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Ruthenium-Catalyzed Redox-Neutral [4+1] Annulation of Benzamides and Propargyl alcohols via C-H Bond Activation Xiaowei Wu, Bao Wang, Shengbin Zhou, Yu Zhou, and Hong Liu ACS Catal., Just Accepted Manuscript • Publication Date (Web): 27 Feb 2017 Downloaded from http://pubs.acs.org on February 27, 2017
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Ruthenium-Catalyzed Redox-Neutral [4+1] Annulation of Benzamides and Propargyl Alcohols via C-H Bond Activation Xiaowei Wu,†, ‡ Bao Wang,†, § Shengbin Zhou,†, ‡ Yu Zhou,*,† and Hong Liu*,† †
Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai, 201203, China. ‡
University of Chinese Academy of Sciences, No.19A Yuquan Road, Beijing 100049, China. School of Life Science and Technology, ShanghaiTech University, 100 Haike Road, Pudong, Shanghai, 201210, China.
§
ABSTRACT: Internal alkynes have been used widely in transition metal-catalyzed cycloaddition reactions in which they generally serve as two-carbon reaction partners. Herein, we reported ruthenium(II)-catalyzed redox-neutral [4+1] annulation of benzamides and propargyl alcohols, in which propargyl alcohols acted as one-carbon units. This synthetic utility of propargyl alcohols led to a series of potentially bioactive N-substituted quaternary isoindolinones with moderate to high yields under mild conditions. Without the requirement for an external metal oxidant, this title transformation is compatible with various functional groups, which further underscores its synthetic utility and versatile applicability. In addition, preliminary mechanism experiments were conducted and a plausible mechanism was proposed.
KEYWORDS: Ruthenium-catalyzed, cyclization, one-carbon units, [4+1] annulation, isoindolinone
INTRODUCTION Transition metal-catalyzed cycloaddition reactions represent a powerful approach for the synthesis of heterocyclic compounds.1 As a consequence of the oxidative character of these coupling reactions, stoichiometric amounts of external oxidants are frequently required. As an elegant and eco-friendly strategy, the use of an oxidizing directing group (acting as an internal oxidant) has received much attention.2 Recently, internal alkynes have been applied widely in the transition metal-catalyzed intermolecular annulations with aromatic compounds. However, in these reactions, internal alkynes generally serve as two-carbon reaction partners1k,3-5 (Scheme 1, eq 1), and are seldom considered as one-carbon components to achieve intermolecular [4+1] annulations 6 with aromatic substrates. Until 2015, Chang’s group7a reported the pioneering example of rhodium(III)-catalyzed [4+1] annulation of arylnitrones to form indolines under external oxidantfree conditions by ingenious introducing the nitrone group as the redox-active functional group (Scheme 1, eq 2), in which internal alkynes are able to function as one-carbon components rather than two-carbon reaction partners. In addition, Tam’s group7b-d documented [2+1] cyclization of bicyclic alkenes with propargylic alcohols in the presence of Cp*Ru(COD)Cl (eq 3, Cp* = pentamethylcyclopentadienyl, COD = 1,4-cyclooctadiene). However, to the best of our knowledge, there are still no reports involving the combination of ruthenium-catalyzed arenes C−H activation and intermolecular [4+1] annulation with internal alkynes. During our studies to develop direct C−H functionalization reactions, we found a new aspect of propargyl alcohols 8 in
Scheme 1. Transition Metal-Catalyzed Redox-Neutral Annulation.
