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Supporting Information © Wiley-VCH 2006 69451 Weinheim, Germany Supporting Information © Wiley-VCH 2006 69451 Weinheim, Germany General Preparation of Primary, Secondary and Tertiary Arylamines via the Oxidative Coupling of Polyfunctional Aryl and Heteroaryl Amidocuprates Vicente del Amo, Srinivas Reddy Dubbaka, Arkady Krasovskiy and Paul Knochel* Ludwig-Maximilians-Universität München, Department Chemie und Biochemie Butenandtstrasse 5-13, Haus F, 81377 München (Germany) Fax: (+49) 089 2180 77680 e-mail: [email protected] General All reactions were carried out under argon atmosphere in dried glassware. All starting materials were purchased from commercial suppliers and used without further purification unless otherwise stated. THF was continuously refluxed and freshly distilled from sodium benzophenone ketyl under nitrogen. (i-Pr)2NH was distilled from CaH2 under nitrogen atmosphere. Yields refer to isolated yields of compounds estimated to be > 95 % pure as determined by 1H NMR and capillary GC. Preparation of the reagent i-PrMgCl·LiCl: Magnesium turnings (110 mmol) and anhydrous LiCl (100 mmol) were placed in an argon- flushed flask, and THF (50 mL) was added. A solution of i-PrCl (100 mmol) in THF (50 mL) was slowly added at room temperature. The reaction starts within few minutes. After the addition was finished, the reaction mixture was stirred for 12 h at room temperature. The grey solution of i-PrMgCl·LiCl was cannulated to a different flask under argon and removed in this way from excess of magnesium. A yield of ca. 95-98% of i-PrMgCl·LiCl was obtained. The reagent was titrated prior to use by the method of Paquette,1 or the method developed by our laboratory.2 Preparation of the reagent TMPMgCl·LiCl: A dry and nitrogen-flushed 250 mL Schlenk-flask, equipped with a magnetic stirring bar and a septum, was charged with freshly titrated i-PrMgCl·LiCl (1.2 M in THF) (100 mL, 120 mmol). 2,2,6,6-Tetramethylpiperidine (TMPH) (19.8 g, 126 mmol, 1.05 equiv) was added dropwise at room temperature. The reaction mixture was stirred at room temperature until gas evolution was completed (ca. 24 h).3 1 Preparation of the reagent CuCl·2LiCl (1 M in THF): A dry and argon-flushed 50 mL Schlenk-flask, equipped with a magnetic stirrer and a glass stopper, was charged with LiCl (1.7 g, 40 mmol) and heated up to 130 oC under high vacuum for 1 h. After cooling to room temperature under argon, CuCl (1.98 g, 20 mmol, 99.5% Cu) was added under inert atmosphere inside a glove-box. The Schlenk-flask was further heated to 130 °C for 5 h under high vacuum, cooled to room temperature, charged with freshly distilled THF (20 mL) under argon and wrapped in aluminium foil to protect it from light. The mixture was vigorously stirred until all solid goes in solution (ca. 6 h.). The reagent CuCl·2LiCl (1 M in THF) appears as a colourless or slightly yellow solution. OPTIMIZATION OF THE REACTION CONDITIONS: In preliminary experiments, we have reacted PhMgCl·LiCl with various copper(I) salts, followed by the addition of Et2NLi (3 equiv) and any of the three representative quinones: 3,3’,5, 5’-tetra-tert-butyldiphenoquinone (A), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,3,5,6-tetrachloro-1,4-benzoquinone 1 (chloranil) (1.2 equiv, addition at -78 oC and 12 h at -40 oC); Table. The reaction was monitored by GC-analysis and the yield of PhNEt2 was determined by the analysis of hydrolyzed reaction aliquots. 3,3’,5,5’-Tetra-tert- butyldiphenoquinone (A) led to sluggish reactions especially by using CuCN·2LiCl (entry 1, Table 1). Better results were obtained with CuCl·2LiCl or CuBr·Me2S (entries 2 and 3), but clearly a more reactive quinone had to be used. The addition of DDQ combined with CuCl·2LiCl led to a faster and more efficient reaction affording a GC-yield of 70% (entry 4). CuBr·Me2S and CuI·LiCl led to lower yields (40-42%; entries 5 and 6). Finally, the best result was obtained with CuCl·2LiCl and chloranil (1.2 equiv) as oxidant leading to the formation of PhNEt2 in 95% by GC-analysis. Table: Reaction of PhMgCl·LiCl (1 equiv) with various copper salts, addition of Et2NLi (3 equiv) and oxidative amination with various quinones (1.2 equiv) leading to PhNEt2. Entry Cu(I) salt Quinone Yield[%][a] 1 CuCN·2LiCl A 9 2 CuCl·2LiCl A 21 3 CuBr·Me2S A 41 2 4 CuCl·2LiCl DDQ 70 5 CuBr·Me2S DDQ 42 6 