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Synlett 2018; 29(06): 759-763
DOI: 10.1055/s-0036-1589129
DOI: 10.1055/s-0036-1589129
cluster
Regioselective and Room-Temperature Carbon–Carbon Bond Activation of Cyclopropanes by Rhodium(II) Porphyrin
This work was supported by Hong Kong Research Grants Council (GRF NO. 400113).Further Information
Publication History
Received: 12 September 2017
Accepted: 10 October 2017
Publication Date:
23 November 2017 (online)
Published as part of the Cluster C–C Activation
Abstract
Regioselective carbon–carbon bond activation of cyclopropanes by RhII(tmp) (tmp = 5,10,15,20-tetramesitylporphyrinato dianion) was achieved at room temperature under neutral conditions to yield corresponding rhodium–porphyrin alkyls. This reaction can tolerate water, and functional groups are compatible.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1589129.
- Supporting Information
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References and Notes
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- 18 Typical Procedure for Rh(tmp)CH2CH2CH2COPh (2a) To the benzene solution of RhII(tmp) (1a, 0.00445 mmol) PPh3 (1.2 mg, 0.00458 mmol) was added, and the reaction mixture was stirred at 25 °C. After 10 min, the benzene solvent was removed by vacuum evaporation and then degassed cyclopropyl phenyl ketone (65 μL, 0.465 mmol) and benzene (430 μL) were added. The mixture was then stirred under nitrogen at 25 °C for 10 min. Excess solvent was removed, and the dark red crude product was then purified by column chromatography on silica gel eluting with hexane/CH2Cl2 (1:1) to give the reddish purple solid of Rh(tmp)CH2CH2CH2COPh (2a, 2.4 mg, 0.00233 mmol, 52% yield). Rf = 0.64 (hexane/CH2Cl2 = 1:1). 1H NMR (500 MHz, CDCl3): δ = –4.73 (dt, 2 H, 2JRh–H = 2.8 Hz, 3JHH = 8.1 Hz), –3.76 (quint, 2 H, J = 8.0 Hz), 0.18 (t, 3 H, J = 7.6 Hz), 1.82 (s, 12 H), 1.92 (s, 12 H), 2.63 (s, 12 H), 6.81 (d, 2 H, J = 7.8 Hz), 7.03 (t, 2 H, J = 7.5 Hz), 7.28 (s, 4 H), 8.50 (s, 8 H). 13C NMR (126 MHz, CDCl3): δ = 12.85 (d, 1JRh–C = 28.5 Hz), 21.60, 21.68, 21.84, 23.62, 36.24, 119.74, 127.40, 127.83,,127.85, 128.06, 130.79, 132.34, 135.83, 137.53, 138.51, 139.08, 139.12, 142.69, 197.52. HRMS (MALDI-MS): m/z calcd for [M]+ (C66H63N4ORh): 1030.4051; found: 1030.4064.