CCS Chemistry, Год журнала: 2021, Номер 3(6), С. 1127 - 1137

Опубликована: Март 19, 2021

Open AccessCCS ChemistryCOMMUNICATION1 Jun 2021Aerobic Heterogeneous Palladium-Catalyzed Oxidative Allenic C−H Arylation: Benzoquinone as a Direct Redox Mediator between O2 and Pd Wei-Jun Kong, Michaela Reil, Lei Feng, Man-Bo Li Jan-E. Bäckvall Kong Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 , Reil Feng Institute Physical Science Information Technology, Anhui Hefei, 230601 *Corresponding authors: E-mail Address: [email protected] Natural Sciences, Mid Sweden SE-85170 Sundsvall https://doi.org/10.31635/ccschem.021.202100816 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesTrack Citations ShareFacebookTwitterLinked InEmail Transition metal-catalyzed aerobic oxidative reactions using molecular oxygen the terminal oxidant play significant role in organic synthesis. (BQ) has been widely used an electron-transfer mediator (ETM) biomimetic palladium-catalyzed reactions, but always together with ETM BQ, such macrocyclic metal complex. Herein, we report on heterogeneous allenic C(sp3)–H arylation only catalytic amounts BQ under air without need additional ETM. A range multisubstituted 1,3-dienes were synthesized mild reaction conditions. Mechanistic studies reveal bifunctional ligand for reductive elimination Pd(0) O2. This new regime oxidation important implications further development other transition reactions. Download figure PowerPoint Introduction Metal-catalyzed are fundamental transformations nature synthesis.1–4 Thus demand selective, mild, sustainable methods attracted considerable attention. Among various reactions,5 oxidations have ideal choice due large abundance environmental friendliness (O2).6,7 Palladium-catalyzed indispensable synthesis.8–12 However, direct reoxidation situ-formed low valent by ambient is generally considered kinetically unfavorable, often leads aggregation black formation.13 One way avoid this problem use air-stable ligands that can stabilize restrain its aggregation. approach worked few cases.14 capable directly oxidizing Pd(0)15,16 Pd-catalyzed C–H functionalizations.17–26 stoichiometric compromised sustainability these sometimes catalyst inhibition27 or undesired side product formation through Diels–Alder cycloaddition.28,29 Inspired processes nature, our group30 developed strategy, where metal-macrocyclic complex mediators (ETMs) redox (Scheme 1a). The key success redox-relay catalysis presence structures activation 1b).31 Notably, recent study Stahl et al.32 revealed tailored quinones could increase turnover number palladium catalysts study, quinone was found non-redox catalysis. hydroquinone addition still inefficient. Scheme 1 | (a) biomimicked system. (b) Macrocyclic complexes ETMs hydroquinone. (c) work: arylation. extensively studied cross-coupling high efficiency recyclability.33–42 application remains elusive. In 2019, Jiang al.43 elegant system (AOS) desulfitative coupling assembly catalyst, phenanthroline ligand, copper into robust metal–organic framework (MOF). Recently, group44–47 immobilized cavities aminopropyl-functionalized siliceous mesocellular foam (Pd-AmP-MCF) addition, also demonstrated ability overcome deactivation prevalent homogeneous reactions.44 oxidations. first C–C Pd-AmP-MCF, occurs 1c). unprecedented observed no required. Results Discussion We initiated sulfonamide 1a p-tolylboronic acid 2a substrates envisioned (Table 1). preliminary experiment, 74% yield desired 1,3-diene 3aa obtained 2.0 mol % Pd-AmP-MCF KOAc (3.0 equiv) Et3N (0.5 additives mixed solvent MeOH/CH3CN (1:5) 10 (entry 1, Table Without Et3N, slightly reduced 2, absence trace detected 3, silver salts might activate scavenging chloride anions bound Pd44 unsuccessful dramatically decreased (entries 4 5, When run MeOH MeCN sole solvent, poor results 30% 16% yield, respectively 6 7, Next, different carboxylate screened 8 9, 1) NaOAc gave best result 98% isolated 8, bold, amount 1.0 equiv, drastically 36% 