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Synlett 2015; 26(12): 1671-1676
DOI: 10.1055/s-0034-1380746
DOI: 10.1055/s-0034-1380746
letter
Ruthenium-Catalyzed Oxidative C–H Bond Alkenylation of 2-Phenylimidazo[1,2-a]pyridine
Further Information
Publication History
Received: 26 January 2015
Accepted after revision: 14 April 2015
Publication Date:
21 May 2015 (online)
Abstract
Monoalkenylation of sp2 C–H bonds directed by the innate reactivity of imidazo[1,2-a]pyridine to afford 2-(2′-alkenylphenyl)imidazo[1,2-a]pyridine with high levels of diastereoselectivity is described. The methodology is employed to generate di-substituted alkenes by using a cationic ruthenium(II) catalyst in the presence of AgSbF6 and Cu(OAc)2·H2O under air.
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- 32 Typical Procedure: A mixture of 5a (100 mg, 0.515 mmol), ruthenium p-cymene dichloride dimer (10 mol%, 0.052 mmol), silver hexafluoroantimonate (20 mol%, 0.103 mmol) and copper acetate monohydrate (0.515 mmol) in dichloroethane (2 mL) was stirred at r.t. for 1 min, then acrylate (0.773 mmol) was added. The mixture was heated to 100 °C in an open air atmosphere for 24 h. On completion of the reaction (monitored by TLC), the mixture was cooled to r.t., diluted with EtOAc, passed through a short Celite bed, and washed repeatedly with pure EtOAc. The combined organic layer was concentrated under reduced pressure. The crude product was purified on a silica gel column (EtOAc–hexane, 1:4) to give 8a as an off-white solid; mp 95 °C. IR (KBr): 3035, 2971, 1729, 1634, 1321, 1173 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.23 (d, J = 15.9 Hz, 1 H), 8.16 (d, J = 6.7 Hz, 1 H), 7.91 (d, J = 7.6 Hz, 1 H), 7.66 (d, J = 7.7 Hz, 2 H), 7.62 (s, 1 H), 7.48 (t, J = 7.4 Hz, 1 H), 7.39 (t, J = 7.4 Hz, 1 H), 7.21 (t, J = 6.9 Hz, 1 H), 6.81 (t, J = 6.7 Hz, 1 H), 6.45 (d, J = 15.8 Hz, 1 H), 3.79 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 167.6, 145.4, 144.6, 143.9, 134.5, 133.1, 130.3, 130.1, 128.2, 127.2, 125.8, 125.1, 119.4, 117.8, 112.7, 112.1, 51.8. MS (ES+): m/z = 279.1 [M + 1]+ .
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For selected reviews for C–H activation, see:
For reviews on catalytic C–H bond activation with a Ru catalyst, see:
For selected examples of Ru-catalyzed C–H activation, see:
For synthetic routes to the imidazo[1,2-a]pyrimidine ring, see: