R&D｜Nature Catalysis 近期报道
引言
1
Gold-catalysed asymmetric net addition of unactivated propargylic C–H bonds to tethered aldehydes
Ting Li,
Xinpeng Cheng,
Pengcheng Qian &
Liming Zhang
Nature Catalysis volume 4, pages164–171 (2021)Cite this article
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Abstract
The asymmetric one-step net addition of unactivated propargylic C–H bonds to aldehydes leads to an atom-economic construction of versatile chiral homopropargylic alcohols, but has not yet been realized. Here we show its implementation in an intramolecular manner under mild reaction conditions. This chemistry—via cooperative gold catalysis enabled by a chiral bifunctional phosphine ligand—achieves asymmetric catalytic deprotonation of propargylic C–H (pKa > 30) by a tertiary amine group (pKa ≈ 10) of the ligand in the presence of much more acidic aldehydic α-hydrogens (pKa ≈ 17). The reaction exhibits a broad scope and readily accommodates various functional groups. The cyclopentane/cyclohexane-fused homopropargylic alcohol products are formed with excellent enantiomeric excesses and high trans-selectivities with or without a preexisting substrate chiral centre. Density functional theory studies of the reaction support the conceived reaction mechanism and the calculated energetics corroborate the observed stereoselectivity and confirm additional metal–ligand cooperation
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Mechanistic investigation of Rh(I)-catalysed asymmetric Suzuki–Miyaura coupling with racemic allyl halides
Lucy van Dijk,
Ruchuta Ardkhean,
Mireia Sidera,
Sedef Karabiyikoglu,
Özlem Sari,
Timothy D. W. Claridge,
Guy C. Lloyd-Jones,
Robert S. Paton &
Stephen P. Fletcher
Nature Catalysis volume 4, pages284–292 (2021)Cite this article
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Abstract
Understanding how catalytic asymmetric reactions with racemic starting materials can operate would enable new enantioselective cross-coupling reactions that give chiral products. Here we propose a catalytic cycle for the highly enantioselective Rh(I)-catalysed Suzuki–Miyaura coupling of boronic acids and racemic allyl halides. Natural abundance 13C kinetic isotope effects provide quantitative information about the transition-state structures of two key elementary steps in the catalytic cycle, transmetallation and oxidative addition. Experiments with configurationally stable, deuterium-labelled substrates revealed that oxidative addition can happen via syn- or anti-pathways, which control diastereoselectivity. Density functional theory calculations attribute the extremely high enantioselectivity to reductive elimination from a common Rh complex formed from both allyl halide enantiomers. Our conclusions are supported by analysis of the reaction kinetics. These insights into the sequence of bond-forming steps and their transition-state structures will contribute to our understanding of asymmetric Rh–allyl chemistry and enable the discovery and application of asymmetric reactions with racemic substrates.
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Regioirregular and catalytic Mizoroki–Heck reactions
Francisco Garnes-Portolés,
Rossella Greco,
Judit Oliver-Meseguer,
Jorge Castellanos-Soriano,
M. Consuelo Jiménez,
Miguel López-Haro,
Juan Carlos Hernández-Garrido,
Mercedes Boronat,
Raúl Pérez-Ruiz &
Antonio Leyva-Pérez
Nature Catalysis volume 4, pages293–303 (2021)Cite this article
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Abstract
The palladium-catalysed cross-coupling reaction between alkenes and aryl halides (the Mizoroki–Heck reaction) is a powerful methodology to construct new carbon–carbon bonds. However, the success of this reaction is in part hampered by an extremely marked regioselectivity on the double bond, which dictates that electron-poor alkenes react exclusively on the β-carbon. Here, we show that ligand-free, few-atom palladium clusters in solution catalyse the α-selective intramolecular Mizoroki–Heck coupling of iodoaryl cinnamates, and mechanistic studies support the formation of a sterically encumbered cinnamate–palladium cluster intermediate. Following this rationale, the α-selective intermolecular coupling of aryl iodides with styrenes is also achieved with palladium clusters encapsulated within fine-tuned and sterically restricted zeolite cavities to produce 1,1-bisarylethylenes, which are further engaged with aryl halides by a metal-free photoredox-catalysed coupling. These ligand-free methodologies significantly expand the chemical space of the Mizoroki–Heck coupling.
