General and Efficient C–P Bond Formation by Quantum Dots and Visible Light

Open AccessCCS ChemistryCOMMUNICATION5 Sep 2022General and Efficient C–P Bond Formation by Quantum Dots and Visible Light Rui-Nan Ci†, Cheng Huang†, Lei-Min Zhao, Jia Qiao, Bin Chen, Ke Feng, Chen-Ho Tung and Li-Zhu Wu Rui-Nan Ci† Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 , Cheng Huang† Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 , Lei-Min Zhao Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 , Jia Qiao Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 , Bin Chen Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 , Ke Feng Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 , Chen-Ho Tung Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 and Li-Zhu Wu *Corresponding author: E-mail Address: [email protected] Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 School of Future Technology, University of Chinese Academy of Science, Beijing 100049 https://doi.org/10.31635/ccschem.021.202101615 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail The photocatalytic C–P bond formation reaction involving phosphoryl radicals provides a powerful strategy in phosphorus chemistry. However, the engagement of the phosphoryl radical-forming reaction without stoichiometric oxidants or radical initiators has proven difficult. Herein, we report our discovery that semiconductor quantum dots can act as the sole catalyst to convert H-phosphine oxide into the phosphoryl radical under visible light irradiation. The radical species thus generated can be utilized to undergo radical addition with alkene or radical coupling with α-amino C–H bonds for C–P bond formation. A radical clock experiment and electron paramagnetic resonance spectroscopy identified the phosphoryl radical and α-amino alkyl radicals, responsible for the construction of valuable phosphorus-containing complexes without external oxidants or radical initiators in a step- and atom-economical fashion. Download figure Download PowerPoint Introduction Phosphorus-containing complexes are a significant class of chemicals because of their wide application in catalysis, organic synthesis, medicinal chemistry, and materials chemistry.1–9 As such, the development of efficient and general synthetic routes for their preparation is currently needed. Of these methods, phosphoryl radicals coming directly from the P(O)–H bond represent a promising and straightforward way for the subsequent reaction.10–14 Owing to its intrinsic sustainability and green chemistry character, visible-light mediated photoredox catalysis15–23 offers a valuable platform to generate the phosphinoyl radical for C–P bond formation.24–26 To generate these radicals, radical initiators, strong bases, stoichiometric oxidants, and high temperatures are always employed.27–32 Benefiting from their excellent light-harvesting ability, adjustable band positions, abundant surface sites, and multiple exciton generation,33–42 colloidal quantum dots (QDs)43–50 have drawn considerable attention as photocatalysts for smart organic transformation.51 It is anticipated that upon irradiation, the photoexcited electrons from QDs can be used to drive reduction reactions, and the holes left can be employed for oxidation reaction. Herein, we disclose that CdSe QDs ( Supporting Information Figure S4) can act as the sole catalyst to execute hydrophosphinylation of unactivated alkenes with H-phosphine oxide and cross-coupling hydrogen evolution of H-phosphine oxide with α-amino C–H bonds, respectively, under visible light irradiation (Scheme 1). In contrast to a molecular photocatalyst that can only be coordinated by one substrate at a time in this reaction, a QD can bind multiple substrates simultaneously. With visible light excitation of the QD, the photogenerated hole can activate H-phosphine oxide to form the phosphoryl radical, and the electron in QDs is immediately captured by the proton to yield a hydrogen radical for subsequent hydrophosphinylation or hydrogen evolution. At the same time, the regenerated QD is further excited to activate α-amino C–H bonds to α-amino radicals and thus enable radical coupling of the phosphoryl radical and the α-amino radical for subsequent C–P bond formation. The ability of photocatalysts to act as both strong oxidants and reductants upon irradiation enables H-phosphine oxide activation and thereby facilitates the construction