Cobalt(III)-Catalyzed 1,4-Addition of C(sp³)–H Bonds to Maleimides

^◇ These authors contributed equally to this work.

Abstract

Quinolines and succinimides play a crucial role in many pharmaceutical and natural products. Although sp² C–H bond addition reactions have been extensively investigated, Co(III)-catalyzed sp³ C–H bond 1,4-addition reactions are relatively unexplored. In this manuscript, an efficient and atom-economic protocol for alkylation reactions of 8-methylquinolines with maleimides is presented. The reaction exhibits exceptional reactivity, satisfactory yields, excellent chemo- and regioselectivity, and tolerates a variety of functional groups.

Key words

cobalt - 1,4-addition reactions - alkylation - C–H functionalization - 8-methylquinolines

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• 13 Representative Procedure for 1,4-Addition of C(sp³)−H Bonds to Maleimides A mixture of 8-methylquionoline (28.6 mg, 0.2 mmol, 1.0 equiv), N-methylmaleimide (44.4 mg, 0.4 mmol, 2.0 equiv), [Cp*Co(CO)I₂] (4.8 mg, 0.01 mmol, 5 mol%), AgOTf (7.7 mg, 0.03 mmol, 15 mol%), and Zn(OAc)₂ (11.0 mg, 0.06 mmol, 30 mol%) in HFIP (1.0 mL) was stirred under argon at 100 °C for 24 h. After cooling to room temperature, the solvent was removed under reduced pressure. The contents were subjected to flash chromatography (petrol ether/EtOAc 2:1) to give the product as white solid (46.7 mg, 0.184 mmol, 92%). 1-Methyl-3-(quinolin-8-ylmethyl)pyrrolidine-2,5-dione (3aa) Yellow solid. ¹H NMR (400 MHz, CDCl₃): δ = 8.90 (dd, J = 1.6, 4.0 Hz, 1 H), 8.14 (dd, J = 1.6, 8.0 Hz, 1 H), 7.73 (dd, J = 1.2, 8.0 Hz, 1 H), 7.57 (d, J = 4.0 Hz, 1 H), 7.46 (t, J = 8.0 Hz, 1 H), 7.41 (dd, J = 4.0, 8.0 Hz, 1 H), 3.97 (dd, J = 8.0, 16.0 Hz, 1 H), 3.54−3.47 (m, 1 H), 3.42−3.36 (m, 1 H), 2.97 (s, 3 H), 2.64 (dd, J = 4.0, 18.4 Hz, 1 H), 2.54 (dd, J = 8.8, 18.4 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 179.84, 176.98, 149.63, 146.84, 136.51, 136.38, 129.99, 128.47, 127.27, 126.25, 121.17, 41.31, 33.73, 32.21, 24.71. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₅H₁₄N₂O₂Na⁺: 277.0953; found: 277.0987.
• 14 The 1,4-addition product with unprotected maleimide was isolated in no more than 10% yield, accompanied with recovered starting materials.
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