Download PDF
Synthesis 2023; 55(21): 3589-3599
DOI: 10.1055/a-2018-0965
special topic
C–H Bond Functionalization of Heterocycles

Aryl Triflates in Phosphorus-Directed Rhodium(III)-Catalyzed C–H Activation

Julien Roger  ∗
,
Charline Sire
,
Anthonia Tsivery
,
Hélène Cattey 
,
Jean-Cyrille Hierso  ∗

This work was supported by the CNRS, the Université de Bourgogne, the Conseil Régional Bourgogne-Franche-Comté, and the Fonds Européen de Développement Régional (FEDER). This work was also funded by the French Agence Nationale de la Recherche via the ANR-JCJC program 2018 FIT-FUN (ANR-18-CE07-0015, for J.R. and a grant for C.S.) and the ANR PRC program 2020 CARAPH (ANR-20-CE07-0001-01, for J.-C.H).
› Further Information
 
 PDF Download Permissions and Reprints All articles of this category


Abstract

Aryl triflates are selected as suitable electrophile coupling partners for the phosphorus-directed rhodium(III)-catalyzed direct C–H arylation of polyaromatic phosphines. We report herein simple conditions for the peri-C–H functionalization of polyarylphosphines, where a [Rh(III)Cl2Cp*]2 precatalyst is employed to provide a convenient access to polyarylated phosphines in up to 93% isolated yield. This synthetic approach tolerates a wide range of different aryl trifluoromethylsulfonate derivatives bearing either electron-donating (COMe, CN, CF3 or Cl) or electron-withdrawing substituents (Me, OMe) at the para-, meta- and ortho-positions, and includes bulky polyaromatic triflate substrates. We further describe access to a large class of polycyclic aromatic hydrocarbon phosphine ligands, their oxidized derivatives (i.e., their oxides and selenides), their coordination modes with Au(I) and Cu(I) coinage metal salts, and their use as efficient ligands for the atom-economic, gold-catalyzed oxidative cyclization of terminal alkynes with nitriles.


#

Key words

arylation - catalysis - P-ligand directed C–H activation - rhodium - trifluoromethylsulfonates - oxazoles

Selective transition-metal-catalyzed C–H activation/functionalization reactions conducted with pseudo(halide) coupling partners obtained from renewable resources, such as alcohols and phenols,[1] complement advantageously the classical use of organic halides that are typically generated from fossil resources.[1a] [b] The reactivity of some organic halides (iodides, fluorides) over phosphine, leading preferentially to the formation of phosphonium salts,[1c,d] is sometimes a limitation to their direct use as ligands in transition-metal catalysis. These findings are pertinent driving forces for the development of pseudo(halide) reactivity in direct C–H functionalization with transitions metals. Many alcohols are directly obtained from widely available and low-cost bioresources, while in addition, the preparation of reactive alcohol derivatives is generally easy to achieve.[1e,f] In this context, investigations on the use of electrophile alternatives to halogenated arenes, such as crystalline, purifiable and fairly robust phenolates, is appropriate.[1f] Besides, the versatile phenolic group can be used for introducing further functionality on the aromatic ring of the substrate, and can then be converted into a coupling function via formation of the corresponding triflate.[1g]

Aryl trifluoromethylsulfonates have been successfully employed in transition-metal-catalyzed C–H bond functionalizations of heteroarenes. The direct C–H arylation of heteroarenes (mainly azole derivatives), pyridines and polyfluorinated arenes has been achieved in the presence of palladium[1g] [2] [3] and nickel precatalysts,[5] but remains limited to single studies with rhodium[6] and copper (Scheme [1], top left).[7] Further, they have also been fruitfully employed for the nitrogen-directed ruthenium-catalyzed ortho-C–H arylation of heteroarenes,[8] and have been extended to the oxygen-directed C–H activation/functionalization of aryl ketones with ruthenium[9] and palladium catalysts (Scheme [1], top right).[10]

Zoom Image
Scheme 1 Previous work using aryl triflates as substrates in transition-metal-catalyzed C–H direct (hetero)arylation (top left), and nitrogen- and oxygen-directed arylation (top right), along with the present work on phosphorus-directed rhodium-catalyzed C–H arylation of PAH phosphines (bottom)

On the other hand, polycyclic aromatic hydrocarbons (PAHs) incorporating phosphorus atoms are useful building blocks in organic electronics and medicine, with wide applications as pharmaceuticals,[11] in ligand design for catalysis,[12] and in materials science.[13] New synthetic routes have been developed including catalyzed C–H activation/functionalization with transition metals using phosphorus as the directing group.[14] [15] As a promising synthetic approach, P-directed, rhodium-catalyzed arylation demonstrates high utility for the direct ortho-arylation of biphenylphosphine[16] and the peri-arylation of naphthyl and related PAHs such as pyrenylphosphines.[17] [18] More recently, Shi et al. reported the ortho-functionalization of triarylphosphines through a 4-membered rhodacycle.[19] These strategies mainly employed bromo- and chloroarenes as the electrophilic reagents. Thus, a general protocol for efficient P-ligand-directed peri-arylation of polyaromatic hydrocarbons using phenolate derivatives remained to be developed.

Based on our recent work on P-directed C–H functionalization,[18] and the valuable use of aryl triflates as alternative electrophilic coupling partners in transition-metal-catalyzed C–H activation and functionalization,[1g] [8] we herein describe our studies on the development of conditions for the exploitation of aryl trifluoromethylsulfonates as substrates in rhodium-catalyzed P-ligand-directing C–H activation/arylation (Scheme [1], bottom).

Polyaromatic and biphenyl motifs are widely applied as pharmaceuticals, agrochemicals and in materials science. We previously reported the efficiency of using rhodium(III) precatalysts to activate and functionalize selectively PAHs by P-directed peri-C–H arylation,[18] while a rhodium(I) species was generally preferred.[13] [17] We hypothesized that similarly the convenient and easy to handle [Rh(III)Cl2Cp*]2 would be a suitable precatalyst for selective functionalization at the K-region of pyrene scaffold 1 with aryl triflates (Scheme [2], top, and Table [1] in the Supporting Information). After optimization, the 10-(4-acetylphenyl)pyrenyl diphenylphosphine 2 was indeed isolated in 93% yield using 2.5 mol% of [RhCl2Cp*]2 with 1.5 equivalents of 4-acetylphenyl triflate, and K3PO4 as the base in trifluoromethylbenzene (PhCF3) (0.165 M based on 1).

Zoom Image
Scheme 2 P-directed C–H arylation of 1-diphenylphosphine pyrene 1 using functional aryl triflates. Conditions: 1-diphenylphosphine pyrene 1 (0.5 mmol, 1 equiv), aryl triflate (1.5 equiv), [RhCl2Cp*]2 (2.5 mol%), K3PO4 (3.0 equiv), in anhydrous trifluoromethylbenzene [0.165 M] at reflux, 18 h under argon. 1H NMR yield are given with isolated yields in brackets. a The corresponding 10-(4-trifluoromethylsulfonate phenyl)-1-diphenylphosphine pyrene 5 was also detected in 14% yield. b The corresponding 10-(4-bromomethylsulfonate phenyl)-1-diphenylphosphine pyrene 5′ was also detected in 8% yield.

Next, we further investigated the scope of functionalized aryl triflates as coupling partners in the Rh(III)-catalyzed C–H arylation of 1-diphenylphosphine pyrene 1 under the optimized conditions (Scheme [2]). The reaction was successfully extended to p-benzonitrile triflate with an 89% isolated yield of product 3 being obtained. With 4-chlorophenyl triflate, a 48% isolated yield was obtained for 4, together with 7% of the side product 10-(4-trifluoromethylsulfonate phenyl)-1-diphenylphosphine pyrene 5 (selectivity of 86:14 in favor of C–OTf bond cleavage). Due to the higher reactivity of the C–Br bond compared to C–OTf under our reaction conditions, 1-(diphenylphosphino)-10-(4-trifluoromethyl sulfonate phenyl) pyrene 5 was obtained in 76% isolated yield with a selectivity 91:9 (see also Table [2] in the Supporting Information).