of valuable phosphorus-containing complexes without introducing external oxidants or radical initiators in a step- and atom-economical fashion. Scheme 1 | C–P bond formation enabled by QDs. Download figure Download PowerPoint Results and Discussion To commence our study, we selected diphenylphosphine oxide ( 1a) and 1-pentene ( 2a) as the standard substrates to examine the reaction condition (Table 1). Following 0.1 mmol diphenylphosphine oxide 1a, 0.5 mmol 1-pentene 2a was added into CdSe QDs dimethylformamide (DMF) solution (4.0 × 10−5 M), the reaction mixture was irradiated with blue light-emitting diodes (LEDs) (λ = 450 nm) in an argon atmosphere for 16 h at room temperature. Pleasingly, the desired product 3a was obtained in 98% yield (entry 1). Further screen of solvents, including DMF, CH3CN, dimethyl sulfoxide (DMSO), and N,N-dimethylacetamide (DMA), showed that DMF as solvent gave the highest yields (entries 1–4). However, the desired hydrophosphinylation product was not observed in acetone (entry 5). To figure out whether the reduced hydrogen in the product came from diphenylphosphine oxide or solvents, we performed hydrophosphinylation of unactivated alkene using DMF-d7 as solvent and did not detect the deuterium product 3b′. Instead, the desired product 3b and a small amount of H2 were obtained (Figure 1a2 and Supporting Information Figure S4). It thus became clear that the reduced hydrogen in the product come from diphenylphosphine oxide rather than the solvent. The control experiment revealed that CdSe QDs, visible light, and the inert condition were required for successful implementation of the reaction (Table 1, entries 6–8). Moreover, when equal amounts of 1-hexene and cyclohexene were added to the reaction system simultaneously, the corresponding desired products were obtained with a ratio of 2.5∶1 (Figure 1a4), which suggests their intimate coordination interactions with the surface of QDs. In fact, the QDs reaction was a surface reaction such that a large ratio of alkenes and other C–H substrates were able to guarantee the interaction of QDs and substrates, and thereby efficiently realized the synthesis of hydrophosphinylation derivates with no oxidation by-products and only residual raw materials. Table 1 | Optimization of Conditionsa Entry Change from Standard Conditions 3a (%)b 1 None 98 2 CH3CN instead of DMF 91 3 DMSO instead of DMF 87 4 DMA instead of DMF 89 5 Acetone instead of DMF n.d. 6 No CdSe QDs n.d. 7 No visible light n.d. 8 Air instead of argon n.d. 9 Added 2.0 equiv TEMPO n.d. aStandard conditions: 1a (0.1 mmol), 2a (0.5 mmol, 5 equiv), and CdSe QDs which were dispersed by 3 mL DMF (4.0 × 10−5 M), irradiated by blue LEDs (λ = 450 nm) for 16 h at room temperature under Ar atmosphere. bYields detected by 1H NMR using diphenylacetonitrile as an internal standard based on 1a. n.d. = not detected. Figure 1 | Mechanistic studies. (a) Control experiments. (b) EPR experiments. (1) A solution containing CdSe QDs (dispersed by DMF) and DMPO (0.2 M) was irradiated for 10 s with blue LEDs (λ = 450 nm) under argon atmosphere. (2) Diphenylphosphine oxide 1a was added into the solution containing CdSe QDs (dispersed by DMF) and DMPO (0.2 M) under the irradiation of blue LEDs (λ = 450 nm). (3) N-phenyltetrahydroisoquinoline 4a was added into the solution containing CdSe QDs (dispersed by DMF) and DMPO (0.2 M) under the irradiation of blue LEDs (λ = 450 nm). Download figure Download PowerPoint To shed more light on the photocatalytic reaction, a series of control experiments were further carried out. When a well-known radical scavenger 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) was added to the reaction system, the desired hydrophosphinylation product 3a was completely suppressed (entry 9). When 1,6-heptadiene reacted with diphenylphosphine oxide under standard conditions, the five-membered ring compound was obtained in 76% yield (Figure 1a1). Light on–off experiments proved that constant irradiation was necessary for the reaction to proceed ( Supporting Information Figure S5). Electron paramagnetic resonance (EPR) spectroscopy was performed to identify the P-centered radical intermediates formed, as shown in Figure 1b and Supporting Information Figure S3. When a mixture of CdSe QDs and 5,5-dimethyl-pyrroline-N-Oxide (DMPO) was irradiated with blue LEDs (λ = 450 nm) for 10 s under an argon atmosphere, no spectral signal was