Reductive CO2 Homocoupling: Synthesis of a Borylated C3 Carbohydrate

• Published in: ChemCatChem Vol. 11; no. 2; pp. 760 - 765
• Main Authors: Béthegnies, Aurélien, Escudié, Yannick, Nuñez‐Dallos, Nelson, Vendier, Laure, Hurtado, John, del Rosal, Iker, Maron, Laurent, Bontemps, Sébastien
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 23.01.2019
• Subjects: borane; Boron; carbine; carbohydrate; Carbohydrates; Carbon dioxide; CO2; Coupling; formose; Organic chemistry; Reaction time; Stereoselectivity; Synthesis
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.201801875

To use carbon dioxide as a source of carbon, recent progress has been made toward the synthesis of higher value chemicals and in particular toward Cn compounds. In this context, we report here the synthesis of a borylated C3‐carbohydrate from CO2 as the only source of carbon. This result corresponds to the unprecedented formation of a polyol chain and of asymmetric carbon atoms from CO2. The adopted strategy involves the Fe‐catalysed selective 4e− reduction of CO2 into bis(boryl)acetal followed in one‐pot by a carbene‐mediated C−C coupling reaction. Boron is shown to play a key role in the coupling step enabling to observe the first diastereoselective formose‐type reaction. This result is in addition obtained under mild reaction conditions (T<80 °C, 1 atm of CO2) and short reaction time (t<2 h). Such a boron: The combination of organometallic catalysis and carbene‐mediated C−C homocoupling enables the unprecedented generation of asymmetric carbon centres from CO2.