CuI·LiCl DDQ 40 7 CuCl·2LiCl 1 95 [88][b] [84][c] [a] GC-yields determined by the analysis of hydrolyzed reaction aliquots using tetradecane as an internal standard. Reaction conditions: Addition of the oxidant at -78 oC and then 12 h at - 40 oC. [b] 10% vol. of NMP used as co-solvent. [c] isolated yield of analytical pure compound. Synthesis of N,N-diethylaniline NEt2 Prepared in preliminary experiments from PhMgCl·LiCl (1.22 M in THF; 0.82 mL, 1.0 mmol) and N-lithium-diethylamine (3.0 mmol, prepared by adding n-BuLi to diethylamine at -40 °C and stirring for 45 min). Flash chromatography (pentane/5 % CH2Cl2) afforded N,N- diethylamine (125 mg, 84 %) as a colourless oil. The 1H NMR spectrum matches with that of the commercially available product. 1 H NMR (200 MHz, CDCl3): d = 7.50-7.39 (m, 2 H, ArH), 6.92-6.84 (m, 3 H, ArH), 3.58- 3.51 (m, 4 H, CH2), 1.40-1.33 (m, 6 H, CH3). MS (EI+): m/z (%) = 149 (100) [M]+. TYPICAL PROCEDURES: 3 Synthesis of 4-amino-5-tert-butoxycarbonyloxy-isophthalic acid diethyl ester (7a) (TP1) (Scheme 1) O t-BuO O NH2 EtO2C CO2Et A dry and argon-flushed Schlenk-flask, equipped with a magnetic stirrer and a septum, was charged with a solution of 5-tert-butoxycarbonyloxy-isophthalic acid diethyl ester 2a (338 o mg, 1.0 mmol) in dry THF (3 mL). After cooling to 0 C, TMPMgCl·LiCl (1.20 M in THF; 0.92 mL, 1.1 mmol) was added dropwise and stirred for 1 h to afford the corresponding Grignard reagent (3a). This reagent was added dropwise to a solution of CuCl·2LiCl (1.0 M in THF; 1.2 mL, 1.2 mmol) and bis[2-(N,N-dimethylamino)ethyl] ether (192 mg, 1.2 mmol) at - 50 °C and the mixture was stirred for 45 min. To the resulting aryl cuprate (5a), LiHMDS (1.0 M in THF) (2.0 mL, 2.0 mmol) was added dropwise and the mixture was further stirred for 90 min at -50 °C. The reaction mixture was cooled to -78 oC, then chloranil (1) (295 mg, 1.2 mmol), in dry THF (7 mL), was added slowly over a period of 45 min. The reaction mixture was allowed to reach -50 °C and stirred for 12 h. Diethyl ether (10 mL) was poured to the crude reaction mixture and it was filtered through Celite, washed with Et2O thoroughly (ca. 100 mL), and the liquors washed with 2 x 10 mL portions of NH4OH (aq., 2.0 M) and extracted with Et2O. The combined organic layers were dried (MgSO4), filtered and concentrated under reduced pressure. This crude material was redissolved in Et2O (3 mL) before tetrabutylammonium fluoride (TBAF) (1.0 M in THF; 2 mL, 2 mmol) was added in one portion and the mixture was stirred at room temperature for 10 min, poured over EtOAc (10 mL) and washed with deionised water (3 x 10 mL). The combined organic extracts were dried (MgSO4), filtered and concentrated in vacuum. Purification by flash chromatography (pentane/Et2O; 4:1) afforded the title amine 7a (254 mg, 72 %) as a white crystalline solid. mp.: 87–88 oC. -1 IR (neat): ?max (cm ) = 3260, 3070, 2981, 2936, 1715, 1680, 1538, 1451, 1394, 1366, 1331, 1318, 1288, 1218, 1187, 1154, 1111, 1063, 1021, 937, 891, 864, 795, 764, 700. 1 H NMR (300 MHz, CDCl3): d = 10.58 (broad. s, 1H, NH), 9.95 (s, 1H, NH), 8.29 (d, 4J(H,H) = 1.6 Hz, 1H, ArH), 7.84 (d, 4J(H,H) = 1.6 Hz, 1H, ArH), 4.42 (q, 3J(H,H) = 7.2 Hz, 4 3 3 2H), 4.39 (q, J(H,H) = 7.2 Hz, 4H, CH2), 1.57 (s, 9H, C(CH3)3), 1.45 (t, J(H,H) = 7.2 Hz, 3 3H, CH3), 1.41 (t, J(H,H) = 7.2 Hz, 3H, CH3). 13 C NMR (75 MHz, CDCl3): d = 168.1, 165.6, 156.1, 150.0, 133.1, 126.7, 129.9, 124.8, 119.0, 83.7, 62.2, 61.4, 28.4, 14.5, 14.4. MS (70 eV, EI): m/z (%) = 353 (1), 297 (30), 279 (34), 253 (100), 233 (57), 207 (36), 179 (10), 150 (4), 59 (16), 57 (40), 41 (7). HRMS (EI): m/z calc. for [C17H23NO7] 353.1475, found: 353.1455. Synthesis of 4-aminobenzonitrile (7b) (Table 1, entry 1) (TP2) NH2 CN A dry and argon-flushed Schlenk-flask, equipped with a magnetic stirrer and a septum, was charged with i-PrMgCl·LiCl (1.39 M in THF; 0.79 mL, 1.1 mmol) and cooled to 0 oC. 4- Bromobenzonitrile (182 mg, 1.0 mmol) was added dropwise and the mixture was stirred at 0 °C for 2 h to afford the Grignard reagent 3b. The I/Mg-exchange was completed after 2 h as determined by GC analysis of a reaction aliquot. This solution was cooled to -50 °C before CuCl·2LiCl (1.0 M in THF; 1.2 mL, 1.2 mmol) and bis[2-(N,N-dimethylamino)ethyl] ether (192 mg, 1.2 mmol) were added dropwise and the mixture was stirred for 45 min.
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