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Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis
Tao Ju,
Yu-Qin Zhou,
Ke-Gong Cao,
Qiang Fu,
Jian-Heng Ye,
Guo-Quan Sun,
Xiao-Feng Liu,
Li Chen,
Li-Li Liao &
Da-Gang Yu
Nature Catalysis volume 4, pages304–311 (2021)Cite this article
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Abstract
Light-driven utilization of CO2 in organic synthesis is highly attractive because it mimics nature. However, such transformations are mainly limited to the incorporation of only a single CO2 molecule into organic compounds, far less than the number of CO2 molecules fixed in the product in photosynthesis. Here we report the visible-light photoredox-catalysed dicarboxylation of alkenes, allenes and (hetero)arenes with the incorporation of two CO2 molecules. This method realizes the formation of multiple C–C bonds with high chemo- and diastereoselectivities under mild conditions, which represents a simple, rapid and sustainable approach to valuable dicarboxylic acids. Moreover, this transition-metal-free protocol exhibits a low catalyst loading, good functional group tolerance, broad substrate scope, facile scalability and easy product derivatizations to give drug and material molecules. Mechanistic studies indicate a pathway by which a visible-light-induced two-electron reduction via sequential single electron transfer generates radical anions of such unsaturated substrates, broadening the repertoire of strategies.
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Metal–support cooperation in Al(PO3)3-supported platinum nanoparticles for the selective hydrogenolysis of phenols to arenes
Xiongjie Jin,
Rio Tsukimura,
Takeshi Aihara,
Hiroki Miura,
Tetsuya Shishido &
Kyoko Nozaki
Nature Catalysis volume 4, pages312–321 (2021)Cite this article
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Abstract
The hydrogenolysis of phenols to yield arenes is of importance to the production of fine chemicals, as well as biorefinery application; however, the conversion of phenols through cleavage of their strong C(sp2)–OH bonds remains a highly challenging task in synthetic chemistry. Here we report the use of Al(PO3)3-supported platinum nanoparticles for the selective hydrogenolysis of a broad range of phenols (including sterically highly demanding phenols and lignin model compounds) to afford arenes under relatively low temperatures (<150 °C) and ambient pressure (Ar/H2 = 9/1, 1 atm). This heterogeneous catalyst is expected to find a broad application in fine chemical synthesis and biorefinery.
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Development of a versatile and efficient C–N lyase platform for asymmetric hydroamination via computational enzyme redesign
Yinglu Cui,
Yinghui Wang,
Wenya Tian,
Yifan Bu,
Tao Li,
Xuexian Cui,
Tong Zhu,
Ruifeng Li &
Bian Wu
Nature Catalysis volume 4, pages364–373 (2021)Cite this article
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Abstract
Although C–N bonds are ubiquitous in natural products, pharmaceuticals and agrochemicals, biocatalysts forging these bonds with high atom-efficiency and enantioselectivity have been limited to a few select enzymes. In particular, ammonia lyases have emerged as powerful catalysts to access C–N bond formation via hydroamination. However, the use of ammonia lyases is rather restricted due to their narrow synthetic scope. Herein, we report the computational redesign of aspartase, a highly specific ammonia lyase, to yield C–N lyases with cross-compatibility of non-native nucleophiles and electrophiles. A wide range of non-canonical amino acids (ncAAs) are afforded with excellent conversion (up to 99%), regioselectivity >99% and enantioselectivity >99%. The process is scalable under industrially relevant protocols (exemplified in kilogram-scale synthesis) and can be facilely integrated in cascade reactions (demonstrated in the synthesis of β-lactams with N-1 and C-4 substitutions). This versatile and efficient C–N lyase platform supports the preparation of ncAAs and their derivatives, and will present opportunities in synthetic biology.