Ru(II)-catalyzed cycloaddition reactions with benzamides, in which it can fulfill an unusual [4+1] instead of [4+2] transformation (eq 4) to prepare isoindolinone derivatives which represent one of the most prevalent scaffolds in pharmaceuticals and complex natural products. 9 Because of their varieties of biological activities, 10-12 the development of highly efficient approach to access these compounds has been intensively studied by the synthetic community.13 Although there are sev-
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Table 1. Optimization of reaction conditions.a
3a yield (%)b
3a/4ac
CsOAc
0
-
CH3CN
CsOAc
Trace
-
Et
Dioxane
CsOAc
10
-
4
Et
THF
CsOAc
71
98:2
5
Et
DCE
CsOAc
82 (78)
98:2
6
Et
DCE
Na2CO3
0
-
7
Et
DCE
KOAc
55
95:5
8
Et
DCE
NaOAc
59
95:5
entry
R
solvent
base
1
Et
MeOH
2
Et
3
9
d
t-Bu
DCE
CsOAc
50
96:4
10e
Me
DCE
CsOAc
69
94:6
f
11
Piv
DCE
CsOAc
Trace
-
12
Et
DCE
-
0
-
13
Et
DCE
CsOAc
0
-
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using different substituted hydroxamic acid-type substrates in the reaction. When we introduced the bulkier tert-butyl or the methyl groups, the corresponding product was obtained in obviously decreased yield and the selectivity reduced slightly (entries 9 and 10). Moreover, it failed to give the desired product while using pivaloyl instead of ethyl group (entry 11). Additionally, the reaction did not proceed in the absence of Scheme 2. Scope of benzhydroxamic acids.a,b
a
Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), Catalyst (5 mol %), Base (1 equiv) in Solvent (4 mL) at 60 °C, Ar atmosphere. bNMR yields using CH2Br2 as an internal standard, isolated yield in parentheses. c Determined by HPLC analysis of the crude reaction mixtures. dtert-butyl group instead of ethyl group. emethyl group instead of ethyl group. fpivaloyl group instead of ethyl group.
eral strategies for N-substituted quaternary isoindolinones using transition-metal catalysts, these reactions require functionalized starting materials or dangerous diazo compounds. 13ch Therefore, it remains a challenge to develop a more efficient, safe, and inexpensive approach for the synthesis of novel Nsubstituted quaternary isoindolinone scaffolds from simple starting materials. Herein, we describe a novel discovery of an intermolecular coupling between benzamides and propargyl alcohols via an unusual [4+1] annulation to access novel Nsubstituted quaternary isoindolinone derivatives, which are difficult to access with conventional methods.
RESULTS AND DISCUSSION Our investigations started with the reaction of Nethoxybenzamide 1a and easily available propargyl alcohol 2a, catalyzed by ruthenium complexes in the presence of CsOAc at 60 °C. An initial screen of solvents (Table 1, entries 1-5) revealed that no reaction took place in MeOH and CH 3CN, and the use of 1,4-dioxane gave a low yield of the desired product. By contrast, performing the reaction in tetrahydrofuran (THF) produced the desired -lactam 3a at 71% yield with a trace amount of [4+2] cyclization byproduct 4a (the ratio of 3a/4a = 98/2, see the Supporting Information (SI) for details). The 1H NMR yield was improved to 82% when Dichloroethene (DCE) was selected as a solvent and the ratio of 3a/4a was also 98:2 (entry 5). Further screening of a variety of bases demonstrated that CsOAc was the optimal base for the reaction. Switching to other bases such as KOAc, NaOAc or Na2CO3 led to significantly lower coupling efficiencies (entries 6-8). Subsequently, we investigated the consequence of
a
Reaction conditions: 1 (0.3 mmol), 2a (0.6 mmol), [RuCl2(p-cymene)]2 (5 mol %), CsOAc (1 equiv) in anhydrous DCE (6 mL) at 60 °C for 1~6 hours, Ar atmosphere. b Isolated yields are reported. c Isolated as a 2.3:1 ratio of regioisomers. d Isolated as a 1.1:1 ratio of regioisomers. eFor 6 hours, 35% of 1q was recovered.
