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Molecules 2019, 24, x FOR PEER REVIEW 22 of 42 Molecules 2019, 24,S1c8h2eme 21. Zinc complex-catalyzed methylation of amines using hydrosilanes. 22 of 41 Subsequently, they described the first iron catalysts able to promote the reductive Subsequently, they described the first iron catalysts able to promote the reductive functionalization functionalization of CO2 with amines using hydrosilanes as reductants to formamide and of CO2 with amines using hydrosilanes as reductants to formamide and methylamine derivatives under methylamine derivatives under mild reaction conditions (Scheme 22a) [120]. At room temperature, mild reaction conditions (Scheme 22a) [120]. At room temperature, the chemoselectivity of formamide the chemoselectivity of formamide was almost 100%. After increasing the temperature to 100 °C, the was almost 100%. After increasing the temperature to 100 ◦C, the selectivity of N-methylation was selectivity of N-methylation was greatly improved and the majority methylamine derivatives were greatly improved and the majority methylamine derivatives were obtained under the elevated loading obtained under the elevated loading of catalyst. Similarly, iron-rich natural mineral Gibeon of catalyst. Similarly, iron-rich natural mineral Gibeon meteorite was used as an efficient heterogeneous meteorite was used as an efficient heterogeneous catalyst for the N-formylation or N-methylation of catalyst for the N-formylation or N-methylation of amines with CO2 and hydrosilanes recently amines with CO2 and hydrosilanes recently (Scheme 22b) [121]. In the work, a wide range of amines (Scheme 22b) [121]. In the work, a wide range of amines was converted into their corresponding was converted into their corresponding formamides in high yields at room temperature. By simply formamides in high yields at room temperature. By simply varying the conditions e.g., increasing varying the conditions e.g. increasing the temperature (25→100 °C) and catalytic loading (1→10 the temperature (25→100 ◦C) and catalytic loading (1→10 mol%), the selectivity was switched from mol%), the selectivity was switched from N-formylated to N-methylated products. Moreover, the N-formylated to N-methylated products. Moreover, the Gibeon meteorite catalyst was recycled and Gibeon meteorite catalyst was recycled and reused at least five times without appreciable activity reused at least five times without appreciable activity loss. loss. a) R1 b) N R2 Cat: 5 mol%; Yield: 34-99% H Cat: 10 mol%; Yield: 15-99% 1 eq. PhSiH3 THF, rt., 18 h R1 O H N +CO2 0.1 MPa Fe(acac)3 + PP3 PP3: R2 4 eq. PhSiH3 THF,100oC,18h P PPh2 3 1 R N Me Cat:5mol%;Yield:<1-99% Gibeon powder (1 mol% Fe) 1 eq. PhSiH3, dry DMF (0.75 mL) 25 oC, 15 h +3 99% 0% CH3 CH3 R2 Cat: 10 mol%; Yield: <1-99% CH3 CH3 NO NCH HCO H N 2 (1 MPa) Gibeon powder (10 mol% Fe) 1 eq. PhSiH3, dry DMF (0.75 mL) 100 oC, 30 h N O H+ 1% N CH3 98% Scheme 22. Fe-based catalysis for temperature controlled N-formylation/N-methylation. Scheme 22. Fe-based catalysis for temperature controlled N-formylation/N-methylation. In 2015, the Dyson group reported an effective thiazolium carbine-based catalyst for the In 2015, the Dyson group reported an effective thiazolium carbine-based catalyst for the N-formylation of amines, using polymethylhydrosiloxane (PMHS) as a reducing reagent under N-formylation of amines, using polymethylhydrosiloxane (PMHS) as a reducing reagent under ambient pressure [122]. A board range of primary amines could be converted into the corresponding ambient pressure [122]. A board range of primary amines could be converted into the corresponding formamides with PMHS (200–300 mL) at 50 ◦C under atmospheric pressure of CO2. Notably, formamides with PMHS (200–300 mL) at 50 °C under atmospheric pressure of CO2. Notably, a a interesting discovery, namely that the variation of reaction temperature could change the reaction interesting discovery, namely that the variation of reaction temperature could change the reaction products, was also made. For example, the N-formylation could be turned into N-methylation by products, was also made. For example, the N-formylation could be turned into N-methylation by changing the reaction temperature from 50 to 100 ◦C with PMHS (200–300 mL), and methylamine was changing the reaction temperature from 50 to 100 °C with PMHS (200–300 mL), and methylamine obtained in high yield (Scheme 23). was obtained in high yield (Scheme 23).PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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