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Stereoselective 1,2-Dicarbofunctionalization of Trisubstituted Alkenes by Palladium-Catalyzed Heck/Suzuki or Heck/Sonogashira Domino Sequence

2020; Chinese Chemical Society; Volume: 3; Issue: 9 Linguagem: Inglês

10.31635/ccschem.020.202000506

2096-5745

Jiawen Zhu, Bo Zhou, Zhong‐Yan Cao, Ren‐Xiao Liang, Yi‐Xia Jia,

Cyclopropane Reaction Mechanisms

Open AccessCCS ChemistryCOMMUNICATION1 Sep 2021Stereoselective 1,2-Dicarbofunctionalization of Trisubstituted Alkenes by Palladium-Catalyzed Heck/Suzuki or Heck/Sonogashira Domino Sequence Jia-Wen Zhu, Bo Zhou, Zhong-Yan Cao, Ren-Xiao Liang and Yi-Xia Jia Jia-Wen Zhu College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014 , Bo Zhou College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014 , Zhong-Yan Cao College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014 , Ren-Xiao Liang College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014 and Yi-Xia Jia *Corresponding author: E-mail Address: [email protected] College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 https://doi.org/10.31635/ccschem.020.202000506 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Highly enantioselective and diastereoselective 1,2-diarylation and 1,2-arylalkynylation of trisubstituted alkenes are reported via the palladium-catalyzed Heck/Suzuki or Heck/Sonogashira domino sequence. These alkenes represent an extension of enantioselective dicarbofunctionalization from terminal alkenes to trisubstituted ones based on anionic capture of the secondary alkyl-Pd intermediate. A wide range of 3,3′-spirooxindoles, featuring vicinal spiro quaternary and tertiary stereocenters, is efficiently constructed in one step with up to 94% enantioselectivities and excellent diastereoselectivities (>19:1 dr). The practicability of this method is shown by its broad substrate scope and versatile transformations of the resulting products. Download figure Download PowerPoint Introduction Consistent with the goal of green chemistry of more economical and efficient synthetic transformations, considerable attention has been paid to the sequential reaction that can quickly construct complex molecular structures along with excellent control of selectivities from simple starting materials.1–3 In this regard, the transition-metal-catalyzed olefin difunctionalization achieved by intercepting Heck alkyl-metal intermediates provides a powerful and straightforward method.4–12 By employing versatile carbon-based trapping agents to capture the alkyl-metal species derived from intramolecular carbometalation, tremendous transformations have been achieved and show their efficiency in the synthesis of cyclic molecules.4–12 Nevertheless, compared with advances in racemic reactions,13–31 the development of enantioselective olefin dicarbofunctionalization has met with limited success. In 2007, Zhu's group32 developed a palladium-catalyzed asymmetric aryl-cyanation of acrylamides through an intramolecular carbopalladation/anionic capture sequence, affording 3-cyanomethyl-2-oxindoles bearing quaternary stereocenters in moderate enantioselectivities (Figure 1a). Subsequently, by applying isonitriles and azoles as terminating agents, Zhu's group33–36 achieved functional oxindoles in high enantioselectivities and applied them as key materials for the synthesis of (+)-esermethole and (+)-physostigmine. By using the carbonylation reaction to interrupt the Heck process, Correia's group,37 Zhu's group,38 and Guan's group39 were able to independently construct 3,3′-disubstituted dihydrobenzofurans, 2-oxindole-based spiro-lactones/lactams, and 3,3′-disubstituted oxindoles in excellent enantioselectivities. Moreover, asymmetric palladium-catalyzed Heck/Suzuki and Heck/Sonogashira domino sequences were developed by Zhang's group40–43 and Lu's group,44 respectively. Alternatively, based on nickel- or copper-based chiral catalysts, Cong and Fu45 and You and Brown46 demonstrated the enantioselective dicarbofunctionalization of olefins through the reactions of aryl-9-Borabicyclo[3.3.1]nonane or aryl-Bpin-tethered alkenes with electrophilic alkyl- or aryl-halides (Figure 1b). Recently, relying on a nickel-catalyzed