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Programmable late-stage C−H bond functionalization enabled by integration of enzymes with chemocatalysis
Elliott J. Craven,
Jonathan Latham,
Sarah A. Shepherd,
Imtiaz Khan,
Alba Diaz-Rodriguez,
Michael F. Greaney &
Jason Micklefield
Nature Catalysis volume 4, pages385–394 (2021)Cite this article
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Abstract
New chemo- and biocatalytic methodology is important for the future sustainable synthesis of essential molecules. Transition metal catalysis enables the late-stage C−H functionalization of some complex molecular scaffolds, providing rapid routes to valuable products, although this is largely dependent on the availability of electronically or sterically predisposed C−H bonds for selective metalation, leaving certain regioselectivities inaccessible. Unlike metal chemocatalysis, enzymes can catalyse C−H bond functionalization, discriminating between near-identical, non-activated C−H bonds, delivering products with exquisite regioselectivity. However, enzymes typically provide access to fewer functionalities than more divergent chemocatalysis. Here we report programmable, regioselective C−H bond functionalization methodologies for the installation of versatile nitrile, amide and carboxylic acid moieties through integration of halogenase enzymes with palladium-catalysed cyanation and subsequent incorporation of nitrile hydratase or nitrilase enzymes. Using two- or three-component chemobiocatalytic systems, the regioselective synthesis of complex target molecules, including pharmaceuticals, can be achieved in a one-pot process operable on a gram scale.
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Catalyst control over sixfold stereogenicity
Xingxing Wu,
Reto M. Witzig,
Rodolphe Beaud,
Christian Fischer,
Daniel Häussinger &
Christof Sparr
Nature Catalysis volume 4, pages457–462 (2021)Cite this article
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A Publisher Correction to this article was published on 03 June 2021
This article has been updated
Abstract
Achieving control over higher-order stereogenicity is a long-standing goal in stereoselective catalysis to deliberately address more than a twofold number of stereoisomers per stereogenic unit. Current methods allow control over 2n stereoisomers and their configurations are routinely assigned using the descriptors (R) and (S) or related binary codes. In contrast, conformational analysis extends beyond this dualistic treatment of stereoisomerism, which constitutes an unmet challenge for catalyst stereocontrol. Here, we report that sixfold stereogenicity is tractable by stereoselective catalysis. By controlling a configurationally stable stereogenic axis with six large rotational barriers, a catalytic [2 + 2 + 2] cyclotrimerization selectively governs the formation of one of six stereoisomers with up to 0:0:2:98:0:0 stereocontrol. Moreover, the stereoselectivity is redirectable by stereodivergent catalysis, providing four of the six stereoisomers as major stereoisomers. The underpinnings of conformational analysis and stereoselective catalysis are thereby conceptually reunited. Novel molecular architectures featuring distinct chemical topologies and unexplored chemical designs are anticipated from catalyst control over higher-order stereogenicity
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Engineering yeast metabolism for the discovery and production of polyamines and polyamine analogues
Jiufu Qin,
Anastasia Krivoruchko,
Boyang Ji,
Yu Chen,
Mette Kristensen,
Emre Özdemir,
Jay D. Keasling,
Michael Krogh Jensen &
Jens Nielsen
Nature Catalysis volume 4, pages498–509 (2021)Cite this article
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Abstract
Structurally complex and diverse polyamines and polyamine analogues are potential therapeutics and agrochemicals that can address grand societal challenges, for example, healthy ageing and sustainable food production. However, their structural complexity and low abundance in nature hampers either bulk chemical synthesis or extraction from natural resources. Here we reprogrammed the metabolism of baker’s yeast Saccharomyces cerevisiae and recruited nature’s diverse reservoir of biochemical tools to enable a complete biosynthesis of multiple polyamines and polyamine analogues. Specifically, we adopted a systematic engineering strategy to enable gram-per-litre-scale titres of spermidine, a central metabolite in polyamine metabolism. To demonstrate the potential of our polyamine platform, various polyamine synthases and ATP-dependent amide-bond-forming systems were introduced for the biosynthesis of natural and unnatural polyamine analogues. The yeast platform serves as a resource to accelerate the discovery and production of polyamines and polyamine analogues, and thereby unlocks this chemical space for further pharmacological and insecticidal studies.
