
==== Front
Nat Commun
Nat Commun
Nature Communications
2041-1723
Nature Publishing Group UK London

52248
10.1038/s41467-024-52248-y
Article
Asymmetric paired oxidative and reductive catalysis enables enantioselective alkylarylation of olefins with C(sp3)−H bonds
Zou Long 1
Zheng Xinyue 1
Yi XueZheng 1
http://orcid.org/0000-0002-2852-3220
Lu Qingquan gci2011@whu.edu.cn

12
1 https://ror.org/033vjfk17 grid.49470.3e 0000 0001 2331 6153 The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei 430072 P. R. China
2 grid.49470.3e 0000 0001 2331 6153 Wuhan University Shenzhen Research Institute, Shenzhen, 518000 P. R. China
7 9 2024
7 9 2024
2024
15 782615 5 2024
28 8 2024
© The Author(s) 2024
2024
https://creativecommons.org/licenses/by-nc-nd/4.0/ Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.
Enantioselective transformations of hydrocarbons to three-dimensional chiral molecules remain a significant challenge in synthetic chemistry. This study uses asymmetric paired oxidative and reductive catalysis to promote the enantioselective alkylarylation of olefins through the functionalization of C(sp3)−H bonds in alkanes. This asymmetric photoelectrocatalytic approach enables the facile construction of a wide range of enantioenriched α-aryl carbonyls with excellent enantioselectivity (up to 96% ee) from readily accessible starting materials. Notably, aryl bromides, aryl iodides, and even aryl chlorides were compatible with the developed catalytic system. Mechanistic studies reveal that alkanes and electrophiles are simultaneously activated on the electrodes.

The pursuit of methods to rapidly construct of molecular complexity from easy-to-obtain starting materials drives chemical synthesis. Here, the authors report an asymmetric three-component coupling of simple alkanes, alkenes, and aryl halides, using asymmetric paired oxidative and reductive catalysis.

Subject terms

Synthetic chemistry methodology
Electrochemistry
https://doi.org/10.13039/501100001809 National Natural Science Foundation of China (National Science Foundation of China) 22271227 Lu Qingquan Guangdong Basic and Applied Basic Research Foundation (2024A1515011322) Fundamental Research Funds for the Central Universities (2042024kf1040) National Key R&D Program of China (2021YFA1500100)issue-copyright-statement© Springer Nature Limited 2024
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pmcIntroduction

Photoelectrochemistry has been harnessed for diverse transformations ever since Xu and co-workers reported the photoelectrochemical C − H alkylation of heteroarenes with organotrifluoroborates in 20191–5. However, the inherently energetic and reactive intermediates (e.g., radicals and radical ions) generated during electrolysis make it challenging to ensure enantioselective control6–10. Moreover, it is difficult to maintain compatibility between the photocatalytic, electrocatalytic, and asymmetric catalytic systems in a single cell. As a result, reports of asymmetric photoelectrocatalysis are scarce11–17. In 2022, the Xu group and the Liu group independently established photoelectrochemical asymmetric catalysis by merging electrophoto- and copper catalysis16,17, which enabled enantioselective cyanation of benzylic C–H bonds, decarboxylative cyanation, and heteroarylcyanation of alkenes11,12,14–17. More recently, Meggers et al. developed a photoelectrochemical asymmetric dehydrogenative [2 + 2] cycloaddition reaction involving cooperation between a chiral rhodium catalyst and ferrocene13. These systems all used single half-electrode reactions, where H2 evolution at the cathode was required to ensure electroneutrality (Fig. 1a). Merging asymmetric paired electrocatalysis with photochemistry should enhance the synthetic utility of such systems by promoting energy efficiency and atom economy, while stimulating further development of asymmetric synthesis18–20.Fig. 1 Introduction.

Asymmetric photoelectrocatalysis enabled C(sp3)−H functionalization. a Single half-electrode reaction. b Asymmetric paired oxidative and reductive catalysis.

Catalytic multicomponent reactions (MCRs) represent a versatile and powerful strategy for assembling complex molecular motifs from readily accessible materials via a single operation, thereby providing elegant retrosynthetic strategies to access natural products, drugs, and functionalized polymers21–23. In particular, radical-based catalytic multicomponent reactions exhibit complementary reactivity and selectivity patterns compared with classical two-electron multicomponent reactions24–27, which has highlighted new synthetic opportunities. However, the exceptionally high reactivity of radical species is notoriously difficult to handle in enantioselective processes, and therefore, catalytic asymmetric radical multicomponent reactions still remain underexploited28–30. To date, the limited examples of enantioselective three-component dicarbofunctionalization of alkenes typically rely on pre-functionalized alkylmetal or organohalide feedstocks31–48, which leads to poor atom and step economies. In contrast, facile direct functionalization of ubiquitous C(sp3)−H bonds in inert hydrocarbons (e.g., alkanes) is an ambitious goal in synthetic chemistry that would revolutionize the field49–53.