Unsubstituted phenyl triflate was coupled to 1 to give product 6 in 78% isolated yield. Electron-donating groups, such as methyl or methoxy, are also tolerated, which can be present on the aryl triflate as one, two or three substituents in various para-, meta- or ortho-positions. These coupling partners furnished lower yields (42–87%) (Scheme [2], products 7–12) compared to the C–H arylations using substrates containing electron-withdrawing groups (Scheme [2], products 2–5). Steric congestion from polyaromatic triflates did not hamper the reaction, and in the presence of 2-naphthyl, 1-naphthyl or 9-phenanthrenyl groups the corresponding coupling products 13 (89%), 14 (32%) and 15 (76%) were obtained. The 3-pyridinyl triflate was employed in our conditions and gave the 1-(diphenylphosphino)-10-(3-pyrinyl) pyrene 16 in 24% isolated yield.

Our protocol was successfully extended to other PAH monophosphines 17–19 (Scheme [3]). 1-Naphthyl diphenylphosphine gave isolated yields of 88%, 93% and 55% for products 20, 21 and 22, respectively, in the presence of triflates with electron-withdrawing groups (acetyl, nitrile and trifluoromethyl groups), and 87%, 55% and 51% for products 23, 24 and 25, respectively, in the presence of electron-rich triflates (with phenyl, methyl or trimethoxy substituents) as coupling partners. 4-Fluoranthenyl and 9-phenanthrenyl phosphines were also found to be convenient partners for the P-directed C–H bond activation/arylation, with isolated yields of 93%, 47% and 79% being obtained for the corresponding products 26, 27 and 28, respectively. The X-ray diffraction (XRD) structure of [2-(3,4,5-trimethoxyphenyl)-3-phenanthryl]diphenyl phosphine 28 confirmed the expected selectivity of the C–H bond arylation at the peri-position of the polyaromatic hydrocarbon core.

Zoom Image
Scheme 3 Selected arylations of other polyaromatic hydrocarbon diphenylphosphines with aryl triflates. Conditions: 1-diphenylphosphine PAH (0.5 mmol, 1 equiv), aryl triflate (1.5 equiv), [RhCl2Cp*]2 (2.5 mol%), K3PO4 (3.0 equiv), in anhydrous trifluoromethylbenzene [0.165 M] at reflux, 18 h under argon. 1H NMR yields; isolated yields are given in brackets.

We examined the impact on the donor character of the phosphino groups after introduction of proximate aryl moieties (Table [1]). This was achieved by the conversion of P(III) into P(V) via oxidation or selenation, and measurement of the resulting nuclear spin–spin coupling constants.[20] [21]

Table 1 31P NMR Data (202 MHz, CDCl3) for Polyaromatic Phosphines 18 and 27, Their Corresponding Oxide and Selenium Products, and Their Complexes with Au(I)Cl and Cu(I)Cla

Phosphine

31P

31PO

31PSe

1 J PSe(Hz)

Au(I)/31P

Cu(I)/31P

18

–13.8

18-O: 30.7

18-Se: 29.8

724

24.5

–8.7 (br)

27

 –6.8

27-O: 29.1

27-Se: 38.0

753

30.5

–6.4 (br)

a Chemical shifts are given in ppm. Benchmark 1 J PSe value for Ph3P(Se) = 730 Hz; 31P NMR (162 MHz, CDCl3) for [(Ph3P)AuCl] = 57.1 ppm.[22] The coordination to gold and copper was achieved in CH2Cl2 by reacting the ligand with [(Me2S)AuCl] or CuCl, respectively (see Scheme [4]); br = broad.

We examined both the polyaromatic diphenylphosphine 18 and its arylated derivative 27, which incorporates three methoxy electron-donating groups on the peri-aryl moiety. The 31P NMR spectroscopic data for these compounds and their corresponding oxide derivatives are collected in Table [1]. The selenide phosphines 18-Se and 27-Se featured 31P NMR signals located at 29.8 and 38.0 ppm, while the corresponding phosphine oxides 18-O and 27-O showed signals at 30.7 and 29.1 ppm, respectively. The benchmark 1 J P,Se value for triphenylphosphine selenide PPh3(Se) in CDCl3 is 730 Hz, which was found to be higher than that of the selenated 1-diphenylphosphine-fluoranthene 18-Se: 1 J P,Se = 724 Hz. The phosphine 18 is thus slightly more electron-donor (basic) than PPh3. Conversely, a notably less basic character for 25 (because 1 J P,Se = 753 Hz for 27-Se) was suggested compared with both PPh3 and the polyaromatic diphenylphosphine 18.

We next achieved complexation of the polyaromatic phosphines 18 and 27 to coinage metals with gold(I) chloride and copper(I) chloride salts (Table [1] and Scheme [4]).[23] [24] For fluoranthenyl diphenylphosphines 18 and 27, the reaction with [(Me2S)AuCl] quantitatively led to complexes A and B that were characterized via 31P NMR spectroscopy (202 MHz, CDCl3), demonstrating singlets at 24.5 ppm and 30.5 ppm, respectively (Scheme [4]; see also the XRD of B in Figure [1]; the XRD for A is reported in the Supporting Information). The complexation of 18 and 27 with Cu(I)Cl quantitatively led to complexes C and D, respectively, which were obtained in 73% and 76% isolated yields after precipitation, and were characterized by 31P NMR spectroscopy (202 MHz, CDCl3), showing broad signals at –8.7 ppm and –6.4 ppm, respectively (see Scheme [4]; the XRD for C, as a classical cubane structure, is reported in the Supporting Information).

Zoom Image
Scheme 4 Au(I)Cl complexes A and B and Cu(I)Cl complexes C and D, stabilized by fluoranthenylphosphines 18 and 27, respectively
Zoom Image
Figure 1 Molecular structure of complex B (thermal ellipsoids at 30% probabilities, H atoms and one CH2Cl2 are omitted for clarity)

Table 2 Gold-Catalyzed Oxidative Cyclization of Terminal Alkynes with Nitrilesa

Entry

R1

R2

Catalyst

Yield

1

4-OMe

Me

AuClSMe2

29: 9%

2

4-OMe

Me

18 + AuClSMe2

29: 76%

3

4-OMe

Me

27 + AuClSMe2

29: 97%

4

4-OMe

Me

[A]

29: 72%

5

4-OMe

Me

[B]

29: 99% (93%)

6

4-OMe

Ph

[A]

30: 97%

7

4-OMe

Ph

[B]

30: 99% (82%)

8

4-F

Me

[A]

31: 72%

9

4-F

Me

[B]

31: 92% (80%)

a Reaction conditions: aryl alkyne (0.6 mmol, 1 equiv), 8-methylquinoline N-oxide (1.3 equiv), [Au] (5 mol%), [AgNTf2] (15 mol%), in acetonitrile [0.2 M] at 50 °C, 5 h under argon. 1H NMR yields are given based on aryl alkyne consumption (isolated yields are in brackets).

To study the effect of gold on the catalytic activity of 18 and 27 used as ligands, the corresponding gold complexes A and B were evaluated in the oxidative cyclization of terminal alkynes with nitriles (Table [2]).[25] The combination of AuClSMe2­ with both polyaromatic diphenylphosphines satisfactorily afforded the 2,5-disubstituted oxazole 29 (Table [2], entries 1–3). However, the introduction of an aryl group at the peri-position that is achieved with ligand 27 significantly enhanced the catalytic activity with a 97% conversion into 29. A lower 76% conversion was achieved under similar conditions using non-peri-arylated 18 (Table [2], entries 2 and 3). Consistent results were achieved with the corresponding preformed gold complexes A and B, with 72% and 99% conversion, respectively (Table [2], entries 4 and 5), and similarly for the formation of the oxazoles 30 and 31 (Table [2], entries 6–9).

In conclusion, we have shown that substituted aryl triflates are appropriate coupling partners in the rhodium-catalyzed direct C–H functionalization of polyaromatic phosphines. Trifluoromethylsulfonates can be obtained from alcohols, themselves being resources acquired from renewable biomass. We have reported herein the practical synthesis of peri-functionalized polyaromatic hydrocarbon phosphines by using aryl phenolate derivatives as the coupling partners. Our rhodium-catalyzed P-directed C–H arylation tolerates aryl triflates incorporating various electron-donating and electron-withdrawing groups at the ortho-, meta- and para-positions. This protocol provides a convenient access to novel polyarylated phosphines that are ready-to-use for further modification, or as ligands for metal coordination and catalysis, as illustrated herein.

