tert-butyl N-(cyclopropylmethyl)-N-[(2-methylpropan-2-yl)oxycarbonylamino]carbamate

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (10.1 g, 140 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.50 g, 28.0 mmol) and triphenylphosphine (44.1 g, 168 mmol) in tetrahydrofuran (100 mL) was added di-tert-butyl azodicarboxylate (38.7 g, 168 mmol) in portions. The mixture was stirred at room temperature for 3 hours then diluted with water and ethyl acetate. The organic extract was washed with brine, dried (MgSO4), filtered, and concentrated. The residue was purified by column chromatography using an Analogix® Intelliflash280™ (SiO2, eluted with a gradient of 0-100% hexanes in ethyl acetate) to provide the title compound (39 g, 97% yield). 1H NMR (300 MHz, CDCl3) δ ppm 0.16-0.27 (m, 2 H), 0.40-0.54 (m, 2 H), 0.94-1.09 (m, 1 H), 1.47 (s, 9 H), 1.48 (s, 9 H), 3.31 (d, J=6.10 Hz, 2 H), 6.38 (s, 1 H). The organic extract was washed with brine dried (MgSO4) filtered concentrated The residue was purified by column chromatography eluted with a gradient of 0-100% hexanes in ethyl acetate)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (7.15 mL, 90 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.30 g, 27.1 mmol) and triphenylphosphine (28.5 g, 109 mmol) in THF (100 mL) was added (E)-di-tert-butyl diazene-1,2-dicarboxylate (25 g, 109 mmol) in portions at ambient temperature. The reaction mixture was concentrated and allowed to stand overnight. The white solid (PPh3O) precipitated was filtered off and the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient) to yield 27.5 g (96%) of the title compound. The reaction mixture was concentrated The white solid (PPh3O) precipitated was filtered off the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (7.15 mL, 90 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.30 g, 27.1 mmol) and triphenylphosphine (28.5 g, 109 mmol) in THF (100 mL) was added (E)-di-tert-butyl diazene-1,2-dicarboxylate (25 g, 109 mmol) in portions at ambient temperature. The reaction mixture was concentrated and allowed to stand overnight. The white solid (PPh3O) precipitated was filtered off and the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient) to yield 27.5 g (96%) of the title compound. The reaction mixture was concentrated The white solid (PPh3O) precipitated was filtered off the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (7.15 ml, 90 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.30 g, 27.1 mmol) and triphenylphosphine (28.5 g, 109 mmol) in THF (100 mL) was added di-tert-butyl azodicarboxylate (25 g, 109 mmol) portion wise at ambient temperature. The mixture was stirred for 2 hours then concentrated. Solid triphenylphosphineoxide was removed by filtration. The filtrate was concentrated and the residue was purified by flash chromatography (silica gel, eluted with a gradient of 5-25% EtOAc in hexane) to provide 27.5 g (96%) of title compound. 1H NMR (300 MHz, CDCl3) δ ppm 0.15-0.26 (m, 2H), 0.42-0.54 (m, 2H), 0.91-1.09 (m, 1H), 1.47 (s, 9H), 1.48 (s, 9H), 3.31 (d, J=6.10 Hz, 2H), 6.38 (s, 1H). then concentrated Solid triphenylphosphineoxide was removed by filtration The filtrate was concentrated the residue was purified by flash chromatography (silica gel eluted with a gradient of 5-25% EtOAc in hexane)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (10.1 g, 140 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.50 g, 28.0 mmol) and triphenylphosphine (44.1 g, 168 mmol) in tetrahydrofuran (100 mL) was added di-tert-butyl azodicarboxylate (38.7 g, 168 mmol) in portions. The mixture was stirred at room temperature for 3 hours then diluted with water and ethyl acetate. The organic extract was washed with brine, dried (MgSO4), filtered, and concentrated. The residue was purified by column chromatography using an Analogix® Intelliflash280™ (SiO2, 0-100% hexane in ethyl acetate gradient) to yield di-tert-butyl 1-(cyclopropylmethyl)hydrazine-1,2-dicarboxylate (39 g, 97% yield). 1H NMR (300 MHz, CDCl3) δ ppm 0.16-0.27 (m, 2H), 0.40-0.54 (m, 2H), 0.94-1.09 (m, 1H), 1.47 (s, 9H), 1.48 (s, 9H), 3.31 (d, J=6.10 Hz, 2H), 6.38 (s, 1H). The organic extract was washed with brine dried (MgSO4) filtered concentrated The residue was purified by column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (7.15 mL, 90 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.30 g, 27.1 mmol) and triphenylphosphine (28.5 g, 109 mmol) in THF (100 mL) was added (E)-di-tert-butyl diazene-1,2-dicarboxylate (25 g, 109 mmol) in portions at ambient temperature. The reaction mixture was concentrated and allowed to stand overnight. The white solid (PPh3O) precipitated was filtered off and the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient) to yield 27.5 g (96%) of the title compound. The reaction mixture was concentrated The white solid (PPh3O) precipitated was filtered off the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (10.1 g, 140 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.50 g, 28.0 mmol) and triphenylphosphine (44.1 g, 168 mmol) in tetrahydrofuran (100 mL) was added di-tert-butyl azodicarboxylate (38.7 g, 168 mmol) in portions. The mixture was stirred at room temperature for 3 hours then diluted with water and ethyl acetate. The organic extract was washed with brine, dried (MgSO4), filtered, and concentrated. The residue was purified by column chromatography using an Analogix® Intelliflash280™ (SiO2, eluted with a gradient of 0-100% hexanes in ethyl acetate) to provide the title compound (39 g, 97% yield). 1H NMR (300 MHz, CDCl3) δ ppm 0.16-0.27 (m, 2 H), 0.40-0.54 (m, 2 H), 0.94-1.09 (m, 1 H), 1.47 (s, 9 H), 1.48 (s, 9 H), 3.31 (d, J=6.10 Hz, 2 H), 6.38 (s, 1 H). The organic extract was washed with brine dried (MgSO4) filtered concentrated The residue was purified by column chromatography eluted with a gradient of 0-100% hexanes in ethyl acetate)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of cyclopropylmethanol (7.15 mL, 90 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.30 g, 27.1 mmol) and triphenylphosphine (28.5 g, 109 mmol) in THF (100 mL) was added (E)-di-tert-butyl diazene-1,2-dicarboxylate (25 g, 109 mmol) in portions at ambient temperature. The reaction mixture was concentrated and allowed to stand overnight. The white solid (PPh3O) precipitated was filtered off and the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient) to yield 27.5 g (96%) of the title compound. The reaction mixture was concentrated The white solid (PPh3O) precipitated was filtered off the filtrate was purified by flash chromatography (silica gel, EtOAc in Hexane in 5-25% gradient)