Catalytic Transfer Hydrogenation Reaction Research Articles

Confining Co-Based Nanocatalysts by Ultrathin Nanotubes for Efficient Transfer Hydrogenation of Biomass Derivatives.

Catalytic transfer hydrogenation (CTH) based on non-noble-metal catalysts has emerged as an environmentally friendly way for the utilization of biomass resources. However, the development of efficient and stable non-noble-metal catalysts is crucially challenging due to their inherent inactivity. Herein, a metal-organic framework (MOF)-transformed CoAl nanotube catalyst (CoAl NT160-H) with unique confinement effect was developed via a "MOF transformation and reduction" strategy, which exhibited excellent catalytic activity for the CTH reaction of levulinic acid (LA) to γ-valerolactone (GVL) with isopropanol (2-PrOH) as the H donor. Comprehensive characterizations and experimental investigations uncovered that the confined effect of the ultrathin amorphous Al2O3 nanotubes could modulate the electronic structure and enhance the Lewis acidity of Co nanoparticles (NPs), thus contributing to the adsorption and activation of LA and 2-PrOH. The synergy between the electropositive Co NPs and Lewis acid-base sites of the CoAl NT160-H catalyst facilitated the transfer of α-H in 2-PrOH to the C atom of carbonyl in LA during the CTH process via a Meerwein-Ponndorf-Verley mechanism. Moreover, the confined Co NPs embedded on am-Al2O3 nanotubes endowed the CoAl NT160-H catalyst with superior stability and the catalytic activity was nearly unchanged for at least ten cycles, far surpassing that of the Co/am-Al2O3 catalyst prepared by the traditional impregnation method.

Organodiphosphonate Zr‐MOF: A highly efficient catalyst for Meerwein–Ponndorf–Verley reduction of furfural

AbstractTetraethyl p‐xylenediphosphate is used as the organic ligand to prepare the organodiphosphonate Zr‐based metal organic frameworks (ZrP‐MOF). The physicochemical characterizations of ZrP‐MOF under different hydrothermal and calcination conditions were performed by various analytical techniques. ZrP‐MOF was then employed as a catalyst for the catalytic transfer hydrogenation of furfural with alcohol as the hydrogen donor, and the preparation parameters and catalytic properties of ZrP‐MOF were investigated. Compared with fresh ZrP‐MOF, the furfural conversion of ZrP‐MOF calcined at 825 K increased from 43.5% to 95.1%. Calcination can significantly increase the Lewis/Brønsted acid ratio and enlarge the pore structure of ZrP‐MOF, which promote the furfural catalytic transfer hydrogenation reaction over Zr‐O based on the Meerwein–Ponndorf–Verley reduction.

Construction of electron-deficient zirconium sites for the efficient catalytic transfer hydrogenation of levulinic acid

Zirconium-derived catalyst with abundant Lewis acid-base pairs has earned it a place of prominence for the catalytic upgrade of bio-based carbonyls to valuable chemicals and fuels through catalytic transfer hydrogenation (CTH) reaction. However, the low catalytic efficiency of Zr-based catalysts urgently needs to be improved to meet the criterion for their industrial deployment. In this contribution, tungstophosphoric acid (HPW) was demonstrated as an effective modifier to the electronic structure of the pristine polyacrylonitrile and lignin-supported Zr nanofiber (Zr-Lig@PAN) to boost the CTH of levulinic acid (LA) into γ-valerolactone (GVL). Especially, an impressive GVL formation rate of 32.5 mmol·g−1·h−1 was implemented over Zr/HPW0.75g-Lig@PAN, significantly prevailing over the previous reported Zr-based catalysts for the CTH of LA or its ester to GVL. Mechanistic investigations well demonstrated that the superior electron-accept ability of HPW allowed the construction of electron-deficient Zr sites, which is beneficial to the adsorption and activation of LA and isopropanol, thus boosting the CTH reaction. These findings open up a new avenue to design efficient Zr-based catalysts for the CTH reaction by elaborately tuning the electronic structure of the catalyst in the presence of a second metal.