All reagents were purchased from commercial suppliers and used without further purification. The polyarylated phosphines were synthesized according to the literature.[18] All reactions were performed under an atmosphere of dry argon in oven-dried glassware using Schlenk and vacuum-line techniques. Flash chromatography was performed on silica gel (40–63 μm). The identities and purities of the products were established at the ‘Chemical Analysis Platform and Molecular Synthesis University of Burgundy’ (PACSMUB Platform – SATT SAYENS) using high-resolution mass spectrometry, elemental analysis and multinuclear NMR. 1H (500 MHz), 31P (202 MHz), 18F (407 MHz), and 13C (125 MHz) NMR spectra were recorded on a Bruker AVANCE III instrument in CDCl3 solutions. Chemical shifts are reported in ppm relative to CDCl3 (1H: 7.26 and 13C: 77.16); coupling constants J are given in Hz. Elemental analysis experiments were performed with a Thermo Electron Flash EA 1112 Series analyzer. High-resolution mass spectrometry (HRMS) was accomplished using a Thermo LTQ-Orbitrap XL instrument with an ESI source. CCDC 2214568 (28), 2214569 (A), 2214570 (B) and 2214571 (C) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.


#

Arylated Diphenylphosphine PAHs; General Procedure

An oven-dried Schlenk tube equipped with a magnetic stir bar was charged with 1-diphenylphosphine PAH (0.5 mmol, 1 equiv), aryl triflate (0.75 mmol, 1.5 equiv), K3PO4 (1.5 mmol, 3.0 equiv, 318 mg) and [RhCl2Cp*]2 (0.0125 mmol, 2.5 mol%, 7.7 mg) in anhydrous trifluoromethylbenzene (0.165 M, 3 mL). The mixture was stirred at reflux under argon for 18 h. After extraction using a CH2Cl2/H2O mixture, the organic layer was concentrated in vacuo. The crude product was purified by column chromatography on silica gel using a mixture of pentane/dichloromethane as the eluent.


#

1-(Diphenylphosphino)-10-(4-acetylphenyl)pyrene (2)[18]

Yield: 234 mg (93%); yellow solid; eluent: pentane/dichloromethane (1:2).

1H NMR (500 MHz, CDCl3): δ = 8.22 (d, J = 7.5 Hz, 1 H), 8.16 (d, J = 7.4 Hz, 1 H), 8.12 (d, J = 8.9 Hz, 1 H), 8.09–8.00 (m, 3 H), 7.96 (s, 1 H), 7.79 (dd, J = 7.9, 4.1 Hz, 1 H), 7.71 (d, J = 8.2 Hz, 2 H), 7.37 (d, J = 8.2 Hz, 2 H), 7.27 (t, J = 6.7 Hz, 2 H), 7.21 (t, J = 7.4 Hz, 4 H), 7.03 (t, J = 7.1 Hz, 4 H), 2.60 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –9.2 (s).


#

1-(Diphenylphosphino)-10-(4-cyanophenyl)pyrene (3)

Yield: 217 mg (89%); yellow solid; eluent: pentane/dichloromethane (3:1).

1H NMR (500 MHz, CDCl3): δ = 8.26 (d, J = 7.5 Hz, 1 H), 8.17 (dd, J = 15.8, 8.2 Hz, 2 H), 8.07 (dt, J = 12.4, 7.8 Hz, 3 H), 7.92 (s, 1 H), 7.75 (dd, J = 8.0, 4.1 Hz, 1 H), 7.38 (d, J = 8.3 Hz, 2 H), 7.34 (d, J = 8.2 Hz, 2 H), 7.29 (t, J = 7.3 Hz, 2 H), 7.25–7.21 (m, 4 H), 7.01 (t, J = 7.7 Hz, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.7 (s).

13C NMR (125 MHz, CDCl3): δ = 149.0 (d, JPC = 4.8 Hz), 138.8 (d, JPC = 15.0 Hz), 138.7, 135.8, 134.6 (d, JPC = 22.6 Hz), 133.7, (d, JPC = 20.3 Hz), 132.5 (d, JPC = 26.6 Hz), 132.1, 132.0, 131.7, 131.4, 131.2 (d, JPC = 7.3 Hz), 129.9, 128.6 (d, JPC = 15.6 Hz), 128.5, 128.4, 127.8, 126.6, 126.3, 126.2 (d, JPC = 5.5 Hz), 125.9, 125.7, 124.4 (d, JPC = 1.8 Hz), 119.5, 110.6.

HRMS (p ESI): m/z [M – H]+ calcd for C35H21NP: 486.14061; found: 486.14031.

Anal. Calcd for C35H22NP: C, 85.23; H, 4.55. Found: C, 84.80; H, 4.69.


#

1-(Diphenylphosphino)-10-(4-chlorophenyl) pyrene(4)[18]

Yield: 104 mg (42%); yellow solid; eluent: pentane/dichloromethane (4:1 then 2:1).

1H NMR (500 MHz, CDCl3): δ = 8.21 (d, J = 7.3 Hz, 1 H), 8.14 (d, J = 7.4 Hz, 1 H), 8.12 (d, J = 8.9 Hz, 1 H), 8.06–7.99 (m, 3 H), 7.92 (s, 1 H), 7.74 (dd, J = 7.9, 4.0 Hz, 1 H), 7.27 (t, J = 7.3 Hz, 2 H), 7.22 (t, J = 7.4 Hz, 4 H), 7.16 (d, J = 8.3 Hz, 2 H), 7.09 (d, J = 8.3 Hz, 2 H), 7.04 (t, J = 7.7 Hz, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.3 (s).


#

1-(Diphenylphosphino)-10-((4-trifluoromethylsulfonyloxy)phenyl)pyrene (5)

Yield: 230 mg (76%); yellow solid; eluent: pentane/dichloromethane (4:1 then 2:1).

1H NMR (500 MHz, CDCl3): δ = 8.16 (d, J = 7.5 Hz, 1 H), 8.07 (dd, J = 13.0, 8.1 Hz, 2 H), 7.97 (dd, J = 15.3, 7.4 Hz, 3 H), 7.84 (s, 1 H), 7.62 (dd, J = 8.0, 4.2 Hz, 1 H), 7.31 (s, 1 H), 7.22–7.18 (m, 3 H), 7.12 (t, J = 7.4 Hz, 5 H), 6.97–6.89 (m, 6 H), 6.84 (d, J = 9.2 Hz, 1 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –7.9 (s).

19F{1H} NMR (470 MHz, CDCl3): δ = –72.8 (s).

13C NMR (125 MHz, CDCl3): δ = 142.4 (d, J PC = 5.2 Hz), 139.3 (d, J PC = 4.7 Hz), 139.1, 135.6, 135.1 (d, J PC = 21.5 Hz), 133.8 (d, J PC = 20.5 Hz), 133.3, 132.8 (d, J PC = 25.4 Hz), 132.0, 131.9 (d, J PC = 7.0 Hz), 131.8, 131.4, 130.2, 128.4, 128.3, 128.3, 128.2, 128.1, 127.8, 126.4, 126.2 (d, J PC = 5.2 Hz), 125.8 (d, J PC = 24.5 Hz), 125.4, 124.2 (d, J PC = 1.6 Hz).

HRMS (p ESI): m/z [M + H]+ calcd for C35H21F3O3PS: 611.10439; found: 611.10521.

Anal. Calcd for C35H22F3O3PS: C, 68.85; H, 3.63. Found: C, 68.76; H, 3.59.


#

1-(Diphenylphosphino)-10-(phenyl)pyrene (6)

Yield: 200 mg (48%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 8.22 (d, J = 7.6 Hz, 1 H), 8.15 (dd, J = 14.9, 8.1 Hz, 2 H), 8.08–8.01 (m, 3 H), 7.97 (s, 1 H), 7.73 (dd, J = 8.0, 4.0 Hz, 1 H), 7.30 (t, J = 7.4 Hz, 1 H), 7.23 (d, J = 7.4 Hz, 3 H), 7.22–7.12 (m, 7 H), 7.02–6.97 (m, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.2 (s).

13C NMR (125 MHz, CDCl3): δ = 144.2 (d, JPC = 5.4 Hz), 140.5 (d, JPC = 5.1 Hz), 139.8 (d, JPC = 7.1 Hz), 135.7, 134.7 (d, JPC = 21.4 Hz), 133.8 (d, JPC = 20.6 Hz), 133.5 (d, JPC = 28.3 Hz), 132.0, 131.8, 131.4, 130.7 (d, JPC = 7.1 Hz), 130.4, 128.2, 128.2, 128.1, 127.8, 127.2, 126.4, 126.2 (d, JPC = 5.1 Hz), 125.5 (d, JPC = 5.0 Hz), 125.2, 124.3 (d, JPC = 1.7 Hz).

