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DOI: 10.1055/a-1912-3059
Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes
This work was supported by the Thousand Young Talents Program of China (Grant No. 15-YINGXIA), the National Natural Science Foundation of China (Grant No. 22001180), and start-up funding from Sichuan University (Grant No. YJ201965).
Dedicated to Professor Jianbo Wang on the occasion of his 60th birthday
Abstract
As a special class of cyclopropanes, gem-difluorinated cyclopropanes have many fascinating properties as a result of the gem-difluoro substitution; thus, their reactions have received much attention from the synthetic chemistry community. Recently, gem-difluorinated cyclopropanes have gradually emerged as a type of novel and unique fluorinated allylic synthon in cross-coupling reactions for the synthesis of monofluoroalkenes. Herein, we briefly summarize recent advances in transition-metal-catalyzed reactions of gem-difluorinated cyclopropanes.
1 Introduction
2 Palladium-Catalyzed Reactions with Linear Selectivity
3 Palladium-Catalyzed Reactions with Branched Selectivity
4 Other Metal-Catalyzed Reactions
5 Conclusions
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Key words
gem-difluorinated cyclopropanes - monofluoroalkenes - transition-metal catalysis - allylation - C–C activation - β-fluorine eliminationIntroduction
Yaxin Zeng (second from left) received his B.E. degree from Sichuan Agricultural University in 2018. He obtained his Master’s degree in 2022 from Sichuan University under the supervision of Professor Ying Xia. He is currently a Ph.D. candidate at Sichuan University.
Zhong-Tao Jiang (second from right) received his B.S. degree from Sichuan Normal University in 2014. He obtained his Master’s degree in 2018 from Sichuan Normal University under the supervision of Professor Bi-Qin Wang and joined Professor Ying Xia’s group in 2019. He is currently a Ph.D. candidate at Sichuan University.
Ying Xia (first from right) was born in 1987 in Yueyang, Hunan Province. He received his B.Eng. degree from Beijing Institute of Technology in 2010 and completed his Ph.D. degree in organic chemistry at Peking University under the supervision of Professor Jianbo Wang and Yan Zhang. He was a postdoctoral fellow in Professor Guangbin Dong’s laboratory at the University of Texas at Austin and the University of Chicago from 2015 to 2019. He began his independent academic career at Sichuan University in May 2019. His research interests focus on transition-metal-catalyzed reactions, in particular small-ring transformations and asymmetric catalysis.
The fluorine atom has the strongest electronegativity (4.0) and an atomic radius comparable to that of the hydrogen atom (F, 1.47 Å vs. H, 1.2 Å), which endows fluorine-containing compounds with unique chemical properties. Owing to these attributes, when a fluorine atom is introduced into an organic molecule, it changes a number of the interrelated structures and chemical features of the fluorine-containing compound.[1] In particular, in comparison with the common monofluoro substitution, gem-difluoro substitution leads to more significant changes in the properties of these compounds.[2] In the field of drug discovery, the lipid solubility and metabolic stability of fluorinated drug molecules are significantly improved relative to those of the original structures, resulting in a remarkable increase in the drug’s biological activity and selectivity.[3] For example, monofluoroalkenes are of great interest in biomedical science because they can be used as bioisosteres to mimic amides.[4]
As shown in Table [1], the benefit from the cumulative effect of the fluorine substitution in the alteration of the structural and thermodynamic properties of gem-difluoro-substituted cyclopropane is much bigger than that of monofluoro substitution.[3] [6] Because of these unique structural changes, gem-difluorinated cyclopropanes have higher reactivity than simple cyclopropane and monofluorocyclopropane.
