Functions Bearing Two Nitrogens

Metal-Free Catalytic Formylation of Amides Using CO2 under Ambient Conditions

“…3 The efficient utilization of this fascinating "diagonal transformation" can lead to the synthesis of versatile chemicals and energy-storage materials, such as formamides, aminals, and methylamines. 4,5 One such direction focuses the hydrosilylation of CO 2 . The major advantages of hydrosilylation of CO 2 are (a) addition of Si−H bond to CO 2 is energetically more favorable than addition of a H−H bond to CO 2 and (b) hydrosilylation of CO 2 can progress in a stepwise manner to allow a series of products with different carbon oxidation states, which includes silyl formates, silyl acetals, methoxysilanes, and methane.…”

“…This reductive functionalization is well documented as “diagonal transformation” by Cantat et al (Figure a) . The efficient utilization of this fascinating “diagonal transformation” can lead to the synthesis of versatile chemicals and energy-storage materials, such as formamides, aminals, and methylamines. , One such direction focuses the hydrosilylation of CO 2 . The major advantages of hydrosilylation of CO 2 are (a) addition of Si–H bond to CO 2 is energetically more favorable than addition of a H–H bond to CO 2 and (b) hydrosilylation of CO 2 can progress in a stepwise manner to allow a series of products with different carbon oxidation states, which includes silyl formates, silyl acetals, methoxysilanes, and methane. , Although there are various reports on hydrosilylation of CO 2 , the reaction usually suffers from the use of precious and rare metal based catalysts at elevated temperature. , As a part of our ongoing investigation to develop an alternative metal-free approach for CO 2 reduction under ambient conditions, herein we report the first catalytic hydrosilylation of CO 2 toward formylation of amides to form a new C–N bond at room temperature (Figure ).…”

Metal-Free α-Amination of Secondary Amines: Computational and Experimental Evidence for Azaquinone Methide and Azomethine Ylide Intermediates

“…Aminal substructures are present in a number of natural products, which makes simple synthetic procedures to their precursors and analogues important to the organic chemist. Recently, one of our groups developed an efficient route to ring-fused aminals , by metal-free, redox-neutral C–H functionalization of cyclic amines (Scheme ). , The procedure is straightforward and only requires heating an aminobenzaldehyde with an excess of amine in ethanol to afford the aminal in one step.…”

Photochemical Cyclopropenation of Alkynes with Diazirines as Carbene Precursors in Continuous Flow

“…Diazo compounds and diazirines, despite being structural isomers, have been developed in entirely separate areas. , Both serve as carbene precursors; , however, diazo compounds have been regarded as essential building blocks in synthetic chemistry, , while diazirines are distinguished as photolabeling and linking reagents. , Trifluoromethyl diazirines, in particular, have found a home in a wide variety of applications from medicinal chemistry (i.e., as photoaffinity probes) , to surface chemistry (i.e., for analyte immobilization), , and polymer cross-linking. , This divided interest has led to diazirines becoming almost forgotten as building blocks in organic synthesis despite their ability to generate carbenes . Hence, it is worthwhile to better develop and elaborate their utility for organic synthesis in the same sense as diazo compounds.…”