HRMS (p ESI): m/z [M + H]+ calcd for C34H24P: 463.16101; found: 463.16070.

Anal. Calcd for C34H23P: C, 88.29; H, 5.01. Found: C, 87.93; H, 4.81.


#

1-(Diphenylphosphino)-10-(4-methylphenyl)pyrene (7)[18]

Yield: 207 mg (87%); yellow solid; eluent: pentane/dichloromethane (3:1).

1H NMR (500 MHz, CDCl3): δ = 8.11 (t, J = 7.9 Hz, 2 H), 8.04 (d, J = 8.9 Hz, 1 H), 8.00–7.95 (m, 3 H), 7.93 (d, J = 7.6 Hz, 1 H), 7.77 (dd, J = 7.9, 4.0 Hz, 1 H), 7.24–7.15 (m, 8 H), 7.05 (t, J = 6.9 Hz, 4 H), 6.94 (d, J = 7.7 Hz, 2 H), 2.38 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.6 (s).


#

1-(Diphenylphosphino)-10-(4-methoxyphenyl)pyrene (8)[18]

Yield: 199 mg (81%); yellow solid; eluent: pentane/dichloromethane (3:2 then 1:1).

1H NMR (500 MHz, CDCl3): δ = 8.20 (d, J = 7.4 Hz, 1 H), 8.15 (d, J = 5.9 Hz, 1 H), 8.12 (d, J = 8.8 Hz, 1 H), 8.07–8.00 (m, 3 H), 7.96 (br s, 1 H), 7.73 (dd, J = 7.9, 4.0 Hz, 1 H), 7.27–7.18 (m, 6 H), 7.16 (d, J = 8.3 Hz, 2 H), 7.04 (t, J = 6.5 Hz, 4 H), 6.69 (d, J = 10.3 Hz, 2 H), 3.82 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.1 (s).


#

1-(Diphenylphosphino)-10-(3-methoxyphenyl)pyrene (9)[18]

Yield: 150 mg (61%); yellow solid; eluent: pentane/dichloromethane (3:1 then 1:1).

1H NMR (500 MHz, CDCl3): δ = 8.04 (d, J = 7.5 Hz, 1 H), 8.01 (d, J = 7.5 Hz, 1 H), 7.96 (d, J = 8.8 Hz, 1 H), 7.93–7.84 (m, 4 H), 7.65 (dd, J = 8.0, 3.9 Hz, 1 H), 7.13–7.00 (m, 7 H), 6.95 (t, J = 7.5 Hz, 2 H), 6.88 (q, J = 7.0 Hz, 3 H), 6.76 (dd, J = 8.2, 2.3 Hz, 1 H), 6.55 (s, 1 H), 3.32 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.6 (s).


#

1-(Diphenylphosphino)-10-(3,5-dimethoxyphenyl)pyrene (10)

Yield: 180 mg (69%); yellow solid; eluent: pentane/dichloromethane (1:1).

1H NMR (500 MHz, CDCl3): δ = 8.20 (dd, J = 11.1, 7.5 Hz, 2 H), 8.13 (d, J = 8.9 Hz, 1 H), 8.10–8.02 (m, 4 H), 7.85 (dd, J = 8.0, 3.7 Hz, 1 H), 7.25 (q, J = 8.6, 7.4 Hz, 6 H), 7.13–7.07 (m, 4 H), 6.53 (t, J = 2.3 Hz, 1 H), 6.50 (d, J = 2.2 Hz, 2 H), 3.56 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –9.1 (s).

13C NMR (125 MHz, CDCl3): δ = 160.7, 146.2 (d, JPC = 5.4 Hz), 140.5 (d, JPC = 18.9 Hz), 140.4 (d, JPC = 4.6 Hz), 136.2, 135.4 (d, JPC = 2.1 Hz), 133.5 (d, JPC = 20.7 Hz), 133.4 (d, JPC = 29.7 Hz), 132.1, 131.4, 131.1, 130.2, 128.3 (d, JPC = 6.0 Hz), 128.3, 128.0, 127.8, 126.4, 126.1 (d, JPC = 5.2 Hz), 125.6 (d, JPC = 12.3 Hz), 125.3, 124.3 (d, JPC = 1.8 Hz), 108.8 (d, JPC = 7.9 Hz), 108.7, 100.3, 55.2.

HRMS (p ESI): m/z [M + H]+ calcd for C36H28O2P: 523.18214; found: 523.18154.

Anal. Calcd for C36H27O2P: C, 82.74; H, 5.21. Found: C, 80.73; H, 5.10.


#

1-(Diphenylphosphino)-10-(3,4,5-trimethoxyphenyl)pyrene (11)

Yield: 141 mg (51%); yellow solid; eluent: pentane/dichloromethane (1:2 then 1:4).

1H NMR (500 MHz, CDCl3): δ = 8.21 (d, J = 7.5 Hz, 1 H), 8.18 (d, J = 7.4 Hz, 1 H), 8.13 (d, J = 8.8 Hz, 1 H), 8.09–8.01 (m, 4 H), 7.80 (dd, J = 7.9, 3.7 Hz, 1 H), 7.28–7.20 (m, 6 H), 7.05 (t, J = 6.7 Hz, 4 H), 6.49 (s, 2 H), 3.98 (s, 3 H), 3.52 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.6 (s).

13C NMR (125 MHz, CDCl3): δ = 153.1, 140.5 (d, JPC = 19.1 Hz), 140.4 (d, JPC = 4.3 Hz), 139.6 (d, JPC = 5.4 Hz), 137.9, 136.1, 135.4 (d, JPC = 21.5 Hz), 133.4 (d, JPC = 21.0 Hz), 133.0, 132.1, 131.4, 131.2, 130.1, 128.4, 128.3, 128.3, 128.1, 127.8, 126.4, 126.1 (d, JPC = 2.1 Hz), 125.6, 125.4 (d, JPC = 13.0 Hz), 124.3 (d, JPC = 1.6 Hz), 108.1 (d, JPC = 8.0 Hz), 61.2, 55.7.

HRMS (p ESI): m/z [M + H]+ calcd for C37H30O3P: 553.19153; found: 553.19271.

Anal. Calcd for C37H29O3P: C, 80.42; H, 5.29. Found: C, 80.80; H, 5.49.


#

1-(Diphenylphosphino)-10-(2-methoxyphenyl)pyrene (12)[18]

Yield: 103 mg (42%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 8.21 (d, J = 7.5 Hz, 1 H), 8.16 (d, J = 7.5 Hz, 1 H), 8.16 (d, J = 8.9 Hz, 1 H), 8.07–8.00 (m, 3 H), 7.98 (s, 1 H), 7.72 (dd, J = 7.3, 3.4 Hz, 1 H), 7.40 (t, J = 7.6 Hz, 1 H), 7.29 (br s, 3 H), 7.22 (t, J = 7.0 Hz, 1 H), 7.16–7.13 (m, 4 H), 7.04 (d, J = 7.0 Hz, 1 H), 6.87 (t, J = 6.9 Hz, 2 H), 6.80 (t, J = 7.2 Hz, 2 H), 3.48 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.3 (s).


#

1-(Diphenylphosphino)-10-(2-naphthyl)pyrene (13)[18]

Yield: 227 mg (89%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 8.23 (d, J = 7.4 Hz, 1 H), 8.18 (d, J = 8.2 Hz, 1 H), 8.16 (d, J = 8.2 Hz, 1 H), 8.09 (d, J = 7.6 Hz, 2 H), 8.07–8.02 (m, 2 H), 7.87 (d, J = 8.2 Hz, 1 H), 7.82 (d, J = 8.3 Hz, 1 H), 7.76 (dd, J = 8.0, 4.2 Hz, 1 H), 7.65 (d, J = 8.3 Hz, 1 H), 7.50–7.44 (m, 2 H), 7.34 (q, J = 8.2, 7.7 Hz, 2 H), 7.24–7.14 (m, 4 H), 7.09 (t, J = 7.1 Hz, 2 H), 6.93 (t, J = 6.9 Hz, 2 H), 6.85 (t, J = 7.3 Hz, 2 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.2 (s).