Amido-ene(amido) Ni(II)-Catalyzed Highly Enantioselective Transfer Hydrogenations of Ketone: Dual Functions of the Ene(amido) Group

Catalytic asymmetric transfer hydrogenation (ATH) reactions of ketones have become an important tool for producing enantiomerically pure alcohols that are widely used in the syntheses of bioactive compounds. However, the high toxicities and low abundances of traditionally employed precious metals serving as catalyst centers have impeded widespread application of precious metal-based catalysts in asymmetric synthesis. Development of catalysts from abundant and less toxic 3d metals is highly desirable but still challenging. We report herein the development of structurally well-defined (R,R)-amido-ene(amido) nickel catalysts for ATH of ketone substrates, facilitating access to a wide range of secondary (S)-configuration alcohols, many of which are synthetic building blocks of biologically relevant molecules, with up to 95% enantiomeric excess (e.e.) and broad scope of functional group tolerance. Catalytic intermediate isolation and density functional theory calculation ascribed the catalytic activity to stabilization of the electron-rich nickel center with the ene(amido) group via a π-backdonation interaction within the catalytic intermediates, while the stereoinduction mainly arises from a catalyst–substrate π–π interaction in the transition state for enantioselective hydride transfer.

Selective catalytic transfer hydrogenation of polyunsaturated fatty acid methyl esters using Pd/organobentonite as catalyst under microwave heating

In this study, the catalytic transfer hydrogenation (CTH) of polyunsaturated fatty acid methyl esters (FAMEs) was carried out using ammonium formate as hydrogen donor and Pd/organobentonite (Pd/OB) as catalyst under the assistance of microwave. The effects of different technology parameters on the content of each FAME composition were investigated during the CTH reaction, and the optimal reaction conditions for the hydrogenation of FAMEs were determined. Under the optimal CTH conditions (40 g as the amount of ammonium formate, 60 g as the water amount, 8 wt.% as the catalyst dosage, 80 °C as the reaction temperature, 140 min as the reaction time and 350 rpm as the agitation speed), methyl linoleate (C18:2) was successfully hydrogenated into methyl oleate (C18:1) with high C18:2 conversion ratio (CRC182) of 78.56% and high C18:1 yield of 72.22%, and high selectivity for cis-C18:1 of 70.29%. Compared with conventional heating, microwave heating used in the CTH could enhance the CRC182 from 60.27% to 78.56% and reduce hydrogenation time. Moreover, the reaction of microwave-assisted CTH accorded with pseudo-first-order dynamic model through analyzing the obtained experimental data. In general, the effective hydrogenation of polyunsaturated FAMEs could be achieved under the microwave-assisted CTH reaction.

Production of γ-valerolactone from ethyl levulinate over hydrothermally synthesized Sn-Beta under mild conditions

Production of γ-valerolactone (GVL) from ethyl levulinate (EL) was studied by catalytic transfer hydrogenation (CTH) strategy under mild conditions. Hydrothermally synthesized Sn-Beta zeolites with high crystallinity show high catalytic activity and selectivity. With isopropanol as hydrogen source, 97.1 % GVL yield with 100 % selectivity was given under 110 °C. Crystallization time for synthesis of Sn-Beta showed great effect on the catalytic performance. Sn-Beta-xd catalysts with longer crystallization time (≥7 days) have high crystallinity and better catalytic performance. Firstly, longer crystallization time is necessary for the formation of large amount of Lewis acid sites which catalyze the conversion of EL to GVL. Secondly, high level of silanol groups in Sn-Beta has negative effect on the catalytic performance. High crystallinity means the amount of silanol groups in Sn-Beta-xd at a low level which is favorable for this CTH reaction. Meanwhile, this is why hydrothermally synthesized Sn-Beta shows higher catalytic activity than post-synthesized Sn-Beta in the conversion of EL to GVL. Furthermore, the catalyst was reusable.

Magnetic graphene oxide-anchored Ni/Cu nanoparticles with a Cu-rich surface for transfer hydrogenation of nitroaromatics