Research related to the chemistry of fluorinated cyclopropanes dates back to 1952, when Atkinson first prepared hexafluorocyclopropane.[7] Shortly thereafter, Tarrant et al. accomplished the construction of 1,1-difluorocyclopropane from 1,3-dibromo-1,1-difluoro-2-methylbutane in 39% yield mediated by excess Zn, which was the first report on the synthesis of gem-difluorinated cyclopropane in history.[8] In 1960, when the first difluorocarbene precursor (sodium chlorodifluoroacetate) was discovered to be useful for the synthesis of a nearly infinite variety of fluorinated cyclopropanes, the research into fluorinated cyclopropanes moved to a higher level.[9] Nowadays, there are many synthetic methods to obtain gem-difluorinated cyclopropanes, all of which facilitate the exploration of their reactivities (Scheme [1]).[10]
The signature specialities of gem-difluorinated cyclopropanes have continually encouraged many chemists to explore their reaction potentials. The pioneering exploration of the reactivity of gem-difluorinated cyclopropanes via transition-metal catalysis was reported by Sakai’s group in 1983, in which they disclosed that gem-difluorinated cyclopropanes can undergo a ring-opening process to provide simple fluoro-olefins via palladium catalysis with H2.[11] It was not until 2015 that transition-metal-catalyzed reactions of gem-difluorinated cyclopropanes re-emerged, and the past several years in particular have witnessed rapid development of this chemistry. In this short review we will recap the studies related to the cross-coupling reactions of gem-difluorinated cyclopropanes catalyzed by transition metals during recent years. The investigation of gem-difluorinated cyclopropanes by other means, such as photocatalysis and organocatalysis, as well as non-catalytic transformations or studies on highly functionalized gem-difluorinated cyclopropanes are not within the scope of this review.[12]
# 2
Palladium-Catalyzed Reactions with Linear Selectivity
In the last few decades, the excellent properties of palladium catalysts have been gradually realized with the development of transition-metal catalysis.[13] Taking advantage of the powerful tool of palladium catalysis in cross-coupling reactions, Fu’s group made a very original contribution to the chemistry of gem-difluorinated cyclopropanes. They disclosed a palladium-catalyzed cross-coupling reaction of gem-difluorinated cyclopropanes with a series of nucleophilic reagents, including amines, alcohols, carboxylic acids, and some special carbon nucleophiles (Scheme [2]).[14] It was proposed that a fluoroallylic palladium species, generated through C–C bond oxidative addition and β-fluorine elimination, was the key intermediate that was trapped by the nucleophiles via allylic substitution. Under the catalytic system of palladium(II) trifluoroacetate (Pd(TFA)2) and t Bu-XPhos, the reaction yielded a range of highly cis-selective fluoroallyl amines, ethers, esters, and alkylated products in good yields. This study laid the foundation for the chemistry of gem-difluorinated cyclopropanes via transition-metal catalysis.
The same group later developed a Suzuki-type reaction between gem-difluorinated cyclopropanes and organoboronic acids. In this reaction, the proposed fluoroallylic palladium species would undergo transmetallation with the boronic acid, and the corresponding product could be delivered through reductive elimination (Scheme [3]).[15] The reaction showed good functional-group tolerance on both the gem-difluorinated cyclopropanes and the boronic acids. In addition, methylboronic acid and alkenylboronic acid were also competent substrates (leading to 3c and 3d, respectively) in this transformation with a combination of Pd-G3 and Q-Phos as the catalytic system.
After achieving C(sp3)–C(sp2) and C(sp3)–C(sp3) bond-forming coupling reactions of gem-difluorinated cyclopropanes under palladium catalysis, Gong and Fu’s group in 2020 reported the palladium-catalyzed cross-coupling reaction of gem-difluorinated cyclopropanes with terminal alkynes to form C(sp3)–C(sp) bonds (Scheme [4a]).[16] Similarly, it was proposed that the fluoroallylic palladium species would react with the terminal alkynes to form the skipped enyne products via reductive elimination. The scope of the alkyne partner in this transformation was very broad, which was demonstrated by the good performance of the silyl- (4a), alkyl- (4b), and aryl-substituted alkynes. Note that 1,1-disubstituted gem-difluorinated cyclopropane also worked well in this coupling to afford the fully substituted fluoro-olefin in good yield (4c). When aryl alkynes were employed as the coupling partner, fluorinated enynes or fluorinated phenanthrenes were selectively obtained by slightly modifying the reaction conditions (Scheme [4b]). The phenanthrene product could be formed via an intramolecular cyclization process of an enallene intermediate that is isomerized from the enyne product. This protocol can produce two types of structurally different fluorine-containing molecules from the same starting materials, which further demonstrates the potential of gem-difluorinated cyclopropanes in synthetic chemistry.
