Copper-Catalyzed Intramolecular C-H Amination
to the mixture with vigorous stirring. After stirring the mixture
overnight, it was poured into saturated aqueous NH4Cl and ex-
tracted three times with CH2Cl2. The separated organic phase was
dried with MgSO4 and concentrated by rotary evaporation. H-
NMR analysis indicated that the product carbamates were formed
in Ͼ 95% purity and were thus used without further purification.
Acknowledgments
We are grateful for financial support provided by the National Sci-
ence Foundation (NSF) and for assistance by Dr. Susan L. Nimmo
in interpreting NMR spectra.
General Procedure for Preparing Sulfamate Substrates: Formic acid
(283 μL, 7.5 mmol) was added to neat ClSO2NCO (653 μL,
7.5 mmol) at 0 °C with vigorous stirring; the mixture gradually so-
lidified. To the resulting white mass was added 5.0 mL of dry aceto-
nitrile and the contents were warmed to room temperature. After
stirring for 5 h, the solvent was removed by rotary evaporation. In
a separate flask the alcohol precursor (3.0 mmol) was treated with
NaH (3.5 mmol) in 10 mL of DMF. The ClSO2NH2 produced
above was then added to the alkoxide mixture at 0 °C with vigorous
stirring. The mixture was warmed to room temp. and stirred over-
night. The reaction was quenched by the addition of 15 mL of H2O
and extracted with ethyl acetate and saturated brine. The combined
organic extracts were dried with MgSO4, and concentrated under
reduced pressure. H-NMR analysis indicated that the product
sulfamates were obtained in Ͼ 95% purity and were thus used
without further purification.
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Characterizational Data for New Compounds: (1) 1H NMR
(300 MHz, CDCl3): δ = 7.12 (t, J = 2.4 Hz, 2 H), 6.83 (dd, J = 3,
1.8 Hz, 2 H), 4.63 (s, 1 H), 4.22 (t, J = 7.2 Hz, 2 H), 3.77 (s, 3 H),
2.86 (t, J = 7.2 Hz, 1 H) ppm. 13C NMR (CDCl3, 75 MHz): δ =
158.2, 156.7, 129.8, 131.2, 113.8, 65.7, 55.2, 34.5 ppm. ESI-MS
calcd. m/z [M + Na] 218.0793, found 218.0789. (2) White solid, Rf
= 0.34, EtOAc/CH2Cl2 (1:4). 1H NMR (300 MHz, CDCl3): δ = 7.2
(d, J = 6.3 Hz, 2 H), 6.86 (d, J = 8.7 Hz, 2 H), 5.34 (s, 1 H), 4.84
(t, J = 7.7 Hz, 1 H), 4.64 (t, J = 8.8 Hz, 1 H), 4.1 (t, J = 7.8 Hz, 1
H), 3.75 (s, 1 H) ppm. 13C NMR (CDCl3, 75 MHz): δ = 160.0,
159.3, 131.2, 127.4, 114.5, 72.7, 55.9, 30.9 ppm. ESI-MS calcd. m/z
[M + Na] 216.0636, found 216.0642. (5) white solid, 1H NMR
(300 MHz, CDCl3): δ = 7.27 (d, J = 9 Hz, 2 H), 7.16 (dd, J = 2.4,
1.5 Hz, 2 H), 4.57 (s, 2 H), 4.26 (t, J = 6.7 Hz, 2 H), 2.91 (t, J =
6.7 Hz, 2 H) ppm. 13C NMR (CDCl3, 75 MHz): δ = 156.6, 136.3,
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4.67 (t, J = 8.4 Hz, 1 H), 4.08 (dd, J = 8.6, 6.9 Hz, 1 H) ppm. 13C
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Received: August 17, 2010
Supporting Information (see also the footnote on the first page of
this article): General procedures for preparing carbamate and sulf-
amate substrates, characterizational data for all oxazolidinone and
oxathiazinane products.
Published Online: December 15, 2010
Eur. J. Org. Chem. 2011, 908–911
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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