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When the CuCl-catalyzed diamination of 2-phenylpropene was carried out with di-tert-butylthiadiaziridine 1,1-dioxide or 1,2-di-tert- butyl-3-(cyanimino)diaziridine as the nitrogen source under the previously reported conditions (refs 9 and 12), only a small amount of diamination product or a messy mixtutre was obtained, respectively.
-
When the CuCl-catalyzed diamination of 2-phenylpropene was carried out with di-tert-butylthiadiaziridine 1,1-dioxide or 1,2-di-tert- butyl-3-(cyanimino)diaziridine as the nitrogen source under the previously reported conditions (refs 9 and 12), only a small amount of diamination product or a messy mixtutre was obtained, respectively.
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42
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66149190597
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Representative diamination procedure (Table 1, entry 1): To a 1.5 mL vial equipped with a stir bar were added CuCl (0.002 g, 0.02 mmol), triphenylphosphine (0.0052 g, 0.02 mmol), and CDCl3 (0.3 mL). After the mixture was stirred at room temperature for 10 min, 2-phenylpropene (1a) (0.047 g, 0.4 mmol) was added. The reaction mixture was warmed to 65 C using an oil bath with stirring, and di-tert-butyldiaziridinone (2) (0.136 g, 0.8 mmol) was added by syringe pump over 8 h. The reaction mixture was stirred at this temperature for an additional 1 h and purified by flash chromatography (silica gel, hexane/ether ) 10/1) to give diamination product 3a as a white solid (0.105 g, 91%).
-
Representative diamination procedure (Table 1, entry 1): To a 1.5 mL vial equipped with a stir bar were added CuCl (0.002 g, 0.02 mmol), triphenylphosphine (0.0052 g, 0.02 mmol), and CDCl3 (0.3 mL). After the mixture was stirred at room temperature for 10 min, 2-phenylpropene (1a) (0.047 g, 0.4 mmol) was added. The reaction mixture was warmed to 65 C using an oil bath with stirring, and di-tert-butyldiaziridinone (2) (0.136 g, 0.8 mmol) was added by syringe pump over 8 h. The reaction mixture was stirred at this temperature for an additional 1 h and purified by flash chromatography (silica gel, hexane/ether ) 10/1) to give diamination product 3a as a white solid (0.105 g, 91%).
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Diamination of olefin 9 with CuCl-PPh3 (1:1) (10 mol %) in CDCl3 at 65 C for 10 h gave compound 10 in 30% yield and 11 in 33% yield. Diamination of 9 with CuCl-(R)-DTBM-SEGPHOS (2:1) (10 mol %)8 in CDCl3 at 65 C for 10 h gave compound 10 in 32% yield and 11 in 29% yield.
-
Diamination of olefin 9 with CuCl-PPh3 (1:1) (10 mol %) in CDCl3 at 65 C for 10 h gave compound 10 in 30% yield and 11 in 33% yield. Diamination of 9 with CuCl-(R)-DTBM-SEGPHOS (2:1) (10 mol %)8 in CDCl3 at 65 C for 10 h gave compound 10 in 32% yield and 11 in 29% yield.
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