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. Author manuscript; available in PMC: 2013 Jun 15.
Published in final edited form as: J Org Chem. 2012 Jun 4;77(12):5313–5317. doi: 10.1021/jo3006733

Table 1.

Nitrile Oxides Substituent Dependence in the Production Rearrangement Productsagraphic file with name nihms-382693-t0003.jpg

entry Ar (2) product 3:4b yield (%)c
1 2-MeOC6H4 (2a) 3a >95:5 92
2 4-MeC6H4 (2b) 3b, 4b 90:10 84
3 4-FC6H4 (2c) 3c, 4c 78:22 89
4 4-ClC6H4 (2d) 3d, 4d 65:35 93
5 4-BrC6H4 (2e) 3e, 4e 55:45 89
6 4-AcOC6H4 (2f) 3f, 4f 39:61 81
7 2-NO2C6H4 (2g) 3g, 4g <5:95 90
a

Reaction conditions: 1a (1.2 mmol) in DCM (3.0 mL) was added over 1 h by syringe pump to mixture of 4 Å molecular sieves (100 mg), Rh2(pfb)4 (2.0 mol %) and nitrile oxide 2 (1.0 mmol) in DCM (5.0 mL) at 0 °C, and stirred for 2 h at room temperature. After solvent removal the product mixture was purified by chromatography on silica gel.

b

Determined by 1H NMR of the reaction mixture.

c

Isolated yield of combined 3 and 4 based on limiting reagent 2.