In addition to two-component reactions, Gong and Fu’s group subsequently developed a three-component reaction of gem-difluorinated cyclopropanes and alkynes with B2pin2 (bis(pinacolato)diboron) by using a copper/palladium dual-catalytic system, which realized the cis-difunctionalization of the alkyne with a boryl and a fluoroallyl group (Scheme [5]).[17] In this reaction, the copper catalyst is responsible for the formation of a borylalkenyl copper intermediate I from the alkyne and B2pin2 via a borylcupration process, while the palladium complex accounts for the generation of the fluorinated allylpalladium intermediate II from the gem-difluorinated cyclopropane via C–C and C–F bond activation. Similar to the previous two-component coupling reactions, transmetallation of the allylpalladium intermediate II with the in situ generated nucleophile (I) would occur to give intermediate III. This is followed by reductive elimination to produce the target product. Notably, terminal alkynes also worked well under the reaction conditions (5a).
Almost simultaneously, they reported another three-component reaction of gem-difluorinated cyclopropanes and olefins with B2pin2 (Scheme [6a]).[18] In this reaction, a similar borylcupration process occurs to generate a β-borylalkyl copper species, which serves as the nucleophile to participate in the palladium-catalyzed coupling process with the gem-difluorinated cyclopropane, resulting in difunctionalization of the olefin with a boryl and a fluoroallyl group. By oxidation of the boronate moiety, a variety of corresponding alcohol products were obtained in decent yields. Notably, a preliminary success in asymmetric catalysis was achieved by using a chiral copper–NHC complex, providing the product in 81% yield with 81:19 enantiomeric ratio after oxidation (Scheme [6b]).[18]
The rich chemistry of gem-difluorinated cyclopropanes catalyzed by palladium has attracted many research groups to explore the reactivity. In 2019, Zhang’s group developed a ring-opening sulfonylation of gem-difluorinated cyclopropanes by using Pd(TFA)2/X-Phos/K3PO4 as the catalytic system (Scheme [7]).[19] This reaction employs sodium aryl sulfinates as the nucleophiles to couple with the fluoroallyl palladium intermediate, which gives a wide range of fluoroallylic sulfones in good yields. The phase-transfer catalyst n Bu4NPF6 is important for this transformation because it enhances the solubility of the sodium aryl sulfites in DCE. The reaction showed good compatibility for sodium aryl sulfites, but CF3SO2Na did not work under these conditions.
In 2020, Lin and Guo’s group achieved a dearomative allylation of β-naphthols and indoles with gem-difluorinated cyclopropanes under the catalytic system of Pd/X-Phos/LiO t Bu (Scheme [8]).[20] The precatalyst [η3-C3H5PdCl]2 was used in the reaction of β-naphthols, whereas Pd(XantPhos)Cl2 worked better for indole nucleophiles. The nucleophilic attack of these electron-rich arenes on the fluoroallyl palladium species accounts for the formation of the dearomative allylated products. This reaction worked well for a wide range of gem-difluorinated cyclopropanes. The 1,1-disubstituted gem-difluorinated cyclopropane was also able to complete the above transformation (yielding 8a), whereas the 1,2-disubstituted one showed no reactivity. This reaction demonstrates the ability of gem-difluorinated cyclopropanes in the construction of all-carbon quaternary centers.
In 2021, Zhou, Liang, and Zhang’s group developed a palladium-catalyzed cross-coupling reaction of electron-deficient polyfluoroarenes with gem-difluorinated cyclopropanes (Scheme [9]).[21] In this reaction, the polyfluoroaromatic anion that is generated under basic conditions serves as the nucleophile to attack the allylpalladium intermediate, providing C–H allylation products in good yields with high Z selectivity. This transformation worked well with aryl gem-difluorinated cyclopropanes bearing either electron-donating (9a) or electron-absorbing substituents (9b), but alkyl-substituted substrates failed to afford the desired product. For fluoroarenes, penta- and tetrafluorobenzenes, as well as polyfluoropyridines (yielding 9c), were suitable substrates. However, the target product was not detected when 1,3-difluorobenzene was used as the substrate.
In the same year, Lian’s group developed a cross-coupling reaction of gem-difluorinated cyclopropanes with 2,2-difluorovinyl tosylate by using a dual-catalytic strategy of palladium and nickel (Scheme [10]).[22] In this reaction, it was proposed that nickel catalysis is responsible for the formation of a vinyl zinc reagent, which acts as the nucleophile to be trapped by the in situ formed fluorinated allyl palladium intermediate. This reaction provides a general approach for the synthesis of highly substituted skipped dienes, in which a monofluoroalkene and a gem-difluoroalkene motif are contained in the skeleton of the cross-coupling products.
