99-72-9Relevant articles and documents
Insight into decomposition of formic acid to syngas required for Rh-catalyzed hydroformylation of olefins
Liu, Lei,Chen, Xiao-Chao,Yang, Shu-Qing,Yao, Yin-Qing,Lu, Yong,Liu, Ye
, p. 406 - 415 (2020/12/07)
Formic acid (FA) is one kind of important bulk chemicals, which is recognized as a sustainable and eco-friendly energy carrier to transport H2 via dehydrogenation or CO via decarbonylation. Expectantly, FA upon decomposition into H2 and CO could be used as the syngas alternative for hydroformylation. In this paper, the behaviors of FA to release H2 as well as CO following the distinct pathways were carefully investigated for the first time, and then established a new hydroformylation protocol free of syngas. It was found that the atmospheric hydroformylation of olefins with formic acid (FA) as syngas alternative was smoothly fulfilled over Xantphos (L1) modified Rh-catalyst under mild conditions (80 °C, Rh concentration 1 mol %, 14 h), resulting in >90% conversion of the olefins along with the high selectivity to the target aldehydes (>93%). By using FA as syngas source, the side-reaction of olefin-hydrogenation was greatly depressed. The in situ FT-IR and the high-pressure 1H NMR spectroscopic analyses were applied to reveal how FA behaves dually as CO surrogate and hydrogen source over L1-Rh(acac)(CO)2 catalytic system, based on which the deeply insight into the catalytic mechanism of hydroformylation of olefins with FA as syngas alternative was offered.
Copper-catalyzed hydroformylation and hydroxymethylation of styrenes
Franke, Robert,Geng, Hui-Qing,Meyer, Tim,Wu, Xiao-Feng
, p. 14937 - 14943 (2021/12/02)
Hydroformylation catalyzed by transition metals is one of the most important homogeneously catalyzed reactions in industrial organic chemistry. Millions of tons of aldehydes and related chemicals are produced by this transformation annually. However, most of the applied procedures use rhodium catalysts. In the procedure described here, a copper-catalyzed hydroformylation of alkenes has been realized. Remarkably, by using a different copper precursor, the aldehydes obtained can be further hydrogenated to give the corresponding alcohols under the same conditions, formally named as hydroxymethylation of alkenes. Under pressure of syngas, various aldehydes and alcohols can be produced from alkenes with copper as the only catalyst, in excellent regioselectivity. Additionally, an all-carbon quaternary center containing ethers and formates can be synthesized as well with the addition of unactivated alkyl halides. A possible reaction pathway is proposed based on our results. This journal is
Styrene Hydroformylation with In Situ Hydrogen: Regioselectivity Control by Coupling with the Low-Temperature Water–Gas Shift Reaction
Chen, Fang,Lang, Rui,Li, Tianbo,Qiao, Botao,Su, Yang,Wang, Aiqin,Wang, Hua,Zhang, Tao
supporting information, p. 7430 - 7434 (2020/03/13)
The hydroformylation of olefins is one of the most important homogeneously catalyzed industrial reactions for aldehyde synthesis. Various ligands can be used to obtain the desired linear aldehydes in the hydroformylation of aliphatic olefins. However, in the hydroformylation of aromatic substrates, branched aldehydes are formed preferentially with common ligands. In this study, a novel approach to selectively obtain linear aldehydes in the hydroformylation of styrene and its derivatives was developed by coupling with a water–gas shift reaction on a Rh single-atom catalyst without the use of ligands. Detailed studies revealed that the hydrogen generated in situ from the water–gas shift is critical for the highly regioselective formation of linear products. The coupling of a traditional homogeneous catalytic process with a heterogeneous catalytic reaction to tune product selectivity may provide a new avenue for the heterogenization of homogenous catalytic processes.
