Reductive Hydroformylation of Isosorbide Diallyl Ether

Abstract

Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%.

Promising Recyclable Ionic Liquid-Soluble Catalytic System for Reductive Hydroformylation

“…The products were analyzed by 1 H NMR using similar procedures to that published previously. 16,17 The conversion was total with isosorbide diallyl ether and an alcohol yield of 49% was reached. However, at the end of the reaction, NMR analysis showed that the products were present in the IL phase and not in the heptane phase, preventing recycling experiments.…”

Auto-Tandem Catalytic Reductive Hydroformylation in a CO2-Switchable Solvent System

“…15 , 16 Recent investigations usually focus on rhodium catalysts due to their superior activity in hydroformylation, which are capable of auto-tandem reductive hydroformylation, e.g., in combination with tertiary alkylamines. 17 − 24 Necessary steric and electronic properties of amines in reductive hydroformylation were previously published by our group. 21 , 25 …”

“…However, auto-tandem catalysisusing the same catalyst for both reaction steps under the same conditionsrepresents the most efficient variant . Auto-tandem reductive hydroformylation was first described for cobalt-based catalysts, although they achieve poor selectivity and require harsh conditions. , Recent investigations usually focus on rhodium catalysts due to their superior activity in hydroformylation, which are capable of auto-tandem reductive hydroformylation, e.g., in combination with tertiary alkylamines. − Necessary steric and electronic properties of amines in reductive hydroformylation were previously published by our group. , …”

Organic Synthesis via Transition Metal-Catalysis

“…In the first original research article, Jérémy Ternel, Adrien Lopes, Mathieu Sauthier, Clothilde Buffe, Vincent Wiatz, Hervé Bricout, Sébastien Tilloy, and Eric Monflier describe the reductive hydroformylation (performed under 80 bar pressure of a 1:1 CO/H 2 mixture, in toluene at 80 • C) of isosorbide diallyl ether (readily available by allylation of bio-sourced isosorbide). The process is catalyzed by a rhodium/amine catalytic system, [typically, Rh(acac)(CO) 2 /Et 3 N], to give the corresponding high value-added bis-primary alcohols [4].…”

“…The subsequent papers report on transition-metal-promoted cyclization processes leading to heterocyclic derivatives. Thus, new polycyclic heterocycles (1H-benzo [4,5]imidazo[1,2c][1,3]oxazin-1-ones) were synthesized by Lucia Veltri, Roberta Amuso, Marzia Petrilli, Corrado Cuocci, Maria A. Chiacchio, Paola Vitale, and Bartolo Gabriele using a ZnCl 2promoted deprotective annulation approach starting from N-Boc-2-alkynylbenzimidazoles under mild conditions (CH 2 Cl 2 as the solvent at 40 • C for 3 h) [6]. N-benzoylindoles were obtained by Zhe Chang, Tong Ma, Yu Zhang, Zheng Dong, Heng Zhao, and Depeng Zhao by Pd(II)-catalyzed oxidative C-H functionalization and annulation of substituted N-(2allylphenyl)benzamides, carried out with Pd(OAc) 2 as the catalyst in the presence of benzoquinone as the oxidant and dibutyl phosphate as the additive in DMSO at 60-70 • C [7].…”