Ag(Ⅰ)/(nC7H15)4NBr-catalyzed reaction of ammonium carbamates and propargylic alcohols:Quantitative conversion of CO2 into β-oxopropylcarbamates
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摘要: 将一种简单的双组分催化体系即Ag(Ⅰ)/(nC7H15)4NBr应用于常压下催化氨基甲酸盐和炔丙醇双组分反应制备β-羰基氨基甲酸酯。该方法具有简便、高效的优点, 并且不需要使用配体, 可以将一系列的炔丙醇和仲胺底物转化为相应的氨基甲酸酯产物。该方法通过CO2的定量催化转化, 提高了CO2的利用效率。Abstract: A simple dual-component catalytic system, i.e., Ag(Ⅰ)/(nC7H15)4NBr was applied for the synthesis of various β-oxopropylcarbamates via dual-component coupling of ammonium carbamates and propargylic alcohols under atmospheric pressure.This simple method was proved to be a highly efficient system without the use of ligand, and capable of converting various propargylic alcohols and secondary amines into corresponding organic carbamates.Notably, quantitative conversion of CO2 was achieved, thus improved the efficiency of CO2 utilization.
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Key words:
- CO2 conversion /
- ammonium carbamates /
- silver catalysis /
- β-oxopropylcarbamates /
- synthetic method
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图 1 过渡金属催化下的氨基甲酸盐转化反应
Figure 1 Transition-metal catalyzed transformation of carbamates
图 2 双组分反应制备β-羰基氨基甲酸酯
Figure 2 Synthesis of β-oxopropylcarbamates through dual-component reaction
图 3 溶剂(a)和温度(b)对反应的影响
Figure 3 Solvent (a) and temperature (b) effect on the transformation reaction conditions:1a(84.1 mg, 1 mmol), 2a(168.2 mg, 1 mmol), AgOAc (8.4 mg, 0.05 equiv.), (nC7H15)4NBr (25.0 mg, 0.05 equiv.), 60 ℃; yield was determined by GC analysis with biphenyl as the internal standard
表 1 双组分反应的条件优化[a]
Table 1 Optimization of the dual-component reaction[a]
Entry Catalyst(0.05 equiv.) Co-catalyst(equiv.) Time t/h Yield[b]w/% 1 - - 12 0 2 AgOAc - 12 4 3 Ag2CO3 - 12 <1 4 AgCl - 12 11 5 (nC7H15)4NBr - 12 0 6 AgOAc (nC7H15)4NBr (0.05) 12 36 7 Ag2O (nC7H15)4NBr (0.05) 12 19 8 Ag2CO3 (nC7H15)4NBr (0.05) 12 22 9 Ag2SO4 (nC7H15)4NBr (0.05) 12 16 10 AgCl (nC7H15)4NBr (0.05) 12 29 11 AgOAc (nC4H9)4NBr (0.05) 12 31 12 AgOAc (nC3H7)4NBr (0.05) 12 20 13 AgOAc (nC3H7)4NCl (0.05) 12 18 14 AgOAc (C2H5)4NCl (0.05) 12 16 15 AgOAc NH4Cl (0.05) 12 12 16 AgOAc (nC7H15)4NBr (0.05) 24 43 17 AgOAc (nC7H15)4NBr (0.07) 24 49 18 AgOAc (nC7H15)4NBr (0.09) 24 51 19[c] AgOAc (nC7H15)4NBr (0.09) 24 73 20[d] AgOAc (nC7H15)4NBr (0.09) 24 85 21[e] AgOAc (nC7H15)4NBr (0.09) 24 94 [a] unless otherwise specified, all the reactions were performed with 1a (84.1 mg, 1 mmol), 2a (168.2 mg, 1 mmol), catalyst (0.05 equiv.), CH3CN (2 mL), 60 ℃; [b] determined by GC analysis with biphenyl as the internal standard; [c] 1a (3 mmol, 3 equiv.); [d] 1a (5 mmol, 5 equiv.); [e] 1a (6 mmol, 6 equiv.) 
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表 2 炔丙醇和氨基甲酸盐双组分反应的底物适用范围[a, b]
Table 2 Scope of the dual-component reaction of propargylic alcohols and carbamates[a, b]
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