reductive-coupling strategy, Kong's group,47,48 Jin and Wang,49 and Shu's group50 have realized enantioselective olefin diarylation, arylalkylation, as well as arylalkenylation reactions, respectively (Figure 1c). The intramolecular carbonickelation followed by intermolecular reductive coupling with organohalides enabled the construction of two C–C σ-bonds. Figure 1 | (a–d) Enantioselective 1,2-dicarbofunctionaliztion of disubstituted alkenes and trisubstituted alkenes. Download figure Download PowerPoint Despite these remarkable achievements, the aforementioned enantioselective dicarbofunctionalization reaction was limited to the use of terminal 1,1-disubstituted or monosubstituted terminal alkenes, and only one single stereocenter was constructed through the termination of a primary alkyl-metal intermediate. Extension of the reaction to sterically more hindered trisubstituted alkenes to generate two consective stereogenic carbon centers through the capture of secondary alkyl-metal species as well as the exquisite control of both diastereoselectivity and enantioselectivity centers has remained a very challenging task.51,52,a Herein, we wish to meet the above challenges and report a palladium-catalyzed 1,2-dicarbofunctionalization of trisubstituted alkenes through a Heck/Suzuki or Heck/Sonogashira domino sequence (Figure 1d). By employing 1,1'-Bi-2,2'-naphthol (BINOL)-derived phosphoramidite as a chiral ligand, both diastereoselectivities and enantioselectivities of 1,2-diarylation and 1,2-arylalkynylation processes were nicely controlled, forming adjacent spiro quaternary and tertiary stereocenters in one step. Broad substrate scope and excellent functional group tolerance were found in the reactions. The 3,3′-spirooxindoles thus obtained are privileged skeletons of natural products and bioactive molecules.53,54 The practicability of this method is shown by the synthetic transformations of the products. Experimental Methods To a dried Schlenk tube were added 1a (0.20 mmol), Ph4BNa (0.30 mmol), Pd(OAc)2 (2.3 mg, 0.010 mmol), ligand L 13 (15.0 mg, 0.020 mmol), Na2CO3 (42.4 mg, 0.40 mmol) under N2. Toluene (2.0 mL) was then introduced via a syringe, and the tube was sealed with a Teflon cap. The resulting mixture was stirred at 60 °C for 24 h. The solvent was then removed under vacuum, and the residue was purified by flash chromatography on silica gel, eluting with ethyl acetate/petroleum ether 1:10 (v/v) to afford product 3a. More experimental details and characterization are available in the Supporting Information. Results and Discussion 1,2-Diarylation reaction: optimization and scope Initially, the model reaction between trisubstituted alkene 1a and Ph4BNa 2a was chosen to identify the optimal conditions for 1,2-diarylation (Table 1). To our delight, with Pd(OAc)2 as a catalyst, BINOL-derived N,N-dimethyl phosphoramidite L 1 as a chiral ligand, and Na2CO3 as a base, the reaction of 1a with 2a proceeded smoothly in toluene at 60 °C for 24 h to deliver product 3a in 90% yield and excellent diastereoselectivity (>19∶1 dr), with only 4% ee (Entry 1). To improve the enantioselectivity, ligands L 2 –L 7 bearing different substituents on the nitrogen atom were then evaluated (Entries 2–7). Ligand L 6 bearing the dibenz[b,f]azepine moiety gave 66% ee (Entry 6).55 A higher ee value of 76% was obtained with its saturated analogue L 7 (Entry 7). Other parameters, including the Pd precursor, base, and solvent, were then screened in the presence of ligand L 7, although no further increase of enantioselectivity was observed (see Supporting Information Table S1). Further ligand modification based on L 7 found that L 9 bearing methyl groups on the 3,3′-position dramatically improved the enantioselectivity to 88% (Entry 9). Among the aryl-substituted ligands, the L 10– L 13, L 13 bearing benzo[d][1,3]dioxol-5-yl group on the 3,3′-position resulted in the best results in our hand (92% yield and 91% ee) (Entry 13). Although employing PhB(OH)2 as a coupling partner could deliver a slightly higher ee of 94%, it was noteworthy that the reaction rate was very slow, and only moderate yield (43%) was afforded (Entry 14). The absolute configuration (1R,2R) of product 3a was determined by X-ray