#

1-(Diphenylphosphino)-10-(1-naphthyl)pyrene (14)[18]

Yield: 82 mg (32%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 8.26 (d, J = 7.0 Hz, 1 H), 8.18 (d, J = 8.2 Hz, 1 H), 8.16 (d, J = 7.5 Hz, 1 H), 8.12–8.03 (m, 4 H), 7.92 (t, J = 6.4 Hz, 2 H), 7.66 (t, J = 7.9, 3.6 Hz, 1 H), 7.42 (t, J = 7.6 Hz, 2 H), 7.25–7.12 (m, 7 H), 7.07 (t, J = 7.4 Hz, 2 H), 6.78 (t, J = 7.7 Hz, 2 H), 6.67 (t, J = 6.8 Hz, 2 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –7.7 (s).


#

1-(Diphenylphosphino)-10-(9-phenanthryl)pyrene (15)[18]

Yield: 202 mg (76%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 8.78 (d, J = 8.2 Hz, 1 H), 8.74 (d, J = 8.3 Hz, 1 H), 8.25 (d, J = 7.5 Hz, 1 H), 8.19–8.13 (m, 3 H), 8.12–8.07 (m, 2 H), 8.03 (t, J = 7.6 Hz, 1 H), 7.67–7.58 (m, 4 H), 7.46 (t, J = 7.3 Hz, 1 H), 7.39–7.30 (m, 3 H), 7.19–7.09 (m, 2 H), 7.09–6.98 (m, 4 H), 6.68 (t, J = 6.8 Hz, 2 H), 6.54 (t, J = 7.2 Hz, 2 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –7.1 (s).


#

1-(Diphenylphosphino)-10-(3-pyridyl)pyrene (16)

Yield: 56 mg (24%); yellow solid; eluent: pentane/dichloromethane (1:1).

1H NMR (500 MHz, CDCl3): δ = 8.65–8.56 (m, 2 H), 8.27 (d, J = 7.5 Hz, 1 H), 8.18 (dd, J = 13.9, 8.2 Hz, 2 H), 8.08 (dd, J = 17.9, 7.8 Hz, 3 H), 7.94 (s, 1 H), 7.71 (dd, J = 8.0, 4.4 Hz, 1 H), 7.44 (d, J = 7.7 Hz, 1 H), 7.34–7.20 (m, 6 H), 7.10 (dd, J = 7.5, 5.0 Hz, 1 H), 7.01 (dt, J = 14.8, 7.2 Hz, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –6.1 (s).

13C NMR (125 MHz, CDCl3): δ = 151.3 (d, JPC = 3.0 Hz), 148.1, 139.6 (d, JPC = 5.5 Hz), 138.6 (d, JPC = 6.2, 5.6 Hz), 137.4 (d, JPC = 7.4 Hz), 136.8 (d, JPC = 3.9 Hz), 134.7, 134.1, 134.0 (d, JPC = 19.7, 5.3 Hz), 133.1, 132.9, 132.6, 132.0, 131.4, 130.1, 128.7 (d, JPC = 19.4 Hz), 128.5, 128.4 (d, JPC = 6.6 Hz), 128.2, 127.9, 126.5, 126.2 (d, JPC = 4.5 Hz), 126.0, 125.6 (d, JPC = 6.6 Hz), 124.4 (d, JPC = 1.7 Hz), 122.7.

HRMS (p ESI): m/z [M – H]+ calcd for C33H21NP: 462.14116; found: 462.14103.

Anal. Calcd for C33H22NP: C, 85.51; H, 4.78. Found: C, 86.03; H, 4.80.


#

[8-(4-Acetylphenyl)naphthalen-1-yl]diphenylphosphine (20)

Yield: 189 mg (88%); yellow solid; eluent: pentane/dichloromethane (1:3 then 0:1).

1H NMR (500 MHz, CDCl3): δ = 7.96 (d, J = 8.1 Hz, 2 H), 7.67 (d, J = 8.2 Hz, 2 H), 7.56–7.51 (m, 1 H), 7.43–7.39 (m, 1 H), 7.33 (dd, J = 7.0, 1.2 Hz, 1 H), 7.29 (q, J = 6.7, 6.0 Hz, 3 H), 7.25–7.19 (m, 6 H), 7.02–6.96 (m, 4 H), 2.62 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –9.0 (s).

13C NMR (125 MHz, CDCl3): δ = 198.0, 148.7 (d, JPC = 4.6 Hz), 140.2 (d, JPC = 4.3 Hz), 138.9 (d, JPC = 5.5 Hz), 137.8, 135.5, 135.0, 134.9, 134.9, 134.8, 134.7, 131.0 (d, JPC = 7.0 Hz), 130.5 (d, JPC = 6.0 Hz), 129.5 (d, JPC = 1.6 Hz), 128.3, 128.2 (d, JPC = 6.5 Hz), 127.7, 125.6, 124.8, 26.7.

HRMS (p ESI): m/z [M + H]+ calcd for C30H22OP: 431.15593; found: 431.15556.

Anal. Calcd for C30H23OP: C, 83.70; H, 5.39. Found: C, 84.51; H, 5.42.


#

[8-(4-Cyanophenyl)naphthalen-1-yl]diphenylphosphine (21)

Yield: 192 mg (93%); yellow solid; eluent: pentane/dichloromethane (3:1).

1H NMR (500 MHz, CDCl3): δ = 7.92 (t, J = 8.5 Hz, 2 H), 7.51–7.47 (m, 1 H), 7.39–7.35 (m, 1 H), 7.30 (d, J = 8.2 Hz, 2 H), 7.27 (d, J = 9.4 Hz, 1 H), 7.24 (d, J = 3.3 Hz, 2 H), 7.23–7.18 (m, 5 H), 7.14 (d, J = 8.0 Hz, 2 H), 6.96–6.91 (m, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.5 (s).

13C NMR (125 MHz, CDCl3): δ = 148.4 (d, JPC = 4.6 Hz), 139.5 (d, JPC = 4.2 Hz), 138.5 (d, JPC = 14.7 Hz), 137.8, 135.0 (d, JPC = 4.7 Hz), 135.7 (d, JPC = 1.1 Hz), 134.6, 134.5 (d, JPC = 4.8 Hz), 133.8, 133.7, 131.5 (d, JPC = 7.1 Hz), 131.2, 130.6 (d, JPC = 6.5 Hz), 130.0 (d, JPC = 1.6 Hz), 128.6, 128.4, 128.3, 125.8, 124.9, 119.4.

HRMS (p ESI): m/z [M – H]+ calcd for C29H19NP: 412.12496; found: 412.12470.

Anal. Calcd for C29H20NP: C, 84.24; H, 4.88. Found: C, 83.71; H, 4.76.


#

[8-(4-Trifluoromethylphenyl)naphthalen-1-yl]diphenylphosphine (22)

Yield: 125 mg (55%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 7.95–7.91 (m, 2 H), 7.76 (d, J = 8.7 Hz, 1 H), 7.50 (t, J = 7.6 Hz, 1 H), 7.43 (d, J = 8.7 Hz, 1 H), 7.40–7.36 (m, 1 H), 7.28 (d, J = 8.2 Hz, 1 H), 7.26–7.18 (m, 8 H), 7.15 (d, J = 7.9 Hz, 2 H), 6.94 (t, J = 7.4 Hz, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.9 (s).

19F{1H} NMR (470 MHz, CDCl3): δ = –62.4 (s).


#

Diphenyl-(8-phenylnaphthalen-1-yl)phosphine (23)[17]

Yield: 169 mg (87%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 7.99–7.91 (m, 2 H), 7.56–7.51 (m, 1 H), 7.42–7.36 (m, 2 H), 7.33–7.21 (m, 8 H), 7.14 (d, J = 6.6 Hz, 4 H), 7.05–6.99 (m, 4 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.2 (s).


#

Diphenyl-[8-(4-tolyl)-naphthalen-1-yl)phosphine (24)[17]

Yield: 110 mg (55%); yellow solid; eluent: pentane/dichloromethane (4:1).

1H NMR (500 MHz, CDCl3): δ = 7.92 (t, J = 8.5 Hz, 2 H), 7.51 (t, J = 7.5 Hz, 1 H), 7.36 (q, J = 7.5 Hz, 2 H), 7.24 (dt, J = 13.9, 7.1 Hz, 7 H), 7.03–6.96 (m, 5 H), 6.90 (d, J = 4.8 Hz, 2 H), 2.38 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.7 (s).


#

[8-(3,4,5-Trimethoxyphenyl)-naphthalen-1-yl]diphenylphosphine (25)

Yield: 122 mg (51%); yellow solid; eluent: pentane/dichloromethane (1:3).