observed (Figure 1b1). However, the addition of diphenylphosphine oxide 1a into the solution of CdSe QDs and DMPO immediately led to new peaks that were assigned to the typical spin adduct of the P-centered radical with DMPO of αN = 13.99, αH = 18.87, and αP = 34.05 under the same condition26,52 (Figure 1b2). On the other hand, when N-phenyltetrahydroisoquinoline 4a was added into the mixture of CdSe QDs and DMPO, the α-amino alkyl radicals signal was obtained with coupling constants of αN = 14.58; αH = 18.1853 (Figure 1b3). In addition, the homo-coupling product of 4a was obtained under standard conditions (Figure 1a3). These results demonstrate the multiple substrates on the surface of QDs that generate P-centered radical and α-amino alkyl radicals simultaneously under visible light irradiation. Based on the above results, we proposed a mechanism for the hydrophosphinylation of unactivated alkenes with diphenylphosphine oxide (Scheme 2). Initially, the substrates coordinate with CdSe QDs on the surface. Upon visible light irradiation, CdSe QD is excited to generate a hole in the valence band (VB) and an electron in the conduction band (CB), respectively. Then the hole transfer from the VB to diphenylphosphine oxide 1a′ is followed by deprotonation furnishes P-centered radical I. The radical subsequently undergoes anti-Markovnikov addition to alkene 2a to provide C-centered radical intermediate II. Simultaneously, the protons eliminated from diphenylphosphine oxide are captured by electrons in the CB of CdSe QD, which is sufficiently negative to reduce the protons to hydrogen radicals. Finally, the C-centered radical intermediate II would combine with hydrogen radicals to access the desired hydrophosphinylation product 3a and a photoredox cycle completes. Scheme 2 | Proposed mechanism for hydrophosphinylation of unactivated alkene with diphenylphosphine oxide enabled by QDs. Download figure Download PowerPoint With the understanding of the underlying mechanism in mind, we next examined the substrate scope and functional group tolerance of the reaction. As shown in Table 2, a variety of unactivated teriminal alkenes were readily transformed into the corresponding products in good yields ( 3a–3g). It was noteworthy that the reaction proceeded regioselectively, and only anti-Markovnikov adducts were obtained. In addition, a wide range of cyclic alkenes were also compatible with this reaction in excellent yields, ranging from 60% to 91% ( 3h–3l). However, styrene and 3,4-dihydro-2H-pyrane failed to afford the desired products. To further extend the application of this protocol, diphenylphosphine oxide-bearing alkyl and halogen were tested, respectively. Gratifyingly, these compounds were transformed into the desired products in good to excellent yields ( 3m–3o). Table 2 | Substrate Scope aReaction conditions: 1a (0.1 mmol), 2a (0.5 mmol, 5 equiv), and CdSe QDs dispersed by 3 mL DMF (4.0 × 10−5 M), irradiated by blue LEDs (λ = 450 nm) for 16 h at room temperature under Ar atmosphere; isolated yield. bReaction was performed on a gram scale. cSunlight instead of blue LEDs (λ = 450 nm). See details in Supporting Information. dReaction conditions: 0.1 mmol 4, 0.2 mmol 5, CdSe QDs (8.0 × 10−5 M), NiCl2•6H2O (5.0 × 10−4 M) in 4 mL of CH3CN under Ar, irradiation with blue LEDs (λ = 450 nm) for 18 h at room temperature; isolated yields; H2 was determined by GC-TCE. See details in Supporting Information Figure S2. We then evaluated the scalability of the C–P bond formation reaction by performing gram-scale reactions ( 3a). Using diphenylphosphine oxide 1a and 1-pentene 2a as substrates under the standard conditions, we were able to obtain 1.26 g (92% yield) of the desired hydrophosphinylation product 3a. Furthermore, the desired product 3a could be obtained in 93% yield under direct sunlight irradiation. These results show the great potential of this protocol in practical synthesis. Given that α-amino alkyl radicals could be generated under visible light irradiation of CdSe QDs (Figure 1b3), we envisioned that the interaction of multiple substrates with CdSe QDs would enable a radical coupling between the P-centered radical and α-amino alkyl radicals to construct C–P bonds. To our delight, via simple trials ( Supporting Information Table S1), irradiation of CdSe QDs with N-phenyltetrahydroisoquinoline 4a and diphenylphosphine oxide 1a, cross-coupling product 6a was