• The Ni/Cu NPs with a Cu-rich surface were prepared by thermal decomposition. • Graphene oxide anchored Ni/Cu NPs to prepare magnetic Ni/Cu-GO catalyst. • Ni/Cu-GO with different composition for CTH of 2-methyl-5-nitrophenol were studied. • Ni 7 /Cu 3 -GO did not dehalogenate for CTH of halogen-containing nitroaromatics. The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell (Ni/Cu NPs) were successfully synthesized by a liquid-phase thermal decomposition method. The content of copper and nickel in Ni/Cu NPs was controllable by adjusting the ratio of two metal precursors, copper formate (Cuf) and nickel acetate tetrahydrate (Ni(OAc) 2 ∙4H 2 O). Ni/Cu NPs were further anchored on graphene oxide (GO) to prepare a magnetic composite catalyst, called Ni/Cu-GO. The dispersibility of Ni/Cu NPs in solution was enhanced by GO anchoring to prevent the sintering and aggregation during the reaction process, thereby ensuring the catalytic and cycling performance of the catalyst. The catalytic transfer hydrogenation (CTH) reaction of nitroaromatics was investigated when ammonia borane was used as the hydrogen source. Cu dominated the main catalytic role in the reaction, while Ni played a synergistic role of catalysis and providing magnetic properties for separation. The Ni 7 /Cu 3 -GO catalyst exhibited the best catalytic performance with the conversion and yield of 99% and 96%, respectively, when 2-methyl-5-nitrophenol was used as the substrate. The Ni 7 /Cu 3 -GO catalyst also exhibited excellent cyclic catalytic performance with the 5-amino-2-methylphenol yield of above 90% after 6 cycles. In addition, the Ni 7 /Cu 3 -GO catalyst could be quickly recycled by magnetic separation. Moreover, the Ni 7 /Cu 3 -GO catalyst showed good catalytic performance for halogen-containing nitroaromatics without dehalogenation.

Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics.

The biomass-derived platform chemicals furfural and 5-(hydroxymethyl)furfural (HMF) may be converted to α-angelica lactone (AnL) and levulinic acid (LA). Presently, LA (synthesized from carbohydrates) has several multinational market players. Attractive biobased oxygenated fuel additives, solvents, etc., may be produced from AnL and LA via acid and reduction chemistry, namely alkyl levulinates and γ-valerolactone (GVL). In this work, hierarchical hafnium-containing multifunctional Linde type L (LTL) related zeotypes were prepared via top-down strategies, for the chemical valorization of LA, AnL and HMF via integrated catalytic transfer hydrogenation (CTH) and acid reactions in alcohol medium. This is the first report of CTH applications (in general) of LTL related materials. The influence of the post-synthesis treatments/conditions (desilication, dealumination, solid-state impregnation of Hf or Zr) on the material properties and catalytic performances was studied. AnL and LA were converted to 2-butyl levulinate (2BL) and GVL in high total yields of up to ca. 100%, at 200°C, and GVL/2BL molar ratios up to 10. HMF conversion gave mainly the furanic ethers 5-(sec-butoxymethyl)furfural and 2,5-bis(sec-butoxymethyl)furan (up to 63% total yield, in 2-butanol at 200°C/24 h). Mechanistic, reaction kinetics and material characterization studies indicated that the catalytic results depend on a complex interplay of different factors (material properties, type of substrate). The recovered-reused solids performed steadily.

Direct epitaxial synthesis of magnetic biomass derived acid/base bifunctional zirconium-based hybrid for catalytic transfer hydrogenation of ethyl levulinate into γ-valerolactone

The development of efficient and reusable catalysts to improve the catalytic transfer hydrogenation (CTH) of biomass-derived platform molecules into high value-added chemicals is always desired. For this purpose, the magnetic Fe3O4@Zr-FDCA hybrid with Lewis acid and Lewis base sites was first designed by simple assembly of biomass derived 2,5-furandicarboxylic acid (FDCA) with zirconium and grown directly on the surface of carboxylated Fe3O4. The resulting Fe3O4@Zr-FDCA exhibited a unique core-shell structure with high specific surface area and proper acid/basic strength, it performed well in CTH reaction of diverse carbonyl compounds, especially for the conversion of ethyl levulinate to γ-valerolactone with the yield of 94.5% at 180 °C for 5 h. Furthermore, the good magnetic responsibility of Fe3O4@Zr-FDCA made it could be easily separated from the reaction mixture by an external magnet, and displayed a good reusability with no significant loss in the activity after reuse for five runs.