1H NMR (500 MHz, CDCl3): δ = 8.78 (d, J = 8.2 Hz, 1 H), 8.74 (d, J = 8.3 Hz, 1 H), 8.25 (d, J = 7.5 Hz, 1 H), 8.19–8.13 (m, 3 H), 8.12–8.07 (m, 2 H), 8.03 (t, J = 7.6 Hz, 1 H), 7.67–7.58 (m, 4 H), 7.46 (t, J = 7.3 Hz, 1 H), 7.39–7.30 (m, 3 H), 7.19–7.09 (m, 2 H), 7.09–6.98 (m, 4 H), 6.68 (t, J = 6.8 Hz, 2 H), 6.54 (t, J = 7.2 Hz, 2 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –7.1 (s).

13C NMR (125 MHz, CDCl3): δ = 152.6, 141.3 (d, JPC = 3.3 Hz), 140.3 (d, JPC = 18.5 Hz), 139.0 (d, JPC = 5.1 Hz), 137.8, 137.7, 135.5 (d, JPC = 23.5 Hz), 135.2 (d, JPC = 13.2 Hz), 135.0 (d, JPC = 4.4 Hz), 133.6 (d, JPC = 21.1 Hz), 130.6, 130.3, 129.3 (d, JPC = 1.8 Hz), 128.4 (d, JPC = 6.3 Hz), 128.1, 125.4, 124.8, 108.4 (d, JPC = 7.8 Hz), 61.2, 55.7.

HRMS (p ESI): m/z [M – H]+ calcd for C31H26O3P: 477.161958; found: 477.16090.

Anal. Calcd for C31H27O3P: C, 77.81; H, 5.69. Found: C, 76.78; H, 5.34.


#

[4-(4-Acetylphenyl)-3-fluoranthenyl]diphenylphosphine (26)

Yield: 234 mg (93%); yellow solid; eluent: pentane/dichloromethane (1:3).

1H NMR (500 MHz, CDCl3): δ = 7.98–7.91 (m, 2 H), 7.89 (dd, J = 6.3, 1.3 Hz, 1 H), 7.83 (d, J = 7.2 Hz, 1 H), 7.73 (d, J = 8.2 Hz, 2 H), 7.43 (qd, J = 7.0, 1.2 Hz, 2 H), 7.38 (d, J = 7.1 Hz, 1 H), 7.34–7.27 (m, 3 H), 7.27–7.20 (m, 6 H), 7.01 (t, J = 7.8 Hz, 4 H), 2.66 (s, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –9.2 (s).

13C NMR (125 MHz, CDCl3): δ = 147.6 (d, JPC = 3.7 Hz), 140.8 (d, JPC = 2.1 Hz), 139.2, 139.0, 138.5 (d, JPC = 5.3 Hz), 138.3, 137.9, 137.8 (d, JPC = 1.7 Hz), 136.3 (d, JPC = 29.3 Hz), 135.8, 134.1, 134.0, 133.5 (d, JPC = 5.4 Hz), 132.0 (d, JPC = 21.3 Hz), 131.8, 131.2 (d, JPC = 6.1 Hz), 128.6, 128.4 (d, JPC = 6.7 Hz), 128.3, 127.9, 127.6, 121.7 (d, JPC = 25.2 Hz), 120.1, 119.6, 26.9.

HRMS (p ESI): m/z [M + H]+ calcd for C36H26OP: 505.17213; found: 505.17099.

Anal. Calcd for C36H25OP: C, 85.70; H, 4.99. Found: C, 81.79; H, 4.88.


#

[4-(3,4,5-Trimethoxyphenyl)-3-fluoranthenyl]diphenylphosphine (27)

Yield: 130 mg (47%); yellow solid; eluent: pentane/dichloromethane (1:3).

1H NMR (500 MHz, CDCl3): δ = 7.94 (d, J = 7.1 Hz, 1 H), 7.89 (dd, J = 21.2, 7.1 Hz, 2 H), 7.81 (d, J = 7.2 Hz, 1 H), 7.47 (d, J = 7.1 Hz, 1 H), 7.43–7.36 (m, 2 H), 7.28–7.25 (m, 3 H), 7.22 (t, J = 7.3 Hz, 4 H), 7.01 (t, J = 7.0 Hz, 4 H), 6.32 (d, J = 1.4 Hz, 2 H), 3.94 (s, 3 H), 3.53 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.9 (s).

13C NMR (125 MHz, CDCl3): δ = 152.0, 142.0, 141.9, 139.5 (d, JPC = 16.6 Hz), 139.3, 139.0, 138.4, 138.0, 137.8, 137.7 (d, JPC = 4.1 Hz), 137.3 (d, JPC = 1.7 Hz), 136.7 (d, JPC = 31.4 Hz), 133.7 (d, JPC = 21.0 Hz), 133.3 (d, JPC = 5.2 Hz), 132.4 (d, JPC = 20.7 Hz), 131.6, 128.5 (d, JPC = 6.6 Hz), 128.4, 127.7, 121.6, 121.4, 120.0, 119.6, 108.5 (d, JPC = 6.7 Hz), 61.2, 55.8.

HRMS (p ESI): m/z [M + Na]+ calcd for C37H29O3PNa: 575.17465; found: 575.17341.

Anal. Calcd for C37H29O3P: C, 80.42; H, 5.29. Found: C, 80.20; H, 5.22.


#

[2-(3,4,5-Trimethoxyphenyl)-3-phenanthryl]diphenylphosphine (28)

Yield: 208 mg (79%); yellow solid; eluent: pentane/dichloromethane (1:3).

1H NMR (500 MHz, CDCl3): δ = 8.72 (d, J = 8.4 Hz, 1 H), 8.61 (d, J = 8.4 Hz, 1 H), 7.59–7.52 (m, 2 H), 7.48–7.35 (m, 4 H), 7.12 (dt, J = 14.8, 7.5 Hz, 6 H), 6.92 (t, J = 6.9 Hz, 4 H), 6.22 (s, 2 H), 3.83 (s, 3 H), 3.43 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –7.1 (s).

13C NMR (125 MHz, CDCl3): δ = 152.6, 142.1 (d, JPC = 3.3 Hz), 140.1 (d, JPC = 18.6 Hz), 139.4, 139.1 (d, JPC = 5.3 Hz), 137.8, 134.2 (d, JPC = 31.4 Hz), 133.6 (d, JPC = 21.4 Hz), 132.9 (d, JPC = 19.3 Hz), 131.6 (d, JPC = 4.7 Hz), 131.0, 130.9, 130.8, 128.7, 128.4 (d, JPC = 6.4 Hz), 128.2, 127.8, 126.9, 125.4, 123.0, 122.8 (d, JPC = 1.0 Hz), 108.7 (d, JPC = 7.8 Hz), 61.2, 55.8.

HRMS (p ESI): m/z [M – H]+ calcd for C35H30O3P: 527.17706; found: 527.17636.

Anal. Calcd for C35H29O3P: C, 79.53; H, 5.53. Found: C, 78.87; H, 5.47.


#

1-Diphenylphosphine HAP Oxides; General Procedure

A round-bottom flask equipped with a magnetic stir bar was charged with 1-diphenylphosphine HAP (0.05 mmol, 1 equiv), excess H2O2 and CH2Cl2 (0.025 M, 2 mL). The solution was stirred at room temperature overnight. After extraction (CH2Cl2/H2O), the organic layer was removed in vacuo to give the corresponding product.


#

2-(Diphenylphosphino)fluoranthene Oxide (18-O)

Yield: 21 mg (99%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 8.31 (d, J = 8.5 Hz, 1 H), 7.89–7.86 (m, 3 H), 7.83 (dd, J = 7.1, 1.3 Hz, 1 H), 7.74–7.70 (m, 4 H), 7.58–7.51 (m, 4 H), 7.49–7.46 (m, 4 H), 7.43–7.36 (m, 2 H).

31P{1H} NMR (202 MHz, CDCl3): δ = 30.7 (s).

13C NMR (125 MHz, CDCl3): δ = 141.7 (d, JPC = 2.9 Hz), 140.4, 138.4, 137.6, 135.5 (d, JPC = 2.4 Hz), 133.6, 133.0 (d, JPC = 10.0 Hz), 132.8, 132.3, 132.2, 132.1 (d, JPC = 2.8 Hz), 131.1 (d, JPC = 8.2 Hz), 129.5, 129.4, 129.1, 128.8 (d, JPC = 12.3 Hz), 128.0, 127.4 (d, JPC = 4.0 Hz), 122.4, 121.8, 120.9, 118.5 (d, JPC = 14.1 Hz).