To date, the direct use of abundant alkanes as sp3-hybridized carbon radical precursors that could participate in the catalytic enantioselective functionalization of alkenes remains elusive54, likely because of the following challenges: (1) the nonpolar alkyl C − H bonds in alkanes have high bond-dissociation energies, and harsh conditions are often required under thermal conditions55; (2) a highly electrophilic radicals is needed to activate alkanes, but the target reactivity is in competition with undesired side reactions; (3) the carbon-centered radicals generated in situ are prone to oxidation to carbocations under oxidative conditions resulting in compromised enantio- and chemo-selectivity; (4) competition between two-component and three-component reactions reduces selectivity, and rate-matching is vital for high reaction selectivity.

Owing to our on-going interest in electrosynthesis56–64, herein, we present the photoelectrochemical alkylarylation of olefins via C(sp3)−H functionalization of alkanes to afford chiral α-aryl carbonyls with good to excellent enantioselectivity. Anodic photoelectrocatalysis is utilized to activate alkanes through ligand-to-metal charge transfer (LMCT), resulting in the production of alkyl radicals, while cathodic transition metal catalysis is employed to activate aryl halides, yielding the corresponding aryl-NiII species. The cross-coupling of the two half-electrode reactions with an olefin as a linkage enables enantioselective three-component reactions (Fig. 1b). The key features of this approach include the following: (1) abundantly available alkanes are used as alkylating reactants to generate valuable chiral molecules; (2) the photocatalytic and electrocatalytic processes remain relatively independent and can be modulated individually by adjusting the light source and the current/electrode potential, thus ensuring rate-matching paired electrocatalysis; (3) An ultra-low oxidative potential is required for recycling Fe2+ to Fe3+ 56,57, which enables mild redox-neutral electrosynthesis, suppresses undesirable over-oxidation, and promotes reaction selectivity.

Results and discussion

Investigation of the reaction conditions

To explore the feasibility of the proposed system, photoelectrochemically-driven three-component reactions involving cyclohexane (1a), 4’-bromoacetophenone (2a), and tert-butyl acrylate (3a) were carried out in the presence of commercially available FeCl3 and Ni(NO3)2•6H2O under irradiation with purple light emitting diodes (LEDs). As shown in Table 1, extensive experimentation and evaluation of key parameters (e.g., catalyst, solvent, electrolyte, current density, light source, ligand) revealed that the desired product 1 could be isolated in 82% yield with 91% ee (entry 1). Low yields of the desired product were detected when Ni(NO3)2•6H2O was replaced with other Ni(II) precatalysts containing different counterions (entries 2-3) because of their poor solubility in acetone, whereas changing the anodic catalyst (entries 4-5) reduced reaction efficiency. The solvent and electrolyte played key roles in promoting the reaction efficiency. For example, the reaction efficiency decreased dramatically when acetonitrile, which could serve as a hydrogen atom donor and take part in undesired radical reaction, or a chlorine-free electrolyte was employed (entries 6-7). As expected, rate-matching between the anodic and cathodic reactions was crucial for this transformation. The tuning of the light source and current intensity, which influenced the anodic and cathodic reaction rates, significantly impacted the reaction efficiency and enantioselectivity (entries 8-10). Chiral biimidazoline (BiIm) ligands were the optimal ligands because they afforded the desired product in good yield with excellent enantioselectivity (entry 11). Notably, the electronic nature of the BiIm ligands had a dramatic effect on the reaction efficiency and enantioselectivity, such that more electron-rich BiIm ligands gave better results (entry 1 vs 11). In contrast, chiral bioxazoline (Biox) ligand, pyridine oxazoline ligand and chiral oxazoline ligand led to lower enantioselectivities and yields (entry 11; additional details are provided in the Supplementary Information, Table 1). Control experiments indicated that paired catalysts, purple light, and the electrical current are all essential because reactions performed in their absence provided poor results (entries 12-13).Table 1 Optimization of the reaction conditions[a]

