, styrene (2j) did not react with 1a at room temperature. At 100 °C, styrene (2j) reacted with 1a in 1,4dioxane, yielding product 3aj in 43% yield (entry 9). The alkenylation reaction was successfully extended to substituted anilides 4 and aromatic ketoximes 6 (Scheme 3). Scheme 3. Scope of Anilides and Aromatic Ketoximes

cleaved and acts as an internal oxidant.7 Tertiary amide 1q also efficiently reacted with 2a, affording 3qa in 60% yield. The scope of the alkenylation reaction was further examined with substituted alkenes 2b−j (Table 2). Ethyl (2c), benzyl (2d), and phenyl (2e) acrylates nicely reacted with 1a, giving alkene derivatives 3ac−ae in 80%, 76%, and 71% yields, Table 2. Alkenylation of Aromatic Amides 1a or 1o with Substituted Alkenes 2b−ja

Treatment of substituted anilides 4a−b with methyl acrylate (2a) under the optimized reaction conditions at ambient temperature gave ortho alkenylated anilides 5aa−ba in 58% and 47% yields, respectively. In a similar fashion, substituted aromatic ketoximes 6a−b reacted with 2a at ambient temperature, affording ortho alkenylated aromatic ketoximes 7aa−ba in 56% and 42% yields, respectively. A possible reaction mechanism for ortho alkenylation of substituted aromatics with alkenes is proposed in Scheme 4. Scheme 4. Proposed Mechanism

AgSbF6 likely removes Cl ligand from [{RuCl2(p-cymene)}2] complex giving a cationic ruthenium species 8. Later, the oxygen atom of amide 1 coordinates with a ruthenium species 8 followed by ortho-metalation providing a five-membered ruthenacycle intermediate 9.11 Coordinative insertion of alkene 2 into the Ru−carbon bond of intermediate 9 gives intermediate 10. β-Hydride elimination of intermediate 10

a

All reactions were carried out using 1a or 1o (100 mg), alkenes 2b−j (2.0 equiv), [{RuCl2(p-cymene)}2] (0.05 equiv), AgSbF6 (0.20 equiv), AcOH (2.0 equiv) in 1,2-dichloroethane (3.0 mL) at room temperature for 24 h. bIsolated yield. c1,4-Dioxane solvent was used, and the reaction was done at 100 °C. 232

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ACS Catalysis affords ortho alkenylated aromatic amides 3 and a ruthenium hydride species 11. Later, a ruthenium hydride species 11 reacts with acetic acid liberating H2 gas and regenerates the active catalyst 8. In the reaction, the whole catalytic reaction has occurred without changing the oxidation state of metal. The role of AcOH is crucial in the reaction in which AcOH directly reacts with a ruthenium hydride species 11, forming the active ruthenium(II) acetate species 8 and preventing the formation of typical ruthenium(0) species. Thus, the extra oxidation step is avoided. In addition, an acetate moiety of ruthenium(II) species 8 acts as a base to deprotonate the ortho C−H bond of aromatic moiety. In the reaction, AgSbF6 plays a dual role; it acts as a halogen scavenger and also the [SbF6]− noncoordinating anion stabilizes the ruthenium species. To prove the formation of intermediate 9 step is a reversible process, 1a was treated with CD3COOD in the presence of [{RuCl2(p-cymene)}2] (5.0 mol %) and AgSbF6 (20 mol %) in 1,2-dichloroethane at room temperature for 6 h. In the reaction, product d-1a′ was observed in 96% yield with 72% and 73% of deuterium incorporation at the both ortho carbons, respectively (Scheme 5). In the meantime, we have tried to isolate the key

the spectrum (see Supporting Information). This result clearly reveals that in the H2 gas evolution, one of the hydrogen comes from the acetic acid and another one from the Ru−H species. It is important to point out that the deuterium incorporation was not observed in the N−H bond of product 3aa. This result clearly supports the carbonyl coordination of amide into the ruthenium species 8. It is interesting to note that the H2 evolution was not observed in the reaction of N-methoxysubstituted benzamide 1o with methyl acrylate (2a). In the reaction, the N-OMe group of 1o acts as an internal oxidant, but this reaction did not proceed without AcOH. In conclusion, we have described a highly regioselective ortho alkenylation of aromatic amides and ketoximes or anilides with alkenes in the presence of a ruthenium catalyst, AgSbF6 and AcOH at room temperature without an oxidant. Interestingly, H2 gas was observed at room temperature. The proposed reaction mechanism was supported by experimental evidence.



ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.5b02218. General experimental procedure and characterization details (PDF)

Scheme 5. Mechanistic Studies



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS We thank the INSA (SP/YSP/99/2014), India for the support of this research. R.M. thanks the CSIR for a fellowship. We thank Dr. Naveen Gandhi (IITM Pune) for checking IR-MS. We would thank the reviewers for their constructive suggestions to improve the mechanism of the reaction.



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