Iridium-Catalyzed Hydrosilylative Reduction of Glucose to Hexane(s)

McLaughlin, Matthew P.; Adduci, Laura L.; Becker, Jennifer J.; Gagné, Michel R.

doi:10.1021/ja3110494

Cited by 74 publications

(57 citation statements)

References 44 publications

(21 reference statements)

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“…This was achieved with two homogeneous catalysts, one a pincer-ligated iridium(III) complex 19 and the other a metal free boron catalyst (B(C 6 F 5 ) 3 , BCF) 20 . The latter catalyst is commercially available and was used in the present studies 21 .…”

Section: Resultsmentioning

confidence: 99%

Chemoselective conversion of biologically sourced polyols into chiral synthons

et al. 2015

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Crude oil currently provides much of the world's energy, but it is also the source of many feedstock chemicals. Methodology for the conversion of biomass into useful chemicals has often focused on either complete deoxygenation or the production of high-volume platform chemicals. Here, we describe the chemoselective partial reduction of silyl-protected C6O6-derived polyols to produce a diverse set of oxygen-functionalized chiral synthons. The combination of B(C6F5)3 and a tertiary silane efficiently generates a reactive equivalent of an electrophilic silylium ion (R3Si(+)) and a hydride (H(-)) reducing agent. The mechanism of oxygen loss does not involve a dehydrative elimination and thus avoids ablation of stereochemistry. Neighbouring group participation and the formation of cyclic intermediates is key to achieving selectivity in these reactions and, where both primary and secondary C-O bonds are present, the mechanism allows further control. The method provides--in one or two synthetic steps--highly improved syntheses of many C6On synthons as well as several previously undescribed products.

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Section: Resultsmentioning

confidence: 99%

Chemoselective conversion of biologically sourced polyols into chiral synthons

et al. 2015

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“…Interestingly, the 1 H NMR studies of Ir–H complexes have only shown the tendency for Ir to self-decouple for 1 J coupling. 39 Considering the spin number ( I = 3/2) of Ir, the coupling of Ir–H ( 3 J) should produce a quartet splitting instead of a triplet splitting as shown in Figure 2c, inset. Despite this inconclusive NMR splitting, the presence of this abnormal multiplicity strongly supports the presence of an Ir–H ( 3 J) interaction and thus the formation of the Ir–S bond.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Insights into the Formation of Dodecanethiolate-Stabilized Magnetic Iridium Nanoparticles: Thiosulfate vs Thiol Ligands

Gavia

et al. 2014

J. Phys. Chem. C

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The synthesis of stable and isolable iridium nanoparticles with an average core size of ∼1.2 ± 0.3 nm was achieved by employing sodium S-dodecylthiosulfate as a ligand precursor during the modified Brust–Schiffrin reaction. Transmission electron microscopy (TEM) of the isolated Ir nanoparticles revealed a high degree of monodispersity. Further characterizations with 1H NMR, FT-IR, UV–vis spectroscopy, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) confirmed that the synthesized Ir nanoparticles are stabilized by dodecanethiolate ligands produced upon the adsorption/cleavage of S-dodecylthiosulfate on the growing Ir nanoparticle surface. By comparison, synthetic attempts employing dodecanethiol as a stabilizing ligand led to the formation of Ir-thiolate species (Ir(SR)3) as an intermediate and Ir-hydroxide species at the completion of reaction. Mechanistic investigations of these two reactions using S-dodecylthiosulfate and dodecanethiol provided deeper understandings on the novelty of thiosulfate ligands, which allow the successful formation of stable thiolate-capped Ir nanoparticles. Moreover, these Ir nanoparticles were shown to have strong magnetic properties.

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“…10,17,18 To transform cellulose into alkanes, hydrodeoxygenation of cellulose-derived water-soluble carbohydrates and sugar alcohols was widely investigated. 26,27 However, the feedstock of the aforementioned approaches is either carbohydrates or sugars/polyols, which require stepwise reactions from cellulose. [19][20][21] They developed an aqueous-phase reforming method to transform sorbitol into light alkanes over platinum-based catalysts.…”

Section: Introductionmentioning

confidence: 99%

High yield of renewable hexanes by direct hydrolysis–hydrodeoxygenation of cellulose in an aqueous phase catalytic system

et al. 2015

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In aqueous phosphoric acid, cellulose was efficiently converted into hexanes using a Ru/C catalyst combined with layered compounds or silica-alumina materials. In this process, the direct production of hexanes from cellulose can be improved by suppressing the formation of isosorbide, which makes it difficult to yield hexanes by further hydrodeoxygenation. As the co-catalyst, layered compounds showed a significant inhibition effect on the formation of isosorbide from sorbitol due to the steric restrictions of sorbitol dehydration within the interlayers of layered compounds. Typically, layered LiNbMoO 6 played a great role in promoting the production of hexanes directly from cellulose and a promising yield (72% carbon mol) of hexanes was obtained. In addition, the protonic acid, H 3 PO 4 , offered efficient catalysis for the hydrolysis of cellulose and the dehydration of the sorbitol hydroxyl moiety.Scheme 1 Direct catalytic conversion of cellulose into hexanes over Ru/C combined with LiNbMoO 6 in aqueous phosphoric acid. Scheme 2The efficient conversion of cellulose to hexanes over LiNbMoO 6 and Ru/C in aqueous phosphoric acid.This journal is

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Iridium-Catalyzed Hydrosilylative Reduction of Glucose to Hexane(s)

Cited by 74 publications

References 44 publications

Chemoselective conversion of biologically sourced polyols into chiral synthons

Chemoselective conversion of biologically sourced polyols into chiral synthons

Mechanistic Insights into the Formation of Dodecanethiolate-Stabilized Magnetic Iridium Nanoparticles: Thiosulfate vs Thiol Ligands

High yield of renewable hexanes by direct hydrolysis–hydrodeoxygenation of cellulose in an aqueous phase catalytic system

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