	
Entry	Variation from standard conditions	Yield (%)[b]	ee (%)[b]	
1	none	82	91	
2	NiCl2 instead of Ni(NO3)2•6H2O	52	90	
3	NiBr2 instead of Ni(NO3)2•6H2O	47	89	
4	CuCl2 instead of FeCl3	7	90	
5	CeCl3 instead of FeCl3	n.d.	--	
6	MeCN instead of Acetone	61	82	
7	nBu4NPF6 instead of LiCl	7	90	
8	I = 10 mA	57	83	
9	10 W 390–392 nm	55	90	
10	20 W 395–400 nm	70	88	
11	L2 − L8 instead of L1	7–81	7–80	
12	w/o FeCl3 or Ni(NO3)2•6H2O	n.d.	--	
13	w/o electricity or light	n.d.	--	
	
n.d. not detected, w/o without.

aReaction conditions: 1a (9 mmol), 2a (0.9 mmol), 3a (1.8 mmol), FeCl3 (10 mol%), electrolyte (2.0 equiv.), catalyst (10 mol%), ligand (10 mol%), solvent (6.0 mL), light, 25 mA, 12 h, argon, graphite felt (GF) as electrodes, undivided cell.

bGC yields using biphenyl as an internal standard. The ee values were determined by HPLC on a chiral stationary phase.

Scope of substrates

After establishing the optimal reaction conditions, we explored the scope of the photoelectrochemical asymmetric alkylarylation of olefins with respect to different aryl bromide. As shown in Fig. 2, a variety of aryl bromides bearing electron-withdrawing groups (R = carbonyl, formyl, sulfone) and electron-donating (R = methylthio) substituents on the aromatic ring, were viable in this transformation, furnishing the corresponding products in 43–75% yields, with good to excellent enantioselectivities (up to 96% ee). Compared with electron-deficient aryl bromides, electron-rich substrates exhibited slightly lower enantioselectivities (e.g., 10, 81% ee). Notably, the absolute configuration of coupling product 2 was unambiguously assigned by single-crystal X-ray diffraction (additional details are provided in the Supplementary Information, Table 7). The described approach could also be applied to heteroaryl bromides (e.g., bromo-pyridines, benzothiophene. 12–15; 43–67% yields; up to 88% ee). Certain functional groups that are typically sensitive to electroreductive conditions (e.g., carbonyl, formyl, sulfone, and heteroarenes) were well tolerated in this transformation. These results highlight the utility of this very mild redox-neutral asymmetric photoelectrocatalysis. Additionally, the reaction scope was explored with respect to the alkanes. Cycloalkanes with various ring sizes (five to eight carbon atoms) were effective coupling partners, affording the corresponding desired products 16–19 in 71–79% yields with good enantioselectivity (up to 92% ee). However, the reaction enantioselectivity decreased appreciably when other hydrocarbon compounds were employed. For example, acyclic alkanes (e.g., pivalonitrile) served as a suitable coupling partner in this reaction, producing product 20 in 47% yield but with moderate ee. Nevertheless, the regioselectivity control for linear alkane (e.g., n-pentane) is unsuccessful in this protocol. In addition to tert-butyl acrylate, a series of acrylates with various substituents were also compatible and yielded the corresponding products (21–26) in 44–66% yields with 78–87% ee. Vinyl phosphonate, as exemplified by dimethyl vinylphosphonate, was also mendable to this protocol and gave the desired product 27 in 53% yield with 94% ee. Other Michael acceptors, such as β-substituted acrylate, enones, acrylamides and acrylonitrile, could also serve as suitable reaction partner, but exhibiting relatively low reactivity and enantioselectivity under the standard conditions. These results indicate that both the structure of the alkanes and the substituents on the acrylates are crucial for achieving high enantioselectivity.Fig. 2 Substrate scope.

Unless otherwise specified, all reactions were performed under standard conditions. For details, see the Supplementary Information. aL5 was used as the Ligand. bConstant potential electrolysis, cathode potential = −2.0 V vs Ag/AgCl.

From a synthetic perspective, this asymmetric paired redox system offers a modular synthetic route for the enantioselective functionalization of inert C(sp3)−H bonds. Delightfully, this catalytic system can be further applied to more challenging aryl chlorides (Fig. 3) via tuning the current intensity/electrode potential to balance anodic and cathodic reaction rates, and the corresponding products can be obtained with moderate yields and excellent enantioselectivities (92–94% ee). Moreover, iodobenzenes were also coupled with cyclohexane and tert-butyl acrylate to provide the corresponding products in moderate yields and good enantioselectivities (87%-90% ee). The practicality of this methodology was further exemplified by a 9 mmol-scale experiment, after which product 2 was isolated in 61% yield, with 94% ee (Fig. 3). These results highlight the potential synthetic applicability of this asymmetric paired oxidative and reductive catalytic system.Fig. 3 Substrate scope.