Synergetic effect of Cu0 −Cu+ derived from layered double hydroxides toward catalytic transfer hydrogenation reaction

As a safe and environmentally friendly selective hydrogenation method, catalytic transfer hydrogenation (CTH) has aroused great interest in preparation of high-value-added products from biomass derived resources. Herein, a Cu-based catalyst (Cu/CuAl-MMO-400) was prepared by structural topological transformation of layered double hydroxides (LDHs) precursor, which displayed promising catalytic behavior toward CTH reaction of furfural (FAL) with 2-propanol (2-POL) as the hydrogen donor. Notably, the reaction rate is as high as 0.125 mol g−1 h−1, which is superior to previously reported non-noble metal catalysts. A combination investigation based on XPS, XANES and Bader charge confirms the co-existence of Cu0 and Cu+ sites on the surface of Cu nanoparticles. Both experimental studies (in situ DRIFTS and isotope labelling MS) and DFT calculations reveal that the Cu0−Cu+ synergistic effect plays a vital role in determining catalytic behavior: the Cu+ species acts as both dehydrogenation and hydrogenation active site; while the Cu0 site promotes the transfer of H atoms between adsorbed substrates. This work substantiates a Cu0 −Cu+ synergetic catalysis by establishing structure-property correlation and revealing reaction pathway, which could be extended to other CTH reactions in the upgrading processes of biomass.

Tuning dual active sites of Cu/CoCeOx catalysts for efficient catalytic transfer hydrogenation of 5-hydroxymethylfurfural to biofuel 2,5-dimethylfuran

Much attention has been attracted on the production of renewable biofuels through efficient catalytic transfer hydrogenation (CTH) reaction. In this study, a series of Cu/CoCeOx catalysts were synthesized by a facile coprecipitation method for CTH of 5-hydroxymethylfurfural (HMF) to different products with 2-propanol as a hydrogen donor, and the dual active sites of CuCo and CoCeOx were tuned via H2-reduction temperature. A 92.2% yield of 2,5-dihydroxymethylfuran (DHMF) was achieved at 150 °C over the Cu4Co8Ce4-300 catalyst, and a 95.4% yield of 2,5-dimethylfuran (DMF) was obtained over the Cu4Co10Ce2-600 catalyst at 170 °C. The roles of the dual active sites were further investigated, and the results showed that Cu species were identified as the major active sites of 2-propanol dehydrogenation, CoCeOx sites were responsible for the conversion of HMF to DHMF, and CuCo bimetallic nanoparticles promoted the cleavage of C-O in DHMF to obtain DMF. XRD, Raman, and HAADF-STEM analysis confirmed the existence of these sites. XPS and H2-TPR verified the formation of CuCo bimetallic nanoparticles, and NH3-TPD was employed to evaluate the acidity of the surface. Furthermore, in situ DRIFT of furfuryl alcohol and performance test experiments were conducted to understand the synergistic mechanism of dual active sites in hydrogen transfer from 2-propanol to HMF. This work provides a strategy to obtain different target products via tuning dual active sites.

Sustainable metal-lignosulfonate catalyst for efficient catalytic transfer hydrogenation of levulinic acid to γ-valerolactone

Production of γ-valerolactone (GVL) from biomass-derived platform levulinic acid (LA) via catalytic transfer hydrogenation (CTH) over renewable lignosulfonate-derived catalyst is reported herein. Lignosulfonate-derived catalysts were prepared by assembled Zr-metals with sodium lignosulfonate (LigS) derived from the industry paper waste. The resulting Zr-LigS catalyst exhibited excellent catalytic performance in 92.5% GVL yield under mild conditions. With the combination of detail catalyst characterizations, catalytic performance of the Zr-LigS catalyst, in-situ ATR-FTIR and poisoning experiments, the hydrothermal treatment of Zr4+ and LigS resulted in the formation of basic sites, which contributed significantly to the CTH reaction. Kinetic experiments demonstrated that the activation energy was as low as 41.9 kJ/mol. Furthermore, isotopic labeling experiments suggested that the β-H in isopropanol is transferred to the CO bond of LA by the formation of six-membered intermediates on the basic sites, which is the rate-determining step.

