Nickel-Catalyzed Regio- and Enantioselective Hydroarylation of 1,3-Dienes with Indoles

Open AccessCCS ChemistryCOMMUNICATION5 Aug 2022Nickel-Catalyzed Regio- and Enantioselective Hydroarylation of 1,3-Dienes with Indoles Lei Cheng, Ming-Ming Li, Mao-Lin Li, Li-Jun Xiao, Jian-Hua Xie and Qi-Lin Zhou Lei Cheng State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 , Ming-Ming Li State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 , Mao-Lin Li State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 , Li-Jun Xiao State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 , Jian-Hua Xie State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 and Qi-Lin Zhou *Corresponding author: E-mail Address: [email protected] State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 https://doi.org/10.31635/ccschem.021.202101472 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail The regio- and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds, yet it remains a challenge for aliphatic dienes. Herein, we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives. Because the reaction is performed under redox-neutral and mild conditions, various functional groups are tolerated in the reaction. Density functional theory calculations elucidate the mechanism of reaction, regioselectivity, and enantioselectivity of the nickel-catalyzed hydroarylation of aliphatic dienes with indoles. Download figure Download PowerPoint Introduction The transition-metal-catalyzed hydrofunctionalization of unsaturated hydrocarbons has emerged as a useful method to produce value-added molecules.1,2 In particular, asymmetric hydrofunctionalization of dienes with carbon nucleophiles offers straight-forward access to chiral compounds containing allylic C–C bonds.3–5 However, the highly selective hydrofunctionalization of dienes is mainly focused on aromatic 1,3-dienes.6–21 In contrast, there are few successful examples of the hydrofunctionalization reactions using aliphatic 1,3-dienes (Scheme 1a).18 Due to the small steric hindrance of the alkyl chain, aliphatic 1,3-dienes are transformed into η3-π-allyl intermediates a and b by hydrometallation at C1 and C4, and three regioisomers can be formed during nucleophilic attack (Scheme 1b).4 Moreover, β-H elimination of intermediate b leads to formation of a 1,4-disubstituted diene. These properties of aliphatic dienes make the selectivity-control of hydrofunctionalization reactions particularly challenging. Previous studies have shown that the selectivities are closely related to the electronic and steric nature of the diene substrate, and the use of cyclic and highly sterically hindered substrates is necessary for achieving good selectivities.8,10,13 Therefore, a general method for the regio- and enantioselective hydrofunctionalization of aliphatic dienes with carbon nucleophiles is highly desirable. Scheme 1 | Catalytic regio- and enantioselective hydrofunctionalization of dienes with carbon nucleophiles. Download figure Download PowerPoint Chiral indole structures are common in natural products and pharmacologically relevant compounds.22–24 The development of methods for the synthesis of chiral indole derivatives is an important task in organic synthesis.13,25–31 As part of our ongoing research aimed at developing nickel-catalyzed C–C bond-forming reactions,15,19,32–36 we herein report a method for nickel-catalyzed asymmetric hydroarylation of aliphatic dienes with indoles to afford chiral indole derivatives with high regio- and enantioselectivities (Scheme 1c). Results and Discussion In initial experiments, we carried out asymmetric hydroarylation of (E)-trideca-1,3-diene ( 2a) with indole ( 1a) to evaluate various reaction parameters (Table 1). Under the optimized conditions, desired 3,4-hydroarylation product 3a was obtained in 60% yield with 94:6 