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A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion
Jie Zhao,
Shufang Ji,
Chenxi Guo,
Haijing Li,
Juncai Dong,
Ping Guo,
Dingsheng Wang,
Yadong Li &
F. Dean Toste
Nature Catalysis volume 4, pages523–531 (2021)Cite this article
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Abstract
Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C–O bonds. Achieving site-selective functionalization of alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report a strategy for selective carbenoid O–H insertion that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities for organic transformations by merging material science and catalysis. This catalytic protocol delivers excellent selectivities (up to 99:1) for the functionalization of aliphatic over phenolic O–H bonds, whereas the analogous homogeneous catalyst, Ir(ttp)COCl (ttp = 5,10,15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest that the site-selectivity derives from the lower oxidation state of the iridium metal centre in the heterogeneous catalyst and its impact on the absorption energies of the reactants. These results showcase an example of a heterogeneous single-atom catalyst providing superior site-selectivity and provide a complementary strategy to address challenges in catalysis for organic synthesis.
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DYW domain structures imply an unusual regulation principle in plant organellar RNA editing catalysis
Mizuki Takenaka,
Sachi Takenaka,
Tatjana Barthel,
Brody Frink,
Sascha Haag,
Daniil Verbitskiy,
Bastian Oldenkott,
Mareike Schallenberg-Rüdinger,
Christian G. Feiler,
Manfred S. Weiss,
Gottfried J. Palm &
Gert Weber
Nature Catalysis volume 4, pages510–522 (2021)Cite this article
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Abstract
RNA editosomes selectively deaminate cytidines to uridines in plant organellar transcripts—mostly to restore protein functionality and consequently facilitate mitochondrial and chloroplast function. The RNA editosomal pentatricopeptide repeat proteins serve target RNA recognition, whereas the intensively studied DYW domain elicits catalysis. Here we present structures and functional data of a DYW domain in an inactive ground state and activated. DYW domains harbour a cytidine deaminase fold and a C-terminal DYW motif, with catalytic and structural zinc atoms, respectively. A conserved gating domain within the deaminase fold regulates the active site sterically and mechanistically in a process that we termed gated zinc shutter. Based on the structures, an autoinhibited ground state and its activation are cross-validated by RNA editing assays and differential scanning fluorimetry. We anticipate that, in vivo, the framework of an active plant RNA editosome triggers the release of DYW autoinhibition to ensure a controlled and coordinated cytidine deamination playing a key role in mitochondrial and chloroplast homeostasis.
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Selective electrocatalytic semihydrogenation of acetylene impurities for the production of polymer-grade ethylene
Jun Bu,
Zhenpeng Liu,
Wenxiu Ma,
Lei Zhang,
Tao Wang,
Hepeng Zhang,
Qiuyu Zhang,
Xinliang Feng &
Jian Zhang
Nature Catalysis volume 4, pages557–564 (2021)Cite this article
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The current thermocatalytic acetylene hydrogenation process suffers from the use of excessive hydrogen and the noble metal Pd, high temperatures and overhydrogenation. Here we report an electrocatalytic semihydrogenation strategy to selectively reduce acetylene impurities to ethylene under ambient conditions. For a crude ethylene flow that contains 1 × 104 ppm acetylene, electrochemically deposited Cu dendrites exhibited a high specific selectivity of 97%, continuous production of a polymer-grade ethylene stream (4 ppm acetylene) at a large space velocity of 9.6 × 104 ml gcat–1 h–1 and excellent long-term stability. Theoretical and operando electrochemical Raman investigations revealed that the outstanding electrocatalytic acetylene semihydrogenation performance of Cu catalysts originates from its exothermic acetylene adsorption and ethylene desorption. Meanwhile, the electrocatalytic semihydrogenation strategy is universally applicable for hydrogenating other alkyne impurities to produce polymer-grade olefins, for example, propylene and 1,3-butadiene.