Unless otherwise specified, all reactions were performed under standard conditions. For details, see the Supplementary Information. aReaction conditions: Table 1, entry 1.

Mechanistic studies

A series of experiments were conducted to gain insights into the reaction mechanism. First, 1-chloromethyl naphthalene 34, which can be generated via chlorination of the benzylic radical, was obtained in 27% yield when the reaction was performed using 1-methylnaphthalene as the substrate in the absence of a nickel catalyst (Fig. 4a). The potential selected for this experiment was more negative than that needed for the direct oxidation of 1-methylnaphthalene, but it was sufficient to oxidize Fe2+ to Fe3+. This result reveals that a highly electrophilic chloride radical is formed in situ via an anodic ligand-to-metal charge transfer (LMCT) process, which effectively activates C(sp3)−H bonds through hydrogen abstraction to afford the corresponding carbon radical. In addition, alkyl chlorides were detected as a major by-product via Gas Chromatography-Mass Spectrometer (GC-MS) analysis after the standard reaction. However, only product 1 was observed when chlorocycloheptane and cyclohexane were simultaneously added to the standard reaction conditions (Fig. 4b). These results exclude the involvement of alkyl chlorides as key intermediates during the reaction. Furthermore, an Ac-C6H4-Ni(II)-Br complex was prepared in situ and introduced to react with cyclohexane and tert-butyl acrylate (3a) in the presence of stoichiometric FeCl3 under light irradiation (Fig. 4c). The desired product 1 was obtained in 31% yield with 91% ee.Fig. 4 Control experiments.

a Radical trapping experiment. b Use of alkyl chloride as a reactant. c Reaction with an Ar-Ni(II)-Br complex.

In addition, the electrode voltage was monitored over the course of the electrolysis for the model reaction using 4 mA. Anodic oxidation was maintained at approximately 0.28 V vs. Ag/AgCl, while cathodic reduction was maintained at approximately −0.83 V vs. Ag/AgCl (Fig. 5a). These results are consistent with the Fe(II)/Fe(III) oxidative catalysis at the anode. The cathodic potential was sufficient to reduce ArNiIII to ArNiII (e.g., for ArNiIII(Mebpy)Br2, Ar = 4-CF3C6H4; calc. Ered ≈ −0.5 V vs. Ag/AgNO3)65 but not enough to reduce ArNiII to ArNiI (e.g., for p-TolylNiII(bpy)Br, Ered ≈ −1.8 V vs. Ag/AgNO3)66. These results suggest that the aryl-Ni(II) species might be a productive intermediates in this transformation.Fig. 5 Mechanistic studies.

a Electrode voltage over the course of electrolysis. b Nonlinear effects for the standard reaction. c The enantiopurity of product 1 hardly varied during the reaction. d Plot showing first-order rate dependence on current. e Possible mechanism.

Next, we investigated the nonlinear effects. A nonlinear relationship was observed between product 1 and the enantiopurities of L1 (Fig. 5b), suggesting that the involvement of at least two chiral BiIm ligands (L1) in the enantioselectivity-determining step67. Moreover, the observed ee of product 1 remained constant over time, indicating that the reaction followed a unified stereo-convergent transformation process, thus ruling out the product deracemization pathway (Fig. 5c). Subsequently, we evaluated the dependence of the average reaction rate on the current. The reaction exhibited a first-order dependence on the current (Fig. 5d), which confirmed that electron transfer at the electrodes was the rate-determining step at the current applied in this reaction.

On the basis of the results presented herein, a plausible mechanism is proposed (Fig. 5e). The process begins with electrophilic chloride-radical formation via ligand-to-metal charge transfer (LMCT) of the excited [FeCl4]− 68,69. This chlorine radical is converted into alkyl radical E via hydrogen abstraction from the alkane. The resulting alkyl radical E is then added to the alkene, affording radical species F. Concomitantly, the catalyst precursor of NiII is reduced at the cathode, affording NiI species G. This NiI species undergoes further oxidative addition with an aryl halide to generate an aryl-NiIII complex, which is subsequently electrochemically reduced to an aryl-NiII species. The aryl-NiII species I intercept the radical species F to yield the NiIII(aryl)(alkyl) species J. Finally, J undergoes reductive elimination to furnish the cross-coupling products and regenerate the NiI catalyst.