crystallographic analysis, showing a cis-configuration between the installed Ph group and the aryl part of the oxindole moiety.b Table 1. | Optimization Studies for 1,2-Diarylation Reactiona Entry L Yield (%)b ee (%)c 1 L 1 90 4 2 L 2 92 11 3 L 3 94 56 4 L 4 90 2 5 L 5 71 13 6 L 6 92 66 7 L 7 91 76 8 L 8 88 38 9 L 9 90 88 10 L 10 87 68 11 L 11 83 81 12 L 12 87 67 13 L 13 92 91 14d L 13 43 94 aReactions were performed on a 0.20 mmol scale. bIsolated yield. cDetermined by chiral High Performance Liquid Chromatography. dWith 1.5 equiv of phenyl boronic acid. With the optimal conditions in hand, the scope of both trisubstituted alkene 1 and sodium tetraarylborate 2 was studied. As summarized in Table 2, the diastereoselectivities of all the products were excellent and higher than 19∶1 dr. Both N-methyl and N-Bn substrates were suitable for this protocol (Entries 1 and 2). Substituents attached on the benzene ring of haloaniline were well tolerated (Entries 3–12). There was no influence of halides (F and Cl) on the reactivity and enantioselectivity at either the C4 or C5 position (Entries 5, 8, and 9). Electron-donating groups (methyl and methoxyl) and electron-withdrawing groups (CF3 and CF3O) were also tested in this reaction (Entries 3, 4, 6, 7, and 10–12). Only a marginal effect on the yields and ee values was observed. Erosion of ee in the presence of 5-CF3 and 6-Me groups was observed (Entries 11 and 12). The scope of sodium tetraarylborate 2 was then investigated. Again, the transformations took place efficiently to afford the desired products 3m– 3q in generally excellent yields and enantioselectivities (Entries 13–17). In addition to indene-derived amide, benzocyclohexene-derived amide also worked smoothly under optimal conditions to give product 3r in 93% yield and 86% ee (Entry 18). Table 2 | Substrate Scope for 1,2-Diarylation Reactiona Entry n R Ar 3 Yield (%)b ee (%)c 1 1 H Ph 3a 92 91 2d 1 H Ph 3b 89 81 3 1 4-Me Ph 3c 92 86 4 1 4-iPr Ph 3d 82 87 5 1 4-F Ph 3e 85 92 6 1 5-Me Ph 3f 82 88 7 1 5-OMe Ph 3g 87 89 8 1 5-F Ph 3h 91 89 9 1 5-Cl Ph 3i 91 86 10 1 5-OCF3 Ph 3j 96 86 11 1 5-CF3 Ph 3k 90 79 12 1 6-Me Ph 3l 91 78 13 1 H 4-MeC6H4 3m 91 92 14 1 H 4-PhC6H4 3n 85 88 15 1 H 3-MeC6H4 3o 69 92 16 1 H 2-Naphthyl 3p 89 92 17 1 H 2-Thienyl 3q 87 94 18 2 H Ph 3r 93 86 aReactions were performed on a 0.2 mmol scale. bIsolated yield. cee was checked by HPLC. dN-Bn 2b was used. In addition to all-carbon cyclic alkenes, our preliminary results demonstrated that dihydrofuran 4 was also a compatible substrate for the stereoselective 1,2-diarylation reaction. The desired diarylation product 5 could be obtained in 83% yield, 68% ee, and >19:1 dr under the optimal conditions (Scheme 1). Scheme 1 | 1,2-Diarylation of alkene 4.*Absolute configuration of the carbon center was not determined Download figure Download PowerPoint 1,2-Arylalkynylation reaction: optimization and scope Having established the enantioselective 1,2-diarylation reaction, we further considered extending the established catalyst system to the reaction with other trapping agents. Encouraged by our previous success in the enantioselective dearomative Heck/Sonogashira domino sequence,51 we commenced the study of the 1,2-arylalkynylation reaction of cyclic trisubstituted alkenes by using terminal alkynes as nucleophilic trapping agents. Therefore, trisubstituted alkene 1a and phenylacetylene 6a were chosen as the model substrates. As shown in Table 3, in the presence of the best ligand L 13 for the 1,2-diarylation reaction, our initial test with 4.0 mol % of CuI as a cocatalyst21and Na2CO3 as a base afforded the desired product 7a in 75% yield, 91% ee, and >19:1 dr (Entry 1). Both inorganic (K2CO3, Cs2CO3, and K3PO4) and organic bases [Et3N, N, N-Diisopropylethylamine (DIPEA), tetramethylethylenediamine (TMEDA), and diaza(1,3)bicyclo[5.4.0]undecane (DBU)] were then screened (Entries 2–8). Although the yield was significantly influenced by the base, the ee values remained at the same level. It turns out K3PO4 was a suitable base in terms of yield and ee (Entry 4). As a comparison, the absence of CuI led to slightly lower yield and ee (Entry 9). Furthermore, the amount of K3PO4 could be decreased to 4.0 equiv, and