HRMS (p ESI): m/z [M + Na]+ calcd for C28H19OPNa: 425.10657; found: 425.10661.

Anal. Calcd for C28H19OP: C, 83.57; H, 4.76. Found: C, 82.89; H, 4.39.


#

[2-(3,4,5-Timethoxyphenyl)-3-fluoranthenyl]diphenylphosphine Oxide (27-O)

Yield: 22 mg (99%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 7.91 (dd, J = 7.6, 10.9 Hz, 3 H), 7.87–7.78 (m, 2 H), 7.45 (t, J = 7.6 Hz, 2 H), 7.39 (m, 7 H), 7.29 (m, 4 H), 6.26 (s, 2 H), 3.95 (s, 3 H), 3.80 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = 29.1 (s).

13C NMR (125 MHz, CDCl3): δ = 152.0, 142.1, 142.1, 141.9 (d, JPC = 3.1 Hz), 141.0, 140.9 (d, JPC = 1.5 Hz), 139.8, 138.1, 137.2, 137.0 (d, JPC = 5 Hz), 135.9, 135.1, 134.2, 130.8 (d, JPC = 9.3 Hz), 129.3, 128.4 (d, JPC = 12.1 Hz), 128.0, 122.3, 121.5, 120.5, 118.7 (d, JPC = 14.7 Hz), 107.9, 60.8, 55.7.

HRMS (p ESI): m/z [M + H]+ calcd for C37H29O4P: 569.18762; found: 569.18568.

Anal. Calcd for C37H29O4P: C, 78.16; H, 5.14. Found: C, 78.66; H, 5.32.


#

Fluoranthenylphosphine Selenides; General Procedure[21]

A round-bottom flask equipped with a magnetic stir bar was charged with 1-diphenylphosphine HAP (1 equiv, 0.055 mmol) and excess selenium powder in CH2Cl2 (0.025 M, 2 mL). The solution was stirred at room temperature overnight, and the mixture was filtered over Celite and washed with CH2Cl2. The solvent was removed under vacuum to give the corresponding selenide as a yellow solid.


#

2-(Diphenylphosphino)fluoranthene Selenide (18-Se)

Yield: 25 mg (99%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 8.25 (d, J = 8.5 Hz, 1 H), 7.90–7.82 (m, 7 H), 7.75 (d, J = 7.2 Hz, 1 H), 7.55 (m, 2 H), 7.49–7.45 (m, 5 H), 7.44–7.32 (m, 3 H).

31P{1H} NMR (202 MHz, CDCl3): δ = 29.5 (singlet with doublet satellites, J PSe = 724 Hz).

13C NMR (125 MHz, CDCl3): δ = 141.6 (d, JPC = 3.5 Hz), 140.4, 138.4, 137.8, 134.6 (d, JPC = 10.8 Hz), 133.7, 133.6, 133.2 (d, JPC = 11.0 Hz), 131.9, 131.9 (d, JPC = 3.0 Hz), 131.3, 130.1 (d, JPC = 9.8 Hz), 129.1, 128.8 (d, JPC = 12.7 Hz), 128.6, 128.2, 128.0, 127.5 (d, JPC = 5.1 Hz), 122.3, 121.7, 120.9, 118.7 (d, JPC = 14.1 Hz).

HRMS (p ESI): m/z [M + Na]+ calcd for C28H19PSeNa: 489.02818; found: 489.02837.

Anal. Calcd for C28H19PSe: C, 72.26; H, 4.12. Found: C, 71.87; H, 4.02.


#

[2-(3,4,5-Trimethoxyphenyl)-3-fluoranthenyl]diphenylphosphine Selenide (27-Se)

Yield: 22 mg (99%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 8.03 (dd, J = 19.0, 7.3 Hz, 1 H), 7.94–7.87 (m, 4 H), 7.58 (dd, J = 12.9, 7.8 Hz, 3 H), 7.45 (t, J = 7.3 Hz, 1 H), 7.41 (t, J = 6.8 Hz, 2 H), 7.29 (t, J = 7.0 Hz, 2 H), 7.21 (m, 4 H), 6.12 (s, 2 H), 3.94 (s, 3 H), 3.81 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = 38.0 (singlet with doublet satellites, J PSe = 753 Hz).

13C NMR (125 MHz, CDCl3): δ = 152.3, 141.7 (d, JPC = 1.6 Hz), 141.2, 140.8, 140.7, 139.7, 138.2, 137.2, 137.1, 134.1, 132.0, 131.9, 130.5, 129.2, 128.2 (d, JPC = 12.5 Hz), 122.3, 121.5, 120.6, 119.2, 60.9, 55.9.

HRMS (p ESI): m/z [M + Na]+ calcd for C37H29O3PSeNa: 655.09117; found: 655.08922.

Anal. Calcd for C37H29O3PSe: C, 70.36; H, 4.63. Found: C, 70.82; H, 4.81.


#

Au(I)Cl and Cu(I)Cl Complexes A–D; General Procedure[23]

A round-bottom flask (50 mL) equipped with a magnetic stir bar was charged with 1-diphenylphosphine HAP (0.055 mmol, 1 equiv), gold chloride [(Me2S)AuCl] (0.055 mmol, 1 equiv) or copper chloride CuCl (0.055 mmol, 1 equiv) and CH2Cl2 (0.025 M, 2 mL). The solution was stirred at room temperature overnight, and the mixture was then filtered over Celite and washed with CH2Cl2. The solvent was removed under vacuum to give the corresponding complex. Crystallization or precipitation was undertaken using CH2Cl2 solution and the slow addition of a minimum quantity of pentane.


#

Gold Complex Stabilized by 2-(Diphenylphosphino)fluoranthene (A)

Yield: 362 mg (99%); white solid.

1H NMR (500 MHz, CDCl3): δ = 8.23 (d, J = 8.4 Hz, 1 H), 7.89 (d, J = 6.9 Hz, 1 H), 7.86 (d, J = 7.5 Hz, 2 H), 7.79 (d, J = 7.1 Hz, 1 H), 7.63 (dd, J = 13.5, 7.6 Hz, 4 H), 7.57 (t, J = 7.2 Hz, 2 H), 7.53 (d, J = 8.1 Hz, 1 H), 7.50 (dt, J = 7.1, 3.9 Hz, 4 H), 7.40 (m, 2 H), 7.17 (dd, J = 14.4, 7.1 Hz, 1 H).

31P{1H} NMR (202 MHz, CDCl3): δ = 24.5 (s).

13C NMR (125 MHz, CDCl3): δ = 141.8 (d, JPC = 2.3 Hz), 140.1, 138.2, 138.0 (d, JPC = 1.3 Hz), 135.3 (d, JPC = 8.5 Hz), 134.9 (d, JPC = 14.1 Hz), 133.1 (d, JPC = 9.4 Hz), 132.4 (d, JPC = 1.7 Hz), 130.5 (d, JPC = 12.1 Hz), 129.8, 129.6 (d, JPC = 12.1 Hz), 129.3, 128.7 (d, JPC = 63.6 Hz), 128.2, 125.3 (d, JPC = 9.7 Hz), 124.8 (d, JPC = 62.4 Hz), 122.4, 121.9, 121.2, 119.1 (d, JPC = 11.5 Hz).

HRMS (p ESI): m/z [M + Na]+ calcd for C28H19AuClPNa: 641.04706; found: 641.04800.

Anal. Calcd for C28H19AuClP: C, 54.34; H, 3.09. Found: C, 53.47; H, 2.93.


#

Gold Complex Stabilized by [2-(3,4,5-Trimethoxyphenyl)-3-fluoranthenyl]diphenylphosphine (B)

Yield: 41 mg (97%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 7.94 (d, J = 7.1 Hz, 1 H), 7.89 (dd, J = 14.2, 7.4 Hz, 2 H), 7.83 (d, J = 7.3 Hz, 1 H), 7.50–7.43 (d, J = 7.1 Hz, 1 H), 7.41–7.36 (m, 4 H), 7.38 (m, 9 H), 6.30 (s, 2 H), 3.93 (s, 3 H), 3.58 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = 30.4 (s).