The Inorganic Perovskite-Catalyzed Transfer Hydrogenation of Cinnamaldehyde Using Glycerol as a Hydrogen Donor

Catalytic transfer hydrogenation reactions (CTHs) produce value-added chemicals in the most economical, safe, green, and sustainable way. However, understanding the reaction mechanism and developing stable, selective, and cheap catalysts has been a significant challenge. Herein, we report on the hydrogenation of cinnamaldehyde utilizing glycerol as a hydrogen donor and metal-oxides (SnO2, LaFeO3, and LaSnO3) as heterogeneous catalysts. The perovskite types were used because they are easy to synthesize, the metal components are readily available, and they are good alternatives to noble metals. The catalysts were synthesized through the nanocasting (hard-template) method with SiO2 (KIT-6) as a template. The template was synthesized using the soft-template (sol-gel) method resulting in a high surface area of 624 m2/g. Furthermore, catalytic evaluations gave high cinnamaldehyde percentage conversions of up to 99%. Interestingly, these catalysts were also found to catalyze the etherification of glycerol in one pot. Therefore, we propose competitive surface catalytic reactions driven by the transition metal cations as the binding sites for the cinnamaldehyde and the sacrificial glycerol.

Ligand-free sub-5 nm platinum nanocatalysts on polydopamine supports: size-controlled synthesis and size-dictated reaction pathway selection.

Noble metal nanoparticles exhibit intriguing size-dependent catalytic activities toward a plethora of important chemical reactions. A particularly interesting but rarely explored scenario is that some catalytic molecule-transforming processes may even inter-switch among multiple reaction pathways when the dimensions of a metal nanocatalyst are deliberately tuned within specific size windows. Here, we take full advantage of the adhesive surface properties of polydopamine to kinetically maneuver the surface-mediated nucleation and growth of Pt nanocrystals, which enables us to synthesize polydopamine-supported sub-5 nm Pt nanocatalysts with precisely tunable particle sizes, narrow size distributions, ligand-free clean surfaces, and uniform dispersion over the supports. The success in precisely tuning the particle size of ligand-free Pt nanocatalysts within the sub-5 nm size window provides unique opportunities for us to gain detailed, quantitative insights concerning the intrinsic particle size effects on the pathway selection of catalytic molecular transformations. As exemplified by Pt-catalyzed nitrophenol reduction by ammonia borane, catalytic transfer hydrogenation reactions may inter-switch between two fundamentally distinct bimolecular reaction pathways, specifically the Langmuir-Hinshelwood and the Eley-Rideal mechanisms, as the size of the Pt nanocatalysts varies in the sub-5 nm regime.

Cobalt nanoparticles supported on microporous nitrogen-doped carbon for an efficient catalytic transfer hydrogenation reaction between nitroarenes and N-heterocycles

Cobalt nanoparticles supported on microporous nitrogen-doped carbon (Co/mNC) were prepared for catalytic hydrogen transfer between nitroarenes and N-heterocycles.

Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review.

The massive burning of a large amount of fossil energy has caused a lot of serious environmental issues (e.g., air pollution and climate change), urging people to efficiently explore and valorize sustainable alternatives. Biomass is being deemed as the only organic carbon-containing renewable resource for the production of net-zero carbon emission fuels and fine chemicals. Regarding this, the selective transformation of high-oxygen biomass feedstocks by catalytic transfer hydrogenation (CTH) is a very promising strategy to realize the carbon cycle. Among them, the important Meerwein-Ponndorf-Verley (MPV) reaction is believed to be capable of replacing the traditional hydrogenation strategy which generally requires high-pressure H2 and precious metals, aiming to upgrade biomass into downstream biochemical products and fuels. Employing bifunctional heterogeneous catalysts with both acidic and basic sites is needed to catalyze the MPV reaction, which is the key point for domino/cascade reaction in one pot that can eliminate the relevant complicated separation/purification step. Zirconium (Zr) and hafnium (Hf), belonging to transition metals, rich in reserves, can demonstrate similar catalytic efficiency for MPV reaction as that of precious metals. This review introduced the application of recyclable heterogeneous non-noble Zr/Hf-containing catalysts with acid-base bifunctionality for CTH reaction using the safe liquid hydrogen donor. The corresponding catalysts were classified into different types including Zr/Hf-containing metal oxides, supported materials, zeolites, metal-organic frameworks, metal-organic hybrids, and their respective pros and cons were compared and discussed comprehensively. Emphasis was placed on evaluating the bifunctionality of catalytic material and the key role of the active site corresponding to the structure of the catalyst in the MPV reaction. Finally, a concise summary and prospect were also provided centering on the development and suggestion of Zr/Hf-containing acid-base bifunctional catalysts for CTH.

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts.

Heterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions. Hafnium-containing TUD-1 type catalysts were the first of ordered mesoporous silicates explored for the conversion of Fur and Hmf via CTH/alcohol strategies. The materials promoted CTH and acid reactions leading to the furanic ethers. The bioproducts spectrum was broader for the reaction of Fur than of Hmf. A Fur reaction mechanism based on literature data was discussed and supported by kinetic modelling. The influence of the Hf loading and reaction conditions (catalyst load, type of alcohol H-donor, temperature, initial substrate concentration) on the reaction kinetics was studied. The reaction conditions were optimized to maximize the yields of 2-(alkoxymethyl)furan ethers formed from Fur; up to 63% yield was reached at 88% Fur conversion, 4 h/150 °C, using Hf-TUD-1(75), which was a stable catalyst. The Hf-TUD-1(x) catalysts promoted the selective conversion of Hmf to bis(2-alkoxymethyl)furan; e.g., 96% selectivity at 98% Hmf conversion, 3 h/170 °C for Hf-TUD-1(50).

On-DNA Transfer Hydrogenolysis and Hydrogenation for the Synthesis of DNA-Encoded Chemical Libraries.

DNA-encoded libraries (DELs) are an increasingly popular approach to finding small molecule ligands for proteins. Many DEL synthesis protocols hinge on sequential additions of monomers using split-pool combinatorial methods. Therefore, compatible protecting group strategies that allow the unmasking of reactive functionality (e. g. amines and alcohols) prior to monomer coupling, or the removal of less desirable functionality (e. g., alkenes and alkynes) are highly desirable. Hydrogenation/hydrogenolysis procedures would achieve these ends but have not been amenable to DEL chemistry. We report a catalytic hydrogen transfer reaction using Pd/C, HCONH4 and the micelle-forming surfactant, TPGS-750-M, which gives highly efficient conversions for hydrogenolysis of Cbz-protected amines and benzyl protected alcohols and hydrogenation of nitros, halides, nitriles, aldehydes, alkenes and alkynes. Application to multicycle synthesis of an encoded compound was fully compatible with DNA-amplification and sequencing, demonstrating its applicability to DEL synthesis. This method will enable synthetic DEL sequences using orthogonal protecting groups.

On-DNA Transfer Hydrogenolysis and Hydrogenation for the Synthesis of DNA-Encoded Chemical Libraries.

DNA‐encoded libraries (DELs) are an increasingly popular approach to finding small molecule ligands for proteins. Many DEL synthesis protocols hinge on sequential additions of monomers using split‐pool combinatorial methods. Therefore, compatible protecting group strategies that allow the unmasking of reactive functionality (e. g. amines and alcohols) prior to monomer coupling, or the removal of less desirable functionality (e. g., alkenes and alkynes) are highly desirable. Hydrogenation/hydrogenolysis procedures would achieve these ends but have not been amenable to DEL chemistry. We report a catalytic hydrogen transfer reaction using Pd/C, HCONH4 and the micelle‐forming surfactant, TPGS‐750‐M, which gives highly efficient conversions for hydrogenolysis of Cbz‐protected amines and benzyl protected alcohols and hydrogenation of nitros, halides, nitriles, aldehydes, alkenes and alkynes. Application to multicycle synthesis of an encoded compound was fully compatible with DNA‐amplification and sequencing, demonstrating its applicability to DEL synthesis. This method will enable synthetic DEL sequences using orthogonal protecting groups.

Catalytic Hydrogen Transfer Reactions

AbstractOur recently studies on three types of reactions with hydrogen transfer as a key step, including catalytic asymmetric proton transfer reactions using “chiral proton transfer shuttle”, catalytic B—H bond insertion containing a hydrogen atom transfer, and iron‐catalyzed hydrosilylation reactions containing hydride transfer were briefly introduced. What is the most favorite and original chemistry developed in your research group?The discovery of B—H bond insertion reaction.How do you get into this specific field? Could you please share some experiences with our readers?The reaction of B—H bond insertion was a serendipitous result during we pursuing the other carbene insertion reactions. My lesson on this project is that the discovery may come from bold hypothesis, cautious verification, and appropriate evaluation on unexpected results.How do you supervise your students?Try my best to stimulate their enthusiasm for innovation, provide them strongest supports, and explore unknown with them as a partner.What is the most important personality for scientific research?Passion for self‐actualization and curiosity.How do you keep balance between research and family?Travel with my family regularly and try to share my research progresses with them.