Very recently, a palladium-catalyzed reaction of gem-difluorinated cyclopropanes with 2-alkynylanilines was disclosed by the group of Qi and Li (Scheme [11]).[23] With the catalytic system of Pd(allyl)Cl2/ t BuPPh2/K3PO4, the electrophilic fluorinated π-allyl palladium intermediate would activate the alkyne moiety of the 2-alkynylaniline substrate to trigger an indole cyclization. After regioselective reductive elimination, the 3-fluoroallyl indole would be produced with regeneration of the palladium catalyst. This reaction offers a practical protocol to introduce fluorine-containing groups into heteroarene molecules.
# 3
Palladium-Catalyzed Reactions with Branched Selectivity
As presented in Section 2, the cross-coupling reactions of gem-difluorinated cyclopropanes under palladium catalysis generally deliver β-fluoroalkenes via linear selectivity, in which the nucleophilic reagent is linked at the less substituted allylic position of the fluoroallyl palladium intermediate. In 2021, Lv and Li developed an elegant strategy to achieve branched selectivity in the palladium-catalyzed coupling reaction of gem-difluorinated cyclopropanes by using hydrazones as the nucleophiles (Scheme [12]).[24] In this work, it was proposed that a diaza-allyl intermediate is firstly formed from the hydrazone in the presence of the base, which reacts with the allylpalladium species to generate a bis(η1-allyl) palladium intermediate. Subsequent 3,3′-reductive elimination of this intermediate would produce a diazo compound, which undergoes deprotonation and N2 extrusion to deliver the target branched product. The use of hydrazones as the nucleophiles not only allows the occurrence of the 3,3′-reductive elimination but also provides the driving force to give the alkylated product via nitrogen extrusion, which is very important for branched selectivity. In addition, the sterically bulky NHC ligand was another key factor in the success of the branched selectivity by forming a sterically less congested bis(η1-allyl) palladium intermediate. The reaction works well for a wide range of substrates and provides a general route to introduce the α-fluoroalkene motif into organic molecules.
Soon after this, the strategy was further adopted by the group of Lv and Li to achieve the palladium-catalyzed branched selective coupling of gem-difluorinated cyclopropanes with simple ketones (Scheme [13]).[25] In this reaction, an oxo-bis(η1-allyl) palladium species was proposed as the key intermediate, which would undergo a similar inner-sphere 3,3′-reductive elimination to give the γ,δ-unsaturated ketone with branched selectivity. Again, the intrinsic ambident nucleophilic property of the enolate species and the bulky NHC ligand are crucial for the branched selectivity. It is worth mentioning that the coupling product can further undergo an intramolecular cyclization via a sequence of enolization, nucleophilic substitution, and aromatization to produce a polysubstituted furan when a less congested Pd-NHC complex is used. The reaction proceeded smoothly for a number of gem-difluorinated cyclopropanes, as well as aromatic and aliphatic ketones, including simple acetone (yielding 13b). For the scope of the furan products, aromatic ketones and aryl gem-difluorinated cyclopropanes proved to be viable substrates. However, alkyl-substituted gem-difluorinated cyclopropane did not afford the corresponding furan product (13f) but rather gave the corresponding ketone product (13c). Besides the excellent branched selectivity, this reaction also shows a good example on chemodivergent synthesis via ligand control.
After achieving branched-selectivity reactions of gem-difluorinated cyclopropanes with hydrazones and ketones that can generate diazo- and oxo-allyl species, respectively, the same group further explored the cross-coupling reaction between gem-difluorinated cyclopropanes and all-carbon allyl nucleophiles. Very recently, they reported a palladium-catalyzed regiodivergent cross-coupling reaction of gem-difluorinated cyclopropanes with allylboronates, providing a series of branched and linear fluorinated 1,5-dienes via a regiocontrollable 3,3′-reductive elimination process (Scheme [14]).[26] The selectivity of the reaction is determined by the different spatial and electronic properties of the NHC ligands, in which a less congested NHC ligand (IMes) favors the formation of linear products, whereas the use of a bulkier NHC ligand (IHept) is the key for branched selectivity. Calculations showed that an NHC ligand with larger neighboring substituents was more favorable for the generation of branched products during the reductive elimination process. As for the scope of the allyl nucleophile partner, the substitution mode of the allylboronate has a crucial influence on the reaction. Simple and 2-substituted allylboronates generally worked smoothly for both linear and branched selectivity, but 1- and 3-substituted allylboronates failed to give the desired products.