13C NMR (125 MHz, CDCl3): δ = 153.0, 141.6 (d, JPC = 2.9 Hz), 141.1 (d, JPC = 3.5 Hz), 140.8 (d, JPC = 7.1 Hz), 139.7, 138.1, 138.0, 137.6, 137.5 (d, JPC = 1.9 Hz), 134.5, 134.3 (d, JPC = 9.7 Hz), 133.9 (d, JPC = 14.0 Hz), 132.3, 131.8, 131.6 (d, JPC = 2.3 Hz), 131.3 (d, JPC = 11.8 Hz), 129.5, 129.3 (d, JPC = 11.8 Hz), 128.2, 125.8, 125.4, 122.3, 121.7, 120.7, 119.0 (d, JPC = 11.0 Hz), 108.4, 61.3, 56.0.

HRMS (p ESI): m/z [M + Na]+ calcd for C37H29AuClO3PNa: 807.11006; found: 807.11375.

Anal. Calcd for C37H29AuClO3P: C, 56.61; H, 3.72. Found: C, 53.06; H, 3.35.


#

Copper Complex Stabilized by 2-(Diphenylphosphino)fluoranthene (C)

Yield: 37 mg (73%); white solid.

1H NMR (500 MHz, CDCl3): δ = 8.33 (d, J = 8.1 Hz, 1 H), 7.81 (d, J = 6.5 Hz, 1 H), 7.73 (d, J = 6.5 Hz, 1 H), 7.67 (d, J = 6.8 Hz, 1 H), 7.57 (s, 3 H), 7.48 (d, J = 6.8 Hz, 1 H), 7.36–7.27 (m, 4 H), 7.17 (t, J = 7.4 Hz, 4 H), 7.08 (s, 1 H), 6.92 (s, 1 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –8.7 (br s).

13C NMR (125 MHz, CDCl3): δ = 140.1, 139.3, 138.8, 137.0, 134.7, 134.6, 134.2 (d, JPC = 2.8 Hz), 132.8 (d, JPC = 6.7 Hz), 132.2 (d, JPC = 36.0 Hz), 131.4, 131.3, 130.1, 128.8 (d, JPC = 8.9 Hz), 128.6 (d, JPC = 36.1 Hz), 127.6, 127.2 (d, JPC = 11.0 Hz), 121.9, 121.5, 120.6, 119.3 (d, JPC = 5.6 Hz).

HRMS (p ESI): m/z [2 M + H]+ calcd for C56H39Cl2Cu2P2: 969.04961; found: 969.21468.

Anal. Calcd for C28H19ClCuP: C, 69.28; H, 3.92. Found: C, 70.06; H, 4.02.


#

Copper Complex Stabilized by [2-(3,4,5-Trimethoxyphenyl)-3-fluoranthenyl]diphenylphosphine (D)

Yield: 26 mg (76%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 7.89 (d, J = 7.1 Hz, 1 H), 7.86–7.82 (m, 2 H), 7.81 (d, J = 7.3 Hz, 1 H), 7.43 (d, J = 7.0 Hz, 4 H), 7.38 (t, J = 10.2 Hz, 10 H), 6.29 (s, 2 H), 3.92 (s, 3 H), 3.22 (s, 6 H).

31P{1H} NMR (202 MHz, CDCl3): δ = –5.3 (br s).

13C NMR (125 MHz, CDCl3): δ = 154.0, 140.7, 140.3 (d, JPC = 8.6 Hz), 139.5, 138.4, 137.9, 137.5, 136.7 (d, JPC = 2.2 Hz), 133.7, 133.7 (d, JPC = 15.6 Hz), 132.9, 132.0 (d, JPC = 16.8 Hz), 130.4, 129.1 (d, JPC = 9.9 Hz), 128.9, 128.0, 122.0, 121.6, 120.2, 119.5 (d, JPC = 6.1 Hz), 104.0, 61.2, 55.5.

HRMS (p ESI): m/z [1/2 M – Cl]+ calcd for C37H29ClCuO3P: 615.11448; found: 615.11487.

Anal. Calcd for C37H29ClCuO3P: C, 68.20; H, 4.49. Found: C, 67.84; H, 4.30.


#

2,5-Disubstituted Oxazoles; General Procedure

An oven-dried Schlenk tube equipped with a magnetic stir bar was charged with a terminal alkyne (0.6 mmol, 1 equiv), 8-methylquinoline N-oxide (0.78 mmol, 1.3 equiv), [Au] (0.03 mmol, 5 mol%), and AgNTf2 (0.09 mmol, 15 mol%) in acetonitrile or benzonitrile (0.2 M, 3 mL). The mixture was stirred at 50 °C under argon for 5 h. The crude product was purified by column chromatography on silica gel using a mixture of pentane/ethyl acetate as the eluent.


#

5-(4-Methoxyphenyl)-2-methyloxazole (29)[25a]

Yield: 105 mg (93%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 7.87 (d, J = 8.9 Hz, 3 H), 7.19 (s, 1 H), 6.87 (d, J = 8.9 Hz, 1 H), 3.80 (s, 3 H), 2.49 (s, 3 H).


#

5-(4-Methoxyphenyl)-2-phenyloxazole (30)[26]

Yield: 123 mg (82%); yellow solid.

1H NMR (500 MHz, CDCl3): δ = 8.10 (d, J = 6.6 Hz, 2 H), 7.65 (d, J = 8.8 Hz, 2 H), 7.50–7.43 (m, 3 H), 7.32 (s, 1 H), 6.97 (d, J = 8.8 Hz, 2 H), 3.85 (s, 3 H).


#

5-(4-Fluorophenyl)-2-methyloxazole (31)[27]

Yield: 85 mg (80%); white solid.

1H NMR (500 MHz, CDCl3): δ = 7.50 (dd, J = 8.8, 5.2 Hz, 2 H), 7.07 (s, 1 H), 7.03 (t, J = 8.7 Hz, 2 H), 2.45 (s, 3 H).

19F{1H} NMR (470 MHz, CDCl3): δ = –112.9 (s).


#
#

Conflict of Interest

The authors declare no conflict of interest.

Acknowledgment

We are grateful to the ‘Chemical Analysis Platform and Molecular Synthesis University of Burgundy’ (PACSMUB) platform for analyses (SATT SAYENS), especially M.-J. Penouilh, Q. Bonnin and T. Régnier.

Supporting Information

    Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-2018-0965.
  • Supporting Information

Corresponding Authors

Julien Roger
Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 6302, Université de Bourgogne
9 Avenue Alain Savary, 21078 Dijon Cedex
France   

Jean-Cyrille Hierso
Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 6302, Université de Bourgogne
9 Avenue Alain Savary, 21078 Dijon Cedex
France   

Publication History

Received: 26 October 2022

Accepted after revision: 23 January 2023

Accepted Manuscript online:
23 January 2023

Article published online:
14 March 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany


   Permissions and Reprints All articles of this category
Zoom Image
Scheme 1 Previous work using aryl triflates as substrates in transition-metal-catalyzed C–H direct (hetero)arylation (top left), and nitrogen- and oxygen-directed arylation (top right), along with the present work on phosphorus-directed rhodium-catalyzed C–H arylation of PAH phosphines (bottom)
Zoom Image
Scheme 2 P-directed C–H arylation of 1-diphenylphosphine pyrene 1 using functional aryl triflates. Conditions: 1-diphenylphosphine pyrene 1 (0.5 mmol, 1 equiv), aryl triflate (1.5 equiv), [RhCl2Cp*]2 (2.5 mol%), K3PO4 (3.0 equiv), in anhydrous trifluoromethylbenzene [0.165 M] at reflux, 18 h under argon. 1H NMR yield are given with isolated yields in brackets. a The corresponding 10-(4-trifluoromethylsulfonate phenyl)-1-diphenylphosphine pyrene 5 was also detected in 14% yield. b The corresponding 10-(4-bromomethylsulfonate phenyl)-1-diphenylphosphine pyrene 5′ was also detected in 8% yield.
Zoom Image
Scheme 3 Selected arylations of other polyaromatic hydrocarbon diphenylphosphines with aryl triflates. Conditions: 1-diphenylphosphine PAH (0.5 mmol, 1 equiv), aryl triflate (1.5 equiv), [RhCl2Cp*]2 (2.5 mol%), K3PO4 (3.0 equiv), in anhydrous trifluoromethylbenzene [0.165 M] at reflux, 18 h under argon. 1H NMR yields; isolated yields are given in brackets.
Zoom Image
Scheme 4 Au(I)Cl complexes A and B and Cu(I)Cl complexes C and D, stabilized by fluoranthenylphosphines 18 and 27, respectively
Zoom Image
Figure 1 Molecular structure of complex B (thermal ellipsoids at 30% probabilities, H atoms and one CH2Cl2 are omitted for clarity)