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CsOAc or the catalyst [RuCl2(p-cymene)]2 (entries 12 and 13). Besides, various ruthenium catalysts with different ligands were also investigated (see the SI for details). Briefly, the optimum results could be obtained when N-ethoxybenzamide (0.2 mmol, 1a) and propargyl alcohol (0.4 mmol, 2a) in DCE were treated with 5 mol % of Ru(II) catalyst at 60 oC for 2 h. With the optimized reaction conditions established, we first examined the scope of differentially substituted benzhydroxamic acids in the cyclization reaction with propargyl alcohol 2a (Scheme 2). In general, benzhydroxamic acids bearing various electron-donating, electron-withdrawing and halide substituents at the para positions all underwent smooth coupling with propargyl alco hol 2a: the desired cyclization products were obtained in acceptable to good yields (33−89%). Introduction of electron-donating groups (-Me, and -OMe) to the para position of the benzene ring (1c and 1f) gave the desired products in good yields, while ortho-substituted methoxyl group substrate (1q) provided the desired product in decreased yield. The structure of 3f was unambiguously confirmed by an X-ray crystallographic analysis (see the SI for details).14 In contrast, substrates bearing electron-withdrawing substituents, such as trifluoromethyl, methyl carboxylate, at the para position of benzohydroxamic acids resulted in slightly decreased yields (3l and 3o), while the use of para- or ortho-substituted cyano (1j), nitro (1h), and fluorine (1p) substrates reduced the yields significantly. In addition, the desired products (3i and 3g) were obtained in good to excellent yields regardless of whether halogen groups, such as bromine and chlorine, were introduced at the para position of the benzene ring. When a bromine group was placed at the meta position (1d), a 2.3:1 ratio of regioisomers was observed. This effect was also observed with naphthyl amides (1n), where a 1.1:1 ratio of regioisomers was detected by 1H NMR. The increasing kinetic acidity of the ortho C−H bond, which exceeded the steric bias of the C−H activation, probably resulted in a decrease in regioselectivity, thus giving a mixture of regioisomers.13e Importantly, a para-vinyl group (3k) is well tolerated in the reaction. This finding underscores the pronounced degree of chemoselectivity inherent in this method.3c In addition, Notably, various functionalized benzamides bearing vinyl, cyano, nitro, methyl carboxylate and halides were compatible with the standard reaction conditions, which guaranteed further transformation. We next explored the scope of propargyl alcohols (Scheme 3). The coupling of N-ethoxybenzamide 1a and various substituted propargyl alcohols gave the desired products in moderate to good yields (3r-3zi). Substrates bearing electronwithdrawing groups, such as trifluoromethyl, nitro, and halides, at the phenyl moiety of propargyl alcohols were well tolerated under the standard reaction conditions (3r-3w). A similar level of efficiency was observed with substrates having p-tolyl and 2-naphthyl groups (3x and 3za); while some other electronrich substrates provided the desired products at decreased yields (3y and 3z). Significantly, substrates changing the phenyl moiety of the propargyl alcohols with N-protected piperidyl, pyridinyl, benzyl or alkyl (e.g., ethyl) also underwent the cyclization smoothly with satisfactory results (3zb, 3zc, 3ze and 3zf). In addition, the introduction of bulkier groups (such as propyl, cyclopropyl, isobutyl, and chloropropyl) in the R1 moiety of substrates also provided the corresponding products in good yields (3zd, 3zg, 3zh, and 3zi). The sensitive
cyclopropane fragment was stable under the reaction conditions. Unfortunately, the reaction didn’t afford the desired products (3zk and 3zl) in the presence of 1-phenyl-2-propyn1-ol 2u and 4,4-dimethyl-1-phenylpent-2-yn-1-ol 2v. The coupling of N-ethoxybenzamide 1a with propargyl alcohol 2t or 2w provided isoquinolones (4zj and 4zm) in moderate yields. Scheme 3. Scope of propargyl alcohols.a,b
a
Reaction conditions: 1 (0.3 mmol), 2a (0.6 mmol), [RuCl2(p-cymene)]2 (5 mol %), CsOAc (1 equiv) in anhydrous DCE (6 mL) at 60 °C for 1~6 hours, Ar atmosphere. bIsolated yields are reported. c89% of Nethoxybenzamide 1a was recovered. ND = no detected.
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Scheme 4. Gram-scale preparation of 3w and the construction of isoindolo[2,1-a]quinoline scaffold.
To evaluate the efficiency and potential for practical applications of our method, a scale-up experiment was carried out under the standard conditions (Scheme 4a). As a result, gramscale preparation of 3w (1.08 g) was obtained in 82% yield. In addition, we explored the transformation of the product 3zn to construct an intriguing privileged scaffold isoindolo[2,1a]quinoline derivative 3zn-1 (Scheme 4b).
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ditions and provided the product [D]n-3w smoothly, with no deuterium incorporation on the -methylene group. Then we performed the coupling reaction using a deuterium-labeled propargyl alcohol 2a-d, approximately 12% and 45% deuteration was observed at the -methylene group. To determine whether proparyl alcohol is first isomerized to a unsaturated ketone under Ru(II) catalysis, we carried out two control experiments (Scheme 6b). We found that the reaction didn’t proceed when using -unsaturated ketone 2y or 2z. Additionally, we hypothesized whether the reaction could produce a similar intermediate 5 which is followed by an azaMicheal addition to afford the product. It failed to give the cyclization product while using compound 5 under standard conditions. To further probe the C−H activation process, kinetic isotope effect (KIE) experiments were carried out. The KIE was measured from the intermolecular competitive coupling of Scheme 6. Mechanism Experiments.
To determine the electronic preference of the reaction, an illustrative competition experiment between the unsubstituted benzamide 1a and substrate 1o was conducted. The result revealed that the reaction favored the electron deficient amide in a 1.9:1 ratio (Scheme 5a). This experiment indicated that C−H activation preferred more acid C−H bonds and the step of C−H activation might be irreversible via acetate assistance.15 In addition, when the propargyl alcohol 2a was used in competition with 2b, the electron-deficient substrate was favored in a 1.7:1 ratio (Scheme 5b). Scheme 5. Intermolecular competition experiments.
To shed more light on the reaction mechanism, a series of deuterium-labeling experiments were performed. The reversibility of the C−H activation was determined by removing the propargyl alcohol and performing the reaction in the presence of methanol-d4 (Scheme 6a. 1H NMR analysis revealed approximately 5% deuteration at the ortho positions of the benzohydroxamic acid (see the SI for details). Carrying out the same reaction in the presence of propargyl alcohol 2g led to no deuterium incorporation into the phenyl ring of -lactam 3w. These results suggested that cycloruthenation is irreversible under the reaction conditions. Importantly, H/D exchange was observed at the -methylene group of 3w, and both protons were partially deuterated (30% D and 40% D). Substrate 1a-d5 was subjected to the reaction with 2g under the standard con-
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an equimolar mixture of 1a and 1a-d5 with propargyl alcohol 2g, and a kH/kD value of 4.0 was obtained on the basis of 1H NMR analysis. In addition, two parallel reactions using 1a and 1a-d5 gave a KIE value of 1.7 (Scheme 6c). These results suggested that C−H cleavage is likely involved in the rate-limiting step. Based on the preliminary mechanistic experiments and previous literature,16,17 a possible mechanism is proposed (Scheme 7). First, an active catalyst is generated through anion exchange with cesium acetate. Coordination of benzamide 1 to Ru(II) and subsequent ortho C−H bond activation forms a five-membered ruthenacycle I. The regioselective coordination and migratory insertion of propargyl alcohol 2a into the Ru-C bond of ruthenacycle I provide a seven-membered intermediate II. Reductive elimination of intermediate II would give rise to the minor product 4a as described with alkynes.16 However, an alternative pathway is the abstraction of the allylic proton by the ruthenium complex or 1,2-hydride migration to afford a -allylic ruthenacycle intermediate III.17b Subsequently, intermediate III undergoes reductive elimination and enol-keto tautomerism to form intermediate IV, which is followed by oxidative addition to break the N−O bond to form intermediate V. Finally, reductive elimination takes place to release product 3 and concomitantly regenerates Ru(II) catalyst to complete the catalytic cycle. Scheme 7. Proposed catalytic cycle.
irreversible via acetate assistance. Detailed mechanistic studies and the application of this unique reaction to other substrates are currently in progress in our laboratory.
ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org. Experimental procedures, characterization data, and copies of NMR and HPLC spectra (PDF) X-ray data (CIF)
AUTHOR INFORMATION Corresponding Author * E-mail:
[email protected]. * E-mail:
[email protected] Notes The authors declare no competing financial interests.
ACKNOWLEDGMENT We gratefully acknowledge financial support from the National Natural Science Foundation of China (81620108027, 21632008, 21602234 and 81220108025), the Major Project of Chinese National Programs for Fundamental Research and Development (2015CB910304).
REFERENCES
CONCLUSIONS In conclusion, we have developed an unprecedented Ru(II)catalyzed redox-neutral [4+1] annulation of benzamides and propargyl alcohols by C−H bond activation for accessing potentially bioactive N-substituted quaternary isoindolinones with moderate to high yields under mild conditions. The most significant characteristic of this study is that a new synthetic aspect of propargyl alcohols is found in Ru-catalyzed cycloaddition reactions with benzamides, in which it can fulfill an unusual [4+1] instead of normal [4+2] transformation. Additionally, this method is compatible with various functional groups, which further underscores its synthetic utility and applicability. Mechanistic studies suggest that C−H activation is
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