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10 mL diethyl ether was added. The ether was decanted from
the solid and washed with H2O (2ꢂ3 mL). The resulting
ether was dried over MgSO4, concentrated, and the residue
was purified by flash chromatography.
4. Winterton, N. Green Chem. 2000, 2, 173–225.
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7.6. In situ generation of 4-chloro-3-(phenylselanyl)-
butanoic acid (16)
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PhSeCl (20 mg, 0.1 mmol) was dissolved in 600 mL CD2Cl2
in an NMR tube to produce an orange solution. To this solu-
tion, 3-butenoic acid (1 equiv) was added with shaking. The
completion of the reaction was noted by a rapid color change
to pale yellow. 1H NMR characterization is consistent with
the assigned structure:25 1H NMR (400 MHz, CD2Cl2)
d 2.70 (dd, J¼8.6, 16.7 Hz, 1H, CHHCHSePh), 3.19 (dd, J¼
4.3, 16.9 Hz, 1H, CHHCHSePh), 3.61 (m, 1H, CHSePh),
3.67 (app. t, J¼10.39 Hz, 1H, CHHCl), 3.96 (dd, J¼3.8,
10.6 Hz, 1H, CHHCl), 7.34 (m, 3H, Ar–H), 7.62 (d, J¼
6.8 Hz, 2H, Ar–H), 10.70 (br s, 1H, CO2H). Allowing the
solution of 16 to stand at room temperature for 2 d led
to complete equilibration to a 1:3.5 mixture of 16 and
3-chloro-4-(phenylselanyl)butanoic acid (15): 1H NMR
(400 MHz, CD2Cl2) d 2.79 (dd, J¼9.1, 16.4 Hz, 1H,
CHHCHCl), 3.22 (m, 1H, CHHCHCl), 3.30 (dd, J¼3.5,
16.3 Hz, 1H, CHHSePh), 3.45 (dd, J¼4.8, 13.1 Hz, 1H,
CHHSePh), 4.38 (dt, J¼4.4, 4.4, 9.1, 9.1 Hz, 1H, CHCl),
7.33 (d, J¼2.5 Hz, 3H, Ar–H), 7.57 (dd, J¼2.3, 5.8 Hz,
2H, Ar–H), 11.00 (br s, 1H, CO2H).
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7.7. In situ generation of selenurane (17)
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A solution of 16 was generated as described above. After
5 min, NCS (14 mg, 0.1 mmol) was added. Shaking this
mixture resulted in the formation of a colorless solution
that contains a 1:1 mixture of succinimide and 17. 1H
NMR (400 MHz, CD2Cl2) d 2.87 (dd, J¼9.1, 17.4 Hz, 1H,
CHHCHSePh), 3.17 (d, J¼17.4 Hz, 1H, CHHCHSePh),
4.22 (dd, J¼12.4 Hz, 1H, CHHCl), 4.62 (dd, J¼4.5,
12.4 Hz, 1H, CHHCl), 4.72 (br s, 1H, CHSePhClO), 7.58
(m, 3H, Ar–H), 7.83 (d, J¼8.0 Hz, 2H, Ar–H); 13C NMR
(75 MHz, CDCl3) d 34.8 (CH2CO2), 43.8 (CH2Cl), 69.6
(CHSe), 129.3 (Ar C–H), 130.5 (Ar C–H), 132.6 (Ar
C–H), 134.5 (q Ar–C).
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7.8. Kinetics
N-Chlorosuccinimide (19–43 mg) was dissolved in dry
CD2Cl2 (580 mL). Upon complete dissolution of the NCS,
2-methyl-2-heptene (10 mL of a 0.97 M standard solution
in CD2Cl2) was added. The NMR tube was sealed with a sep-
tum and immediately taken to the NMR spectrometer. Next,
PhSeCl (10 mL of a 0.05 M standard solution in CD2Cl2) was
injected and the sample was mixed by shaking. The resulting
solutions were quickly inserted into the spectrometer for
analysis.
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References and notes
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23. Radical inhibitors do not inhibit this reaction.
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