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Stereodefined rhodium-catalysed 1,4-H/D delivery for modular syntheses and deuterium integration
Weiyi Wang,
Yibo Yu,
Bao Cheng,
Huayi Fang,
Xue Zhang,
Hui Qian &
Shengming Ma
Nature Catalysis volume 4, pages586–594 (2021)Cite this article
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Deuterium-incorporated compounds are of high interest owing to their importance in the pharmaceutical industry, organic synthesis and materials science. So far, the integration of deuterium into the inert, saturated magic methyl or methylene groups of covalent molecules remains challenging. Here, we present a 1,4-H delivery of allylic metallic species to provide a highly stereoselective and straightforward approach to 3-methyl-2(E)-enals or -enones from readily available 2,3-allenols and organoboronic acids. The reaction accommodates many synthetically versatile functional groups as well as multi-pharmacophores, and is not limited to the formation of 3-methyl derivatives. By applying 1,4-H or D delivery, deuterium atom(s) from differently deuterated allenols can be edited into the methyl or methylene groups of versatile organic skeletons, resulting in the efficient formation of 4-monodeuterated, 1,4- and 4,4-doubly deuterated, and 4,4,4-triply deuterated 2(E)-enals or -enones. These powerful platform molecules can provide straightforward paths to other deuterated compounds for different purposes.
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Copper-catalysed amination of alkyl iodides enabled by halogen-atom transfer
Bartosz Górski,
Anne-Laure Barthelemy,
James J. Douglas,
Fabio Juliá &
Daniele Leonori
Nature Catalysis volume 4, pages623–630 (2021)Cite this article
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Despite the fact that nucleophilic displacement (SN2) of alkyl halides with nitrogen nucleophiles is one of the first reactions introduced in organic chemistry teaching, its practical utilization is largely limited to unhindered (primary) or activated (α-carbonyl, benzylic) substrates. Here, we demonstrate an alternative amination strategy where alkyl iodides are used as radical precursors instead of electrophiles. Use of α-aminoalkyl radicals enables the efficient conversion of the iodides into the corresponding alkyl radical by halogen-atom transfer, while copper catalysis assembles the sp3 C–N bonds at room temperature. The process provides SN2-like programmability, and application in late-stage functionalization of several densely functionalized pharmaceuticals demonstrates its utility in the preparation of valuable N-alkylated drug analogues.
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Iron-catalysed regioselective thienyl C–H/C–H coupling
Takahiro Doba,
Laurean Ilies,
Wataru Sato,
Rui Shang &
Eiichi Nakamura
Nature Catalysis volume 4, pages631–638 (2021)Cite this article
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Regioselective thienyl–thienyl coupling is arguably one of the most important transformations for organic electronic materials. A prototype of ideal organic synthesis to couple two thienyl groups by cutting two C–H bonds requires formal removal of two hydrogen atoms with an oxidant, which often limits the synthetic efficiency and versatility for oxidation-sensitive substrates (for example, donor and hole-transporting materials). Here, we found that diethyl oxalate, used together with AlMe3, acts as a two-electron acceptor in an iron-catalysed C–H activation. We describe the regioselective thienyl C–H/C–H coupling with an iron(III) catalyst, a trisphosphine ligand, AlMe3 and diethyl oxalate under mild conditions. The efficient catalytic system accelerated by ligand optimization polymerizes thiophene-containing monomers into homo- and copolymers bearing a variety of electron-donative π motifs. The findings suggest the versatility of iron catalysis for the synthesis of functional polymers, for which the potential of this ubiquitous metal has so far not been fully appreciated.