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Synlett 2018; 29(15): 2023-2026
DOI: 10.1055/s-0037-1610654
DOI: 10.1055/s-0037-1610654
letter
Rhodium(III)-Catalyzed C–H Activation/Alkylation of Diazabicyclic Olefins with Aryl Ketones: Facile Synthesis of Functionalized Cyclopentenes
S.P.V. thanks UGC for research fellowship. Financial assistance from the Science and Engineering Research Board (SERB), New Delhi (SR/S1/OC-24/2014) and from the Council of Scientific and Industrial Research (12th FYP project, ORIGIN-CSC-0108), New Delhi, is greatly acknowledged.Further Information
Publication History
Received: 13 June 2018
Accepted after revision: 15 July 2018
Publication Date:
23 August 2018 (online)
Abstract
A facile synthesis of biologically important trans-functionalized cyclopentenes by a mild Rh(III)-catalyzed alkylation of strained diazabicyclic olefins with aryl ketones in the presence of ammonium acetate has been developed. The reaction proceeds through C–H bond activation of the aryl ketone groups by transforming them in to an autocleavable directing group, such as in situ-formed imine.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610654.
- Supporting Information
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- 10 Diethyl 1-[(1S*,2R*)-2-(2-Acetylphenyl)cyclopent-3-en-1-yl]hydrazine-1,2-dicarboxylate (4); Typical Procedure Azabicyclic olefin 1a (100 mg, 0.42 mmol), acetophenone (2a; 50 mg, 0.42 mmol), NH4OAc (64 mg, 0.83 mmol), [RhCp*Cl2]2(10 mg, 3 mol%), and Cu(OAc)2 (150 mg, 0.83 mmol) were weighed into a Schlenk tube, and the mixture was degassed for 10 min. Anhyd DCE (1 mL) was added, and the mixture was purged with argon and stirred at 80 °C for 24 h. The solvent was evaporated in vacuo and the residue was purified by column chromatography [silica gel (100–200 mesh); Ethyl acetate-Hexane polarities] to give a viscous liquid; yield: 121 mg (81%); TLC (silica gel): Rf = 0.43 (25% EtOAc–hexane). 1H NMR (500 MHz, CDCl3, TMS): δ = 7.64 (d, J = 7.5 Hz, 1 H), 7.54 (br s, 1 H), 7.50–7.47 (m, 1 H), 7.43–7.42 (m, 1 H), 7.31–7.28 (m, 1 H), 5.89–5.88 (m, 1 H), 5.54–5.52 (m, 1 H), 4.94–4.69 (m, 2 H), 4.26–4.22 (m, 2 H), 4.06–3.76 (m, 2 H), 2.72–2.60 (m, 2 H), 2.59 (s, 3 H), 1.32–1.26 (m, 4 H), 1.15 (br s, 1 H), 0.71 (br s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 201.8, 156.1, 152.9, 143.8, 137.8, 132.8, 132.2, 130.6, 129.3, 129.1, 126.2, 67.9, 61.9, 61.8, 47.2, 34.8, 29.8, 14.5, 13.9. HRMS (ESI-Orbitrap): m/z [M + Na]+ calcd for C19H24N2NaO5: 383.1583; found: 383.1573.