enantiomeric ratio (er) and excellent regioselectivity (3,4- to 1,4-hydroarylation products, >20∶1; entry 1). The yield and enantioselectivity dramatically decreased in the absence of base (20% yield, 72∶28 er; entry 2). Solvent screening showed that the reaction only occurred in alcohols and the steric hindrance of alcohol greatly influenced the reaction regioselectivity, with iPrOH providing the best results (entries 1 and 3–6). Comparison of various ligands revealed that 2,2′-bis(diphenylphosphino)-1,1′-biphenyl ligands were effective for controlling the regioselectivity and enantioselectivity, with L1 being the best choice (entries 1 and 7–13).a When the reaction time was extended to 72 h, the substrate was completely converted, and the yield was slightly increased (69% yield, 94∶6 er; entry 14). Table 1 | Reaction Condition Optimization Entry Conditions Solvent Ligand Yield (%) er (%) rr 1 As shown iPrOH L1 60 94∶6 >20∶1 2 No base iPrOH L1 20 72∶28 >20∶1 3 Solvent change MeOH L1 5 84∶16 3.3∶1 4 Solvent change EtOH L1 21 86∶14 4.2∶1 5 Solvent change nPrOH L1 55 92∶8 10∶1 6 Solvent change iBuOH L1 52 93∶7 14∶1 7 Ligand change iPrOH L2 <5 63∶37 — 8 Ligand change iPrOH L3 42 89∶11 >20∶1 9 Ligand change iPrOH L4 28 82∶18 >20∶1 10 Ligand change iPrOH L5 47 92∶8 >20∶1 11 Ligand change iPrOH L6 53 94∶6 >20∶1 12 Ligand change iPrOH L7 37 78∶22 >20∶1 13 Ligand change iPrOH L8 28 82∶18 >20∶1 14 72 h iPrOH L1 69 94∶6 >20∶1 Reaction conditions: 1a (0.165 mmol), 2a (1.0 equiv), Ni(COD)2 (5 mol %), ligand (5 mol %), tBuOK (0.1 equiv), solvent (0.3 mL) at 60 °C for 36 h. Isolated yields, regioisomeric ratio (rr) was determined by 1H NMR analysis, er was determined by chiral HPLC analysis. DTBM, 3,5-di-tert-butyl-4-methoxyphenyl; TMS, trimethylsilyl. Under the optimal conditions, we investigated the generality of the asymmetric hydroarylation reaction (Table 2). We began by examining the substrate scope with respect to the indole by carrying out reactions of various indoles with (E)-trideca-1,3-diene ( 2a) (Table 2a). All the tested indoles gave 3,4-addition products with excellent regioselectivity (>20∶1). Indoles substituted at C5, C6, or C7 produced the corresponding hydroarylation products ( 3b– 3h) in good yields (66–90%) with high enantioselectivities (93.5∶6.5 to 96.5∶3.5 er). In addition, 2-methylindole afforded desired product 3i in 94% yield, albeit with diminished enantioselectivity (86.5∶13.5 er). However, the N-methylindole is inert in hydroarylation reaction. The absolute configuration of 3a was determined as R by derivatization and comparison to a known compound (see Supporting Information for details). Table 2 | Substrate Scope of Ni-Catalyzed Hydroarylation of Aliphatic 1,3-Dienes Reaction conditions: 1 (0.165 mmol), 2 (0.165 mmol), Ni(COD)2 (5 mol %), L1 (5 mol %), tBuOK (10 mol %), iPrOH (0.3 mL), 60 °C, 72 h. Isolated yields, rr (>20:1) was determined by 1H NMR analysis, er was determined by chiral HPLC analysis. ( a) Variation of the indole substrates. ( b) Variation of the aliphatic diene substrates. a40 °C. b7 mol % catalyst, 40 °C. c7 mol % catalyst, 70 °C. We also evaluated the scope of the reaction with respect to the aliphatic 1,3-diene by carrying out reactions with 7-methylindole (Table 2b). The length and steric bulk of the alkyl chain of diene had little influence on the regio- and enantioselectivity of the hydroarylation reaction (compare 3c with 3j, 3k, 3r, 3t, 3u, 3y, and 3aa). The reaction conditions were compatible with various functional groups such as olefins ( 3l and 3m), ethers ( 3n– 3p and 3v), an ester ( 3s), and halogen atoms ( 3q and 3z), which provide opportunities for subsequent transformations. Dienes with a cyclic alkyl group ( 3t– 3v) gave lower yields than those with linear alkyl groups and needed higher reaction temperature and higher catalyst loading