Synlett 2018; 29(06): 759-763
DOI: 10.1055/s-0036-1589129
cluster
© Georg Thieme Verlag Stuttgart · New York

Regioselective and Room-Temperature Carbon–Carbon Bond Activation of Cyclopropanes by Rhodium(II) Porphyrin

Shiyu Feng
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, P. R. of China   Email: ksc@cuhk.edu.hk
,
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, P. R. of China   Email: ksc@cuhk.edu.hk
› Author Affiliations
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

 
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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.