In summary, we have demonstrated the first example of enantioselective alkylarylation of olefins with aliphatic C − H bonds via asymmetric paired oxidative and reductive catalysis. This protocol employs a binary catalytic system based on earth-abundant iron and nickel in an undivided cell. The key features of this asymmetric photoelectrocatalytic approach include excellent enantioselectivity, utilization of hydrocarbon feedstocks as coupling reagents, and a broad aryl halide substrate scope. Ongoing efforts in our laboratory are focused on applying this catalytic platform to other enantioselective multicomponent reactions.

Methods

General procedure A

In an oven-dried three-necked cell (20 mL) equipped with a Teflon-coated magnetic stir bar and two graphite felt electrodes (20 mm × 14 mm × 2.5 mm), lithium chloride (76.3 mg, 1.8 mmol, 2.0 equiv.), FeCl3 (14.6 mg, 10 mol%), Ni(NO3)2•6H2O (26.2 mg, 10 mol%) (Note: Crush it into a dry powder) and L1 (56.4 mg, 10 mol%) were added in a glovebox. The reaction cell was sealed and moved out from the glovebox. Afterwards, aryl bromides (0.9 mmol, 1.0 equiv.), alkanes (9 mmol, 10.0 equiv.), alkenes (1.8 mmol, 2.0 equiv.), acetone (6 mL) were added to the reaction cell via syringe. The reaction mixture was electrolyzed at a constant current of 25 mA under irradiation by a 20 W purple LED lamp (0.5 cm away, with cooling fan to keep the reaction temperature at 25 °C) for 12 h. After the reaction, the reaction mixture was concentrated (the residual product on electrodes were rinsed with ethyl acetate), and purified by column chromatography (eluted with ethyl acetate/petroleum ether) to afford the pure product. (Note: Since the reaction is sensitive to water and air, the solvent must be deoxygenated prior to using).

General procedure B

In an oven-dried three-necked cell (20 mL) equipped with a Teflon-coated magnetic stir bar and two graphite felt electrodes (20 mm × 14 mm × 2.5 mm), lithium chloride (76.3 mg, 1.8 mmol, 2.0 equiv.), FeCl3 (14.6 mg, 10 mol%), KBr (107.1 mg, 0.9 mmol, 1.0 equiv.) Ni(NO3)2•6H2O (26.2 mg, 10 mol%) (Note: Crush it into a dry powder) and L1 (56.4 mg, 10 mol%) were added in a glovebox. The reaction cell was sealed and moved out from the glovebox. Afterwards, aryl chlorides (0.9 mmol, 1.0 equiv.), alkanes (9 mmol, 10.0 equiv.), alkenes (1.8 mmol, 2.0 equiv.), acetone (6 mL) were added to the reaction cell via syringe. The reaction mixture was electrolyzed at a constant cathode voltage of −2.0 V (vs Ag/AgCl) under irradiation by a 20 W purple LED lamp (0.5 cm away, with cooling fan to keep the reaction temperature at 25 °C) for 12 h. After the reaction, the reaction mixture was concentrated (the residual product on electrodes were rinsed with ethyl acetate), and purified by column chromatography (eluted with ethyl acetate/petroleum ether) to afford the pure product. (Note: Since the reaction is sensitive to water and air, the solvent must be deoxygenated prior to using).

Supplementary information

Supplementary Information

Peer Review File

Supplementary information

The online version contains supplementary material available at 10.1038/s41467-024-52248-y.

Acknowledgements

This work was supported by Guangdong Basic and Applied Basic Research Foundation (2024A1515011322), the Fundamental Research Funds for the Central Universities (2042024kf1040), the National Key R&D Program of China (2021YFA1500100), the National Natural Science Foundation of China (No. 22271227), and Wuhan University. We thank Dr. Ran Zhang from the Core Facility of Wuhan University for his assistance with X-ray crystal testing and crystallographic data analysis.

Author contributions

Q.L. conceived and directed the project. L.Z. conducted most of the experimental studies. X.Z. and X.Y. supported performance of synthetic experiments. Q.L. wrote the manuscript. All authors discussed the results, analyzed the data, and prepared the manuscript.

Peer review

Peer review information

Nature Communications thanks Yanbin Zhang, and the other, anonymous, reviewers for their contribution to the peer review of this work. A peer review file is available.

Data availability

Data relating to the characterization data of materials and products, general methods, optimization studies, experimental procedures, mechanistic studies and NMR spectra are available in the Supplementary Information. All data are also available from the corresponding author upon request.

Competing interests

The authors declare no competing interests.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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