for achieving desirable results. Substrates with a remote aromatic ring ( 3y, 3z, and 3aa) or heteroaromatic ring ( 3w and 3x) worked well; no products resulting from olefin migration to the benzyl position and subsequent hydroarylation were detected.37,38 In addition, this hydroarylation reaction could be used for late-stage modification of a structurally complex molecule bearing multiple stereocenters (87% yield, 97:3 dr, 3ab). Notably, highly conjugated polyene substrate also underwent regioselective hydroarylation, affording product 3ac with a diene moiety. To verify whether this catalyst system could work for aromatic dienes, we performed nickel-catalyzed asymmetric hydroarylation reactions between aromatic 1,3-dienes and indoles, which have been previously reported as sluggish and poorly selective.13 To our delight, the use of chiral ligand L6 or L8 enabled the hydroarylation of aromatic dienes 4 with indoles 1 under modified conditions (see Supporting Information for details). The addition products 5a– 5u were obtained in good yields with high regio- and enantioselectivities (Table 3). The hydroarylation reaction worked well with indoles substituted at C5, C6, or C7 ( 5b– 5h) and was compatible with methoxy and cyano groups and F and Cl atoms. However, N-Bn protected indole was not a suitable substrate ( 5i).b Aromatic dienes bearing an electron-donating group or a fluorine atom at the para-position afforded the corresponding products ( 5j– 5n) in good yields with high enantioselectivity (95:5 to 96:4 er). The diene with a strongly electron-withdrawing p-CF3 group on the aromatic ring showed slightly lower enantioselectivity ( 5o, 93.5:6.5 er). Introducing an ortho- or meta-substituent on the aromatic ring of the diene ( 5p– 5s) had no effect on the enantioselectivity (95:5 to 96.5:3.5 er). In addition, dienes bearing a heteroaromatic ring also afforded the expected products 5t and 5u in good yields with high enantioselectivity (93:7 and 95:5 er, respectively). Table 3 | Substrate Scope of Ni-Catalyzed Hydroarylation of Aromatic 1,3-Dienes Isolated yields, rr (>20∶1) was determined by 1H NMR analysis, er was determined by chiral HPLC analysis. (a) Variation of the indole substrates. (b) Variation of the aromatic diene substrates, Z/E configuration of aromatic dienes did not affect the yield and selectivity of the reaction. aLigand L6 (10 mol %), tBuOK (10 mol %), nPrOH (0.3 mL). bLigand L8 (10 mol %), nBuOH (0.5 mL). Investigation of Mechanism To gain insight into the reaction mechanism, we conducted the hydroarylation reaction of 7-Me-indole and 2a in i-propanol-d8 and terminated the reaction after 2 h (Scheme 2, also see Supporting Information Schemes S1–S3 for details). At this point, we observed 86% deuterium incorporation into the methyl group of the product; 87% deuterium incorporation at C3 of the recovered indole; and 89% deuterium incorporation at C4 of the recovered diene. These results indicated the following: (1) hydrogen transfer occurs at C4 of the diene and C3 of the indole; (2) the nickel catalyst can rapidly and reversibly catalyze the hydrogen/deuterium exchange of diene prior to C–C bond formation. Scheme 2 | Deuterium-labeling experiment. Download figure Download PowerPoint Density functional theory (DFT) calculations were performed to estimate the energetics and enantioselectivity of the hydroarylation of aliphatic diene with indole (Scheme 3).c (E)-Pent-1,3-diene was used as the model substrate and Ni/(S)- L1 as the catalyst. Due to steric hindrance, the nickel catalyst initially coordinates with iPrOH and the terminal C=C bond of the diene to form intermediates Int-I-A and Int-I-B. These intermediates underwent a ligand-to-ligand hydrogen transfer (LLHT)39–41,d via five-membered ring transition states TS-II-R (22.5kcal/mol) and TS-II-S (22.9 kcal/mol), resulting