Almost simultaneously, Shi and Wang’s group disclosed a similar ligand-controlled strategy for the regiodivergent cross-coupling reaction between gem-difluorinated cyclopropanes and allylboronates (Scheme [15]).[27] In this reaction, the selectivity was elegantly controlled by the biaryl monophosphine ligand: a less bulky phosphine ligand (L2) favors linear selectivity, whereas a sterically hindered phosphine ligand (BrettPhos) can result in the formation of branched fluorinated 1,5-dienes as the major products. DFT calculations revealed that the steric hindrance of the phosphine ligand plays an important role in determining the configuration of the key bis(η1-allyl)palladium intermediates, which eventually deliver two types of fluorinated 1,5-dienes via inner-sphere 3,3′-reductive elimination. A wide range of linear and branched fluorinated 1,5-dienes were obtained in good yields with generally high selectivities under this regiodivergent catalytic system.
# 4
Other Metal-Catalyzed Reactions
Despite the extraordinary catalytic features of palladium, there are still limited reports of other metal-catalyzed reactions of gem-difluorinated cyclopropanes. In 2016, Gade’s team achieved a ring-opening reaction of gem-difluorinated cyclopropanes catalyzed by a nickel complex to obtain the corresponding fluorinated olefins in good yields and high cis selectivity (Scheme [16]).[28] In this reaction, [Ni(II)F] 16aF or 16bF was used as the precatalyst, which can form the corresponding Ni(II)-hydride species 16aH or 16bH in the presence of Me2NHBH3. 16aH or 16bH was in equilibrium with the Ni(I) species 16a or 16b, which was supported by a series of mechanistic studies to serve as the real catalyst that activates the gem-difluorinated cyclopropane. In the proposed mechanism, the nickel(I) species would activate the C–F bond in the gem-difluorinated cyclopropane to form a fluoroallyl radical intermediate via homolytic C–F bond cleavage, which then seizes hydrogen from the [Ni(II)H] complex (16aH or 16bH ) to afford the corresponding fluorinated olefin. This method was compatible with many gem-difluorinated cyclopropanes, including α-disubstituted substrate (16c). This nickel-catalyzed protocol offers a new strategy to activate the gem-difluorinated cyclopropanes, and novel transformations using this tactic are expected.
Very recently, another first-row transition metal, cobalt, has been utilized in the coupling of gem-difluorinated cyclopropanes with electrophilic aldehydes to provide fluorinated homoallylic alcohols with moderate to good E/Z selectivities by Yu and co-workers (Scheme [17]).[29] This reaction is initiated by the formation of a Co(I) species from the reduction of Co(II) by Zn. The Co(I) species then reacts with the gem-difluorinated cyclopropane to form a π-allylcobalt(III) intermediate via a sequence of C–C oxidative addition and β–F elimination. The electrophilic π-allylcobalt(III) intermediate is then reduced by Zn to give a nucleophilic π-allylcobalt(I) species, which undergoes nucleophilic addition on the aldehyde to generate the product. The reaction can tolerate both aliphatic (17a) and aromatic (17b, 17c) aldehydes. The use of a vinyl-substituted gem-difluorinated cyclopropane as the substrate can give a fluorinated dienyl alcohol (17c) in decent yield. This reaction demonstrates that gem-difluorinated cyclopropanes can also serve as nucleophilic allyl surrogates, which therefore may open up new possibilities for the application of this type of molecule in organic synthesis.
