Preparation of 3-alkyl-oxindoles by copper(II)-mediated C-H, Ar-H coupling followed by decarboxyalkylation

Synlett

Volumn , Issue 6, 2010, Pages 934-938

  Pugh, David S ^a   Klein, Johannes E M N ^a   Perry, Alexis ^a   Taylor, Richard J K ^a  

^a UNIVERSITY OF YORK   (United Kingdom)

Author keywords

3 alkyl oxindoles; Anilides; C H activation; Copper(II) catalysis; Cyclisation; Decarboxyalkylation; Oxindoles

Indexed keywords

ACID; ANILIDE; ARGON; CARBON; CUPRIC ION; HYDROGEN; INDOLE DERIVATIVE;

ALKYLATION; ARTICLE; BIOTRANSFORMATION; CATALYSIS; CHEMICAL BOND; CROSS COUPLING REACTION; CYCLIZATION; DECARBOXYALKYLATION; DECARBOXYLATION; DEPROTECTION REACTION;

EID: 77949892812     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1219392     Document Type: Article

References (22)

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20. Prepared by the alkylation of amide 8 using the route shown in Scheme 4; all yields were greater than 88% with the exceptions of i-Pr (5c, 55%), PhCH2CH2 (5f, 63%), PhCH2O(CH2)3 (5h, 69%), and 4-PyCH2 (5i, 46%).
21. Representative Procedure for the Copper-Mediated Cyclisation: tert-Butyl 1-Methyl-3-(naphthalen-2-ylmethyl)- 2-oxoindoline-3-carboxylate (5g) A 100 mL round-bottomed flask fitted with a condenser and stirrer-bar was charged with tert-butyl ester 4g (R = naphthalen-2-yl-methyl, 195 mg, 0.50 mmol) and DMF (10 mL). KOt-Bu (62 mg, 0.55 mmol) was added in a single portion, followed by copper(II) acetate monohydrate (100 mg, 0.50 mmol). The green-black suspension was heated to 110 C (oil bath temperature) over 15 min. After stirring at 110 C for 18 h, the reaction was cooled to r.t. and quenched with a sat. solution of NH4Cl (10 mL), diluted with H2O (20 mL), and extracted with EtOAc (20 mL). The organic layer was washed with a sat. brine solution (2 × 20 mL), dried (Na2SO4), filtered, and concentrated in vacuo to give an orange oil. Purification by flash column chromatography (SiO2, 7:2:1 PECH2Cl2EtOAc) gave product 5g (141 mg, 73%) as a colorless gum; Rf = 0.44 (3:1 PEEtOAc). IR (film): nmax = 3056, 2978, 2932, 1734, 1715, 1610, 1493, 1471, 1370, 1351, 1306, 1251, 1155, 1086, 997, 909, 750 cm1. 1H NMR (400 MHz, CHCl3-d1): d = 1.41 (9 H, s, CMe3), 2.89 (3 H, s, NMe), 3.64 (1 H, d, J = 13.5 Hz, CH2), 3.69 (1 H, d, J = 13.5 Hz, CH2), 6.50 (1 H, d, J = 7.5 Hz, ArH), 6.98 (1 H, dd, J = 8.5, 2.0 Hz, ArH), 7.06 (1 H, ddd, J = 7.5, 7.5, 1.0 Hz, ArH), 7.17 (1 H, ddd, J = 7.5, 7.5, 1.5 Hz, ArH), 7.337.37 (3 H, m, ArH), 7.38 (1 H, ddd, J = 7.5, 1.5, 0.5 Hz, ArH), 7.48 (1 H, d, J = 8.5 Hz, ArH), 7.60 (1 H, dd, J = 6.0, 3.5 Hz, ArH), 7.67 (1 H, dd, J = 6.0, 3.5 Hz, ArH). 13C NMR (100 MHz, CHCl3-d1): d = 26.1 (NMe), 27.8 (CMe3), 39.7 (CH2), 61.8 (C), 82.6 [OC(CH3)3], 108.1 (ArH), 122.3 (ArH), 123.6 (ArH), 125.4 (ArH), 125.5 (ArH), 126.9 (ArH), 127.3 (ArH), 127.7 (ArH), 127.8 (Ar), 128.3 (ArH), 128.8 (2 ArH), 132.1 (Ar), 132.5 (Ar), 132.9 (Ar), 144.1 (Ar), 168.1 (C=O), 173.8 (C=O). ESI-MS: m/z = 410 [MNa]+. ESI-HRMS: m/z calcd for C25H25NNaO3: 410.1727; found: 410.1731 [MNa]+; 0.6 ppm error.
22. Representative Procedure for Decarboxyalkylation: 1-Methyl-3-(naphthalen- 2-ylmethyl) indolin-2-one (3g) A 10 mL round-bottomed flask with stirrer bar was charged with tert-butyl ester 5g (97 mg, 0.25 mmol) and anisole (82 mL, 0.75 mmol), a septum was fitted and the flask purged with argon(balloon). TFA (1 mL) was added, and the resulting brown solution was stirred for 2 h. The reaction mixture was concentrated in vacuo to give a yellow gum. Purification by flash column chromatography (SiO2, 4:1 PE EtOAc) gave oxindole 3g (67 mg, 93%) as a yellow solid. Rf = 0.39 (3:1 PEEtOAc); mp 9193 C. IR (film): nmax = 3053, 2920, 2853, 1709, 1612, 1493, 1469, 1422, 1375, 1350, 1256, 1127, 1089, 750, 732 cm1. 1H NMR (400 MHz, CHCl3-d1): d = 3.04 (1 H, dd, J = 13.5, 9.5 Hz, CH2), 3.17 (3 H, s, NMe), 3.67 (1 H, dd, J = 13.5, 4.5 Hz, CH2), 3.84 (1 H, dd, J = 9.5, 4.5 Hz, CH), 6.716.77 (2 H, m, J = 7.5 Hz, ArH), 6.88 (1 H, ddd, J = 7.5, 7.5, 1.0 Hz, ArH), 7.21 (1 H, dd, J = 8.0, 8.0 Hz, ArH), 7.34 (1 H, dd, J = 8.5, 1.5 Hz, ArH), 7.437.47 (2 H, m, ArH), 7.60 (1 H, br s, ArH), 7.73 7.82 (3 H, m, ArH). 13C NMR (100 MHz, CHCl3-d1): d = 26.2 (NMe), 37.0 (CH2), 46.9 (CH), 107.9 (ArH), 122.1 (ArH), 124.5 (ArH), 125.5 (ArH), 126.0 (ArH), 127.6 (3 ? ArH), 127.9 (2 × ArH), 128.0 (ArH), 128.3 (Ar), 132.3 (Ar), 133.3 (Ar), 135.5 (Ar), 144.1 (Ar), 177.0 (C=O). ESI-MS: m/z = 310 [MNa]+. ESI-HRMS: m/z calcd for C20H17NNaO: 310.1202; found: 310.1196 [MNa]+; 1.6 ppm error.