10, control experiment argon 14% confirmed 11, Pd(OAc)2 place proceeded well selectivity, 13% byproduct 3' identified 73% 12, 2,5-dimethyl-p-benzoquinone (DMBQ) showed better reproducibility than therefore DMBQ 13, Note when loading 0.4 %, afford 62% 20 14, Reaction Condition Optimizationa Entry Additive Solvent (%) MeOH/MeCN 22 74 2 72b 3 95 <3c 48 18d 5 50 22e 66 30 7 43 16 99(98)f 9 NaOPiv 26 73 36g 11 83 14h 12 73i,j 13 0 99k 14 36 62l Note: major p-methylphenol. (0.1 mmol), (0.2 additive equiv), (2 %), 40 °C, h, air, yields based 1H NMR CH2Br2 internal standard. bWithout Et3N. cWithout BQ. dAgOAc added. eAgOTf fIsolated parenthesis, optimal gNaOAc (1.0 additive. hUnder argon. iPd(OAc)2 (10 %) catalyst. j13% identified. kWith instead lWith DMBQ. With optimized conditions hand, probed versatility boronic acids 2). broad arylboronic bearing electron-donating ( 2a- d) electron-withdrawing groups Ac, CF3, F, Cl, Br 2e- i) at para position applicable reaction. 4-Vinylphenyl 2-naphthyl deliver products excellent 3aj 3ak). For meta-substituted 2l) donating 2m 2n), corresponding good yields. Heterocyclic lower reactivity exemplified thiophen-3-yl- N-methyl-indol-5-yl-boronic giving 3ao 3ap 32% 55% yields, respectively. alkenyl dendralenes 3aq 3ar 94% 37% likely instability 2r. Substrate scope 2. 3.0 equiv 4-methoxyphenylboronic 2c. variety sulfonamides substituents evaluated 3). phenyl group replaced (R3), benzyl 1b), cyclopentyl 1c), isopropyl 1d), ester 1e), 3ba- 3ea) moderate α-phenyl- α-methyl-substituted 1f 1g) well. bond not limited dimethyl R1 R2, it R1, R2 = Ph, Me 1h) –CH2)n– 1i 1j) reacted successfully give 3ha, 3ia, 3ja Scope 1. motivated us delineate mechanism. Deuterium kinetic isotope effect (KIE) experiments conducted initially 4). competitive KIE carried out 1:1 mixture 1a-d6 °C h. ratio 3aa/ 3aa-d5 measured 18.4% conversion 4.8:1 calculated be kH/kD 5.5 (see Supporting Figure S1). parallel two separate vials value 1.0. discrepancy KIEs indicates step irreversible and, furthermore, rate-determining (RDS) cycle. As able catalyze reaction, following mechanistic studies. treated room temperature signals activated intermediate (Figure see S2). observation demonstrates essential contrast some previous allylic functionalizations.48–54 both DMBQ, 5a), indicating plays steps before Pd(0), most elimination.55–59 step. experiments. (a–c) Experiments may consider act oxidized O2.32,a Reactions correlation observed. 110 90% obtained, respectively, demonstrating acts efficient reoxidant Information). These strongly suggest serves electron-deficient alkene cannot oxidize promote elimination, investigated 5b).60–63 Maleic anhydride L1), dialkyl fumarates L2 L3), dibenzylideneacetone (dba, L4) thus added all cases (<2%) detected.b verifies 2,5-dimethyl (DMHQ) rate (21% 5c) increased (33% h). explain long time (more h) needed Recycling (with 10% BQ) possible 59% second basic condition lead complicating recyclabilty. Characterizations, including scanning electron microscopy (SEM), transmission (TEM), X-ray diffraction (XRD), photoelectron spectroscopy (XPS), after rationalize Particularly, XPS spectra Pd(II)/Pd(0) from about 90/10 65/35 recycling, which active Pd(II) species slowly aggregated catalytically inert (Figures 2b). (b). To investigate kinetics loadings profiled S3). 10–30 range, increasing loading, RDS aforementioned consistent above did change loading. Interestingly, 4) changed 1.2 1.1 Based studies, cycle proposed 6. After coordination int A), methyl assistance B),64,65 affording 4. Transmetalation would C. proton N-tosyl amide C comes HOAc, generated coordinated promotes release Pd(0). Then subsequently regenerate Pd(II). DMHQ reoxidized oxygen, used. Proposed Conclusions reported air. selectivity. Detailed the: (1) (2) reoxidation. shed light available includes experimental procedures compound characterization data. Conflict Interest authors declare competing interests. 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