Our group has also contributed to the reaction diversity of this fascinating molecule. In 2021, we disclosed a rhodium-catalyzed cross-coupling reaction between gem-difluorinated cyclopropanes and simple arenes (Scheme [18]).[30] The arene C–H allylation products were obtained in high yields and excellent regioselectivity under the catalytic system of [Rh(CO)2Cl]2/rac-BINAP/AgBF4. Mechanistically, the gem-difluorinated cyclopropane undergoes a sequence of oxidative addition and β-F elimination to generate a cationic fluoroallyl rhodium species, which is supposed to be highly electrophilic and can trigger C–H activation of the simple arene via an electrophilic metallation process. The generated aryl–Rh–allyl species undergoes reductive elimination to deliver the allylation product. In addition to aryl gem-difluorinated cyclopropanes, alkyl- (18c) and alkenyl- (18d) substituted ones also gave the corresponding products in good yields and selectivity. As for the scope of the arenes, both electron-rich (18e) and electron-deficient (18f) substituted aromatics react well, with the latter requiring an elevated reaction temperature or increased catalyst loading. It is worth mentioning that preliminary success in ligand-controlled linear/branched selectivity has been achieved by using phenol as a coupling partner. Such results, along with the tolerance of electron-withdrawing arenes, suggest that a typical Friedel–Crafts allylation mechanism can be ruled out.[31]
Just recently, our group realized a site-divergent fluoroallylation of simple olefins with gem-difluorinated cyclopropanes, which can produce two types of fluorinated 1,4-dienes in good yields with excellent selectivities (Scheme [19]).[32] The reaction involves a sequence of formation of the fluoroallyl rhodium(III) species, olefin migratory insertion, and β-hydride elimination. The site-divergent selectivity can be controlled by modulating the electronic properties of the rhodium catalyst: a neutral rhodium catalytic system favors α-selectivity, and a cationic rhodium system would form fluorinated 1,4-dienes with almost exclusive β-selectivity. In addition, the use of a sterically congested pyridine and B(OH)3 as additives in the neutral rhodium catalytic system can further increase the α-selectivity to a ratio of about 50:1. DFT calculations by Lu’s group disclosed that the olefin migratory insertion is the regio-determining step. In a neutral Rh system, the Rh atom would locate at the sterically less crowded position during the migratory insertion step via steric-effect control, resulting in the formation of the α-selective product. By comparison, the migratory insertion would favor the formation of a more stable benzyl rhodium species (R2 is generally an aryl group) via electronic-effect control when a cationic Rh catalytic system is employed. This work unveils how steric and electronic properties of the metal complex can affect the site selectivity, which might provide inspiration for tuning the selectivity in transition-metal-catalyzed reactions.
# 5
Conclusions
In the past few years, significant progress has been achieved in the transition-metal-catalyzed cross-coupling reaction of gem-difluorinated cyclopropanes, in which the fluoroallyl metal species is the key intermediate in these transformations. The transition-metal catalysts currently used in this chemistry are still dominated by Pd, and there are only limited reports about other metals such as Ni, Co, and Rh. In terms of the molecular structure, the products are generally monofluorinated olefins owing to β-F elimination, and strategies that can retain the CF2 moiety during the reaction of gem-difluorinated cyclopropanes are highly anticipated.[12h] In addition, a chiral carbon center is generated in the branched products; thus, the development of asymmetric catalysis to construct enantioenriched fluorine-containing molecules would be a promising direction. In conclusion, as an important class of fluorinated three-carbon synthon, gem-difluorinated cyclopropanes have just shown development momentum. More explorations on new reaction models as well as applications in synthetic and medicinal chemistry are expected in the future via transition-metal catalysis.
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Conflict of Interest
The authors declare no conflict of interest.
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- 32 Zeng Y, Gao H, Zhu Y, Jiang Z.-T, Lu G, Xia Y. ACS Catal. 2022; 12: 8857
Corresponding Author
Publication History
Received: 24 June 2022
Accepted after revision: 28 July 2022
Accepted Manuscript online:
28 July 2022
Article published online:
21 September 2022
© 2022. Thieme. All rights reserved
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Yaxin Zeng (second from left) received his B.E. degree from Sichuan Agricultural University in 2018. He obtained his Master’s degree in 2022 from Sichuan University under the supervision of Professor Ying Xia. He is currently a Ph.D. candidate at Sichuan University.
Zhong-Tao Jiang (second from right) received his B.S. degree from Sichuan Normal University in 2014. He obtained his Master’s degree in 2018 from Sichuan Normal University under the supervision of Professor Bi-Qin Wang and joined Professor Ying Xia’s group in 2019. He is currently a Ph.D. candidate at Sichuan University.
Ying Xia (first from right) was born in 1987 in Yueyang, Hunan Province. He received his B.Eng. degree from Beijing Institute of Technology in 2010 and completed his Ph.D. degree in organic chemistry at Peking University under the supervision of Professor Jianbo Wang and Yan Zhang. He was a postdoctoral fellow in Professor Guangbin Dong’s laboratory at the University of Texas at Austin and the University of Chicago from 2015 to 2019. He began his independent academic career at Sichuan University in May 2019. His research interests focus on transition-metal-catalyzed reactions, in particular small-ring transformations and asymmetric catalysis.