obtained and hydrogen was detected. No reaction occurred in the presence of molecular photocatalysts, [Ir(dtbbpy)(ppy)2][PF6] and Ru(bpy)3(PF6)2, under identical conditions ( Supporting Information Table S1, entries 6 and 7). However, a QD can execute the activation of C–H and P–H bonds at the same time to obtain the radical–radical cross-coupling product. Our protocol bypasses stoichiometric oxidant and uses QDs as the sole photocatalysts for direct C–P bond formation and produces hydrogen (H2) as a by-product or directly proceeds to the subsequent radical addition. In this system, cocatalyst Ni(II) salts can act as electron acceptors to facilitate the capture of electrons from QDs and H+ in solution for hydrogen evolution. As a result, the photogenerated hole is prolonged to fully interact with substrate and ultimately improve the reaction efficiency ( Supporting Information Table S1, entry 1). As shown in Table 2, a wide range of N-aryl tetrahydroisoquinolines derivatives were amenable to react with dibenzyl phosphonate, affording the desired cross-coupling products in good to excellent yields ( 6b– 6k). N-aryl tetrahydroisoquinolines bearing substituents such as alkyl, alkoxy, and phenyl at the benzene ring on the nitrogen atom afforded the corresponding cross-coupling products in moderate to high yields ( 6b– 6f, 76–93%). Halogen substituents such as F, Cl, and Br were tolerated in this photocatalytic system to deliver the corresponding products in 75–93% yields ( 6g– 6i), which demonstrated feasibility for further synthetic elaborations of the cross-coupling products. Additionally, the substitutes on the phenyl ring of tetrahydroisoqunolines were well tolerated in the reaction, affording the desired product in good yield ( 6j). N-Substituted 4,5,6,7-tetrahydrothieno [3,2-c] pyridine, which is a core structure of many popular medicines, could afford the corresponding product in 83% yield ( 6k) except electron-withdrawing groups in an isqoquinoline framework like CN, NO2, and CO2CH2Ph ( Supporting Information Scheme S1). Other dialkyl phosphonates substrates such as ethyl phosphonates and isopropyl phosphonates enabled coupling with N-phenyltetrahydroisoquinoline to afford the corresponding products in moderate yields ( 6l and 6m). Also, diarylphosphine oxide substrates with an alkyl group could also furnish the desired cross-coupling products, albeit in low yields ( 6n-6o). Conclusion We have demonstrated the advantages of semiconductor QDs for the atom- and step-economical C–P bond formation. The key to the success of the reaction reported in this work is that QDs can be used as the sole photocatalysts to bind multiple substrates simultaneously and execute for P–H bond functionalization under extremely mild reaction conditions. The phosphoryl radical, generated from H-phosphine oxide on the surface of QD under visible light irradiation, enabled coupling with either the α-amino carbon radical of amine or, by addition to unactivated alkenes for C–P bond formation. The established system herein features high efficiency, good functional group tolerance, and high atomic economy. From these encouraging results, we believe that photocatalysis with QDs and visible light in C–X bond formation can substantially facilitate development of direct conversion of solar energy into chemical energy in an efficient and sustainable way. Supporting Information Supporting Information is available and includes general information, experimental procedures, product characterization, and references. Conflict of Interest There is no conflict of interest to report. Acknowledgments We are grateful for financial support from the National Natural Science Foundation of China (nos. 22088102, 21933007, and 22193013), the Ministry of Science and Technology of China (nos. 2017YFA0206903, 2021YFA1500102, and 2021YFA1500802), the Strategic Priority Research Program of the Chinese Academy of Science (no. XDB17000000), and the Key Research Program of Frontier Sciences of the Chinese Academy of Science (no. QYZDY-SSW-JSC029). References 1. Baumgartner T.; Réau R.Organophosphorus π-Conjugated Materials.Chem. Rev.2006, 106, 4681–4727. Google Scholar 2. Chen X.; Kopecky D. 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XDB17000000), and the Key Research Program of Frontier Sciences of the Chinese Academy of Science (no. QYZDY-SSW-JSC029). Downloaded 999 times PDF DownloadLoading ...