Iron-Catalyzed Reduction of CO₂ into Methylene: Formation of C–N, C–O, and C–C Bonds

Abstract

We report herein the use of the (dihydrido)iron catalyst, Fe(H)2(dmpe)2, for the selective reduction of CO2 into either bis(boryl)acetal or methoxyborane depending on the hydroborane used as a reductant. In a one-pot two-step procedure, the in situ generated bis(boryl)acetal was shown to be a reactive and versatile source of methylene to create new C-N but also C-O and C-C bonds.

Reductive CO2 Homocoupling: Synthesis of a Borylated C3 Carbohydrate

“…In the course of these studies, we reported the first formation of bis(boryl)acetal . Subsequently, we described a rare selective generation of the bis(boryl)acetal 1 (Scheme b) and proved that this compound reacts as a surrogate of formaldehyde in the case of condensation processes and Wittig reaction . We report herein the first generation of asymmetric carbon centres from CO 2 , with the synthesis of a borylated C 3 carbohydrate.…”

Future perspectives for formaldehyde: pathways for reductive synthesis and energy storage

“…Later the authors showed that an iron catalysed pathway involving metal hydride catalyst is also feasible for the generation of borylmethylene derivatives with good selectivities. 65 Likewise most recently in 2016, Cantat and Berthet showed that besides iron, also copper and cobalt phosphine complexes are active for the borylation of CO2 yielding mixtures of bisboryl acetal and methoxy borane with a broad range of selectivity for these two products. 66 Please do not adjust margins Please do not adjust margins Scheme 10.…”

Direct synthesis of dicarbonyl PCP-iron hydride complexes and catalytic dehydrogenative borylation of styrene

“…5i-k, 8 Based on our interest in iron catalysis involving hydroboranes, namely hydroboration of alkenes, 12d C-H borylation of arenes, 18 and CO 2 functionalization, 19 we decided to test the newly prepared complexes in the reaction of styrene with pinacolborane (HBpin). 5i-k, 8 Based on our interest in iron catalysis involving hydroboranes, namely hydroboration of alkenes, 12d C-H borylation of arenes, 18 and CO 2 functionalization, 19 we decided to test the newly prepared complexes in the reaction of styrene with pinacolborane (HBpin).…”