in neutral allyl nickel intermediates Int-II-S and Int-II-R, in which only one P atom of ligand (S)- L1 coordinates with nickel. Ligand exchange between the alkoxy and indole anion generates intermediates Int-III-S and Int-III-R. The calculated energy barriers of the transition states TS-III-R and TS-III-S of the C−C reductive elimination step are 26.9 and 30.3 kcal/mol, respectively, which means that the reductive elimination is the rate- and enantio-determining step of the reaction. The energy difference between TS-III-R and TS-III-S (ΔΔG≠ = 3.4 kcal/mol) shows that the product (R)- 3 is more favorable for formation, which is consistent with the experimental result. The structural comparison of TS-III-R and TS-III-Se shows that the interatomic distances between the olefin group and nickel center in TS-III-R (2.06 and 2.31 Å) are shorter than those in TS-III-S (2.11 and 2.47 Å), indicating that the coordination of olefin with nickel in TS-III-R is stronger. This stronger coordination likely contributes to the lower energy of TS-III-R. Scheme 3 | Computed energy profile for the nickel-catalyzed asymmetric hydroarylation of dienes with indoles. Download figure Download PowerPoint Conclusion We have developed a highly regio- and enantioselective hydroarylation reaction of aliphatic and aromatic dienes with indoles by using chiral nickel catalysts. The reaction features redox-neutral, mild conditions, a broad substrate scope and good functional group tolerance, providing an efficient method for the synthesis of chiral indole derivatives. Mechanism studies show that the reaction is initiated by LLHT of nickel-alcohol-diene complex, and the C–C reductive elimination is the rate- and enantio-determining step of the reaction. Computational studies demonstrate that the chiral catalyst can differentiate various possible transition states, which explains the origin of the observed enantioselectivity. Footnotes a For results using other types of chiral ligands, see Supporting Information. b N-protected indoles, such as N-Me, N-Bn, N-Boc, and N-Ts, are inert in hydroarylations with both aliphatic and aromatic dienes. These facts suggest that the hydroarylation reaction of indoles might depend on the (reversible) deprotonation of the indole N–H bond with KOtBu to form highly nucleophilic indole anion, which participates in the C–C bond formation step. c The DFT calculations for the hydroarylation reaction were performed at the PBE0-D3(BJ)/def2-TZVPP-SMD(iPrOH)//B3LYP-D3/6-31G*!+LANL2DZ (Ni)-gas level of theory. d For the hydrogen transfer process, a stepwise pathway via Ni(II)−H species was also taken into consideration. However, the energy barrier for the iPrO−H oxidative addition by nickel catalyst is up to 31.7 kcal/mol. Thus, the LLHT is more energetically favorable. See Supporting Information Table S3 and Scheme S6 for more details of DFT calculations. e All the possible geometries of reductive elimination transition states are listed in Supporting Information Schemes S7 and S8. 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetailsCited ByHe F, Hou L, Wu X, Ding H, Qu J and Chen Y (2022) Enantioselective Synthesis of α-Alkenylated γ-Lactam Enabled by Ni-Catalyzed 1,4-Arylcarbamoylation of 1,3-Dienes, CCS Chemistry, , (1-9) Issue AssignmentVolume 4Issue 8Page: 2612-2619Supporting Information Copyright & Permissions© 2021 Chinese Chemical SocietyKeywordsC–C bond formationchiral indole derivativesasymmetric hydroarylationaliphatic dienenickel catalystAcknowledgmentsThe authors thank the National Natural Science Foundation of China (nos. 21790330 and 91956000) and the "111" Project (no. B06005) of the Ministry of Education of China for financial support. Dedicated to Prof. Christian Bruneau for his outstanding contribution to catalysis. Downloaded 3,390 times PDF DownloadLoading ...