product 7a was obtained in 90% yield and 94% ee (Entry 10). Table 3. | Optimization Studies for 1,2-Arylalkynylation Reactiona Entry Base Yield (%)b ee (%)c 1 Na2CO3 75 91 2 K2CO3 74 92 3 Cs2CO3 65 92 4 K3PO4 90 94 5 Et3N 81 94 6 iPr2NEt 85 92 7 TMEDA 62 94 8 DBU 55 92 9d K3PO4 88 91 10e K3PO4 90 94 11f K3PO4 82 94 Note: DBU, diaza(1,3)bicyclo[5.4.0]undecane; TMEDA, tetramethylethylenediamine. aReactions were performed on a 0.2 mmol scale. bIsolated yield. cee was checked by HPLC. dWithout CuI. e4.0 equiv K3PO4. f3.0 equiv K3PO4. As listed in Figures 2a and 2b, the scope of the 1,2-arylalkynylation reaction was examined. The reactions of alkene 1 bearing different substituents, including alkyl, halides, and alkyloxyl groups, on the benzene ring of the haloaniline moiety delivered the anticipated products 7 in generally excellent yields, diastereoselectivities, and enantioselectivities. Although the ee of product 7k bearing an electron-withdrawing CF3O group was moderate, the yield and diastereoselectivity were excellent. The benzocyclohexene-derived amide substrate was also tested in this reaction, which led to product 7w in 91% yield and 90% ee. The scope of terminal alkynes 6 was also investigated. Both aryl and aliphatic alkynes were well tolerated to give products 7n– 7s in excellent enantioselectivities, although the yields of products derived from aliphatic alkynes were relatively lower. Noticeably, heteroaryl alkynes such as 2-thienyl and 3-thienyl ethynes as well as ferrocenyl ethyne were compatible with the optimal conditions, and the corresponding products 7t– 7v were obtained in excellent yields and enantioselectivities. The absolute configuration of product 7e was determined to be (1R,2R) by X-ray crystallographic analysis.b Figure 2 | (a and b) Substrate scope of the 1,2-arylalkynylation reaction. Download figure Download PowerPoint Synthetic Applications To demonstrate the synthetic application of the present methodology, a few transformations were conducted. As shown in Figure 3a, the Heck/Suzuki domino reaction between 1a and 2a was carried out on a 1.0 mmol scale, which delivered product 3a in 87% yield and 91% ee. The reduction of amide moiety in 3a with LiAlH4 led to indoline-based spiro N-heterocycle 8 in 88% yield and 90% ee (Figure 3b). Product 7a was easily transferred to ketone 9 in 90% yield via an oxidative cleavage of the alkyne moiety with KMnO4 (Figure 3c). As a comparison, a Pd/C-catalyzed hydrogenation reaction of 7a under a H2 balloon at room temperature enabled the formation of compound 10 in 80% yield. No obvious erosion of enantioselectivity was observed under the oxidation and reduction conditions. It is noteworthy that such spiro-oxindole moieties are the core structures of some patented bioactive agents.56,57 Figure 3 | (a–c) Scale-up reaction and synthetic transformations. Download figure Download PowerPoint Conclusion Highly enantioselective 1,2-diarylation and 1,2-arylalkynylation of trisubstituted alkenes have been developed via domino Heck/Suzuki or Heck/Sonogashira sequences with Pd(OAc)2 as a catalyst and a modified phosphoramidite L 13 as chiral catalyst. Relying on the termination of secondary alkyl-Pd species derived from carbopalladation of cyclic trisubstituted alkenes, a number of chiral 3,3′-spirooxindoles bearing vicinal quaternary and tertiary stereocenters were formed in excellent enantioselectivities and diastereoselectivities. Footnotes a During the preparation of this manuscript, Yao and Lin reported a palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes, building two consecutive stereogenic centers in a bridged bicyclic framework. b CCDC number 1963224 for compound 3a and 1963227 for compound 7e. Supporting Information Supporting Information is available. 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 3Issue 9Page: 2340-2349Supporting Information Copyright & Permissions© 2020 Chinese Chemical SocietyKeywordsspirooxindoletrisubstituted alkeneasymmetric catalysisdicarbofunctionalizationpalladiumAcknowledgmentsThe authors are grateful for the financial support from the National Natural Science Foundation of China (nos. 21702184, 21772175, and 91956117). Downloaded 1,829 times PDF downloadLoading ...