Carbon dioxide (CO 2 ) is an intrinsically stable molecule. However, its reactivity toward nucleophilic bases has constituted an appealing characteristic for applications such as CO 2 capture and functionalization. To shed light on the role of nucleophilic bases in CO 2 functionalization, we performed some mechanistic studies using nitrogen-containing bases as an additivein catalytic amountsfor carboxylation reactions of Grignard reagents. Our kinetic analysis and in situ infrared spectroscopy revealed the role of nucleophilic bases, particularly that of DBU (1,8-diazabicycloundec-7-ene), in CO 2 (de)activation for carboxylation reactions.
We report the use of CO2 to curb the reactivity of NaBH4 enabling its use in reductive amination reactions. CO2 readily reacts with NaBH4 to decrease its capacity to reduce aldehydes to alcohols while remaining able to reduce imines and iminium ions for desired alkylation reactions. The formation of NaBH(OCHO)3 as a reducing reagent was critical to achieve the desired selectivity. A general protocol was established for C–N bond formation reactions and replacing NaBH4 with NaBD4 allowed for reductive amination with concomitant deuteration to be carried out.
Diamides are ubiquitous in chemical structures of organic molecules with a variety of applications. Most of these diamides are accessed via acylation of diamines with the corresponding acyl donors, using...
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