Dynamics and Conformational Stability of Chiral Bay‐Phenolate‐Substituted Twisted Octaazaperopyrenedioxides (OAPPDOs)

TL;DR

Researchers created stable chiral fluorophores by adding BINOL units to OAPPDOs, enabling the study of their chiroptical properties like CPL.

Contribution

The paper introduces a new class of chiral fluorophores with conformational flexibility and high thermal stability.

Findings

Chiral OAPPDO derivatives show remarkable thermal stability and low racemization.

DFT modeling revealed an activation barrier above 170 kJ mol−1 for racemization.

The fluorophores exhibit circular polarized luminescence with a g_lum of 2×10−4.

Abstract

Configurationally stable chiral octaazaperopyrene dioxide (OAPPDO) derivatives were obtained by nucleophilic substitution of chiral BINOL and related fragments as bridging units onto the bay position. The addition of these phenolate derivatives has given rise to a new group of bright chiral fluorophores with remarkable thermal stability, which allowed the study of their chiroptical properties, in particular, their circular dichroism characteristics as well as circular polarized luminescence (CPL), albeit with a low dissymmetry factor (g
lum) in the range of 2*10−4. The introduction of the BINOL bridging groups in the bay position led to equilibria between chiral conformers in solution, the interconversion of which has been studied by DFT modeling, with the two lowest energy species being directly observable in situ by NMR. Insight into the stability of these derivatives with respect to overall racemization has been obtained by DFT modeling which established an overall activation barrier for the process of above 170 kJ mol−1.

Chiral octaazaperopyrenedioxide (OAPPDO) fluorophores were obtained by functionalizing with BINOL and related fragments bridging the bay position. They possess conformational flexibility but remarkable thermal stability with respect to racemization of the central chromophore, which allowed the study of their chiroptical properties, including circular polarized luminescence (CPL).

Figures

(A) Synthesis of bay‐phenoxy functionalized OAPPDO derivatives; (B) Synthesis of bay‐bridged phenoxy substituted OAPPDO derivatives.

Molecular structures of 8 (top) and 10 (bottom), front and side view. Thermal displacement ellipsoids at 50 % probability level (for simplicity purposes the n‐hexyl chains and H atoms were omitted). Torsion angle = ∡ϕ, is measured between the tetraazaphenalenylone units of one molecule.

Absorption and emission spectra of compounds 3–14.

Top: Molecular structure of 11, front and side view of compound; Bottom: Molecular structure of 14, front and side view. Thermal displacement ellipsoids at 50 % probability level (for simplicity the n‐hexyl and neopentyl chains and H atoms were omitted). The bisphenol and BINOL bridges are displayed as faded scaffolds in the front views of the molecules for reasons of clarity. Torsion angles are measured between the tetraazaphenalenylone units within the molecules.

Top: CD spectra of 12–14 measured in dichloromethane at 293 K; Bottom: CPL spectra of enantiomers of derivatives 12–14 in dichloromethane at 293 K upon excitation at 407 nm.

Experimentally identified low‐energy conformers of compound 13 (front and side view) assigned to well separated aromatic proton resonances in the low‐temperature 1H NMR spectrum (185 K in CD2Cl2), alongside their computed and experimentally derived relative free Gibbs energies. A range was given depending on the level of theory for ΔGDFT.

Conformational space of a CH3─N truncated structure for 13 computed on the B3LYP‐GD3(BJ)/Def2‐TZVP level of theory. Relative free Gibbs energies in brackets (below minimum structures; for transition states: next to the arrows) are given in kJ mol−1.

Relative Gibbs free energy profile of the lowest‐energy racemization pathway starting at the global minimum structure 13‐CONF1. Only one half of the complete symmetrical inversion mechanism is depicted leading to the achiral intermediate RAC‐INT4. Energies are given in kJ mol−1.

Tables

TABLE 1. Photophysical and chiroptical data of 12–14.

	λ abs,max (nm) (log ε) a	λ abs,max (nm) (Φ em) a , b	|g lum| x 10−3	BCPL (M−1 cm−1)
12	504 (4.55)	510 (80%)	0.24	2.83
13	502 (4.47)	508 (72%)	0.20	2.13
14	502 (4.45)	510 (83%)	0.17	1.17

Full text

Introduction

1

Perylene diimides (PDIs) are among the most extensively studied polycyclic hydrocarbons due to their combination of high photostability and high emission quantum yields as well as rich redox chemistry [1, 2, 3, 4]. In addition, through peripheral modification of the aromatic core the packing in the solid state and morphology of PDI‐derived materials has been shown to be readily controllable [4, 5, 6, 7, 8, 9, 10, 11, 12, 13]. Helical chirality can be induced by twisting the perylene core [14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34], substituting chiral moieties [35, 36, 37, 38, 39], or coassembly of achiral PDIs and chiral guests [40, 41, 42, 43, 44, 45, 46, 47, 48]. This provides the basis of a wide range of applications [13, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58].

Würthner and coworkers succeeded in distorting the central perylene scaffold by introducing bulky substituents in the bay position, including various arene groups [27, 32] and a 2,2’‐biphenol unit [38, 39]. In these cases, the racemization barrier could be increased, although using 2,2’‐biphenol as linking substituent for neighboring bay positions only proved to have a minimal effect. However, in recent work the substitution of benzo[ghi]‐perylene trisimides (BPTIs) with a BINOL unit has given rise to a twisted product with a racemization barrier of ΔG483K‡ = 160 kJ mol^−1^ which proved to be effective for the enantioselective recognition of helicenes via adduct formation [36].

We previously reported a new class of functional dyes based on a tetraazaperylene core which are decorated with urea units in the peri positions. This structural motif may be viewed as formally inverted with respect to the carboximide groups in the PDIs [59, 60]. These octaazaperopyrenedioxides (OAPPDOs) possess a twisted tetraazaperylene core with chlorine atoms or other substituents in the bay position, leading to helically chiral isomers. In most cases rapid interchange between the twisted conformations makes it impossible to isolate the enantiomers at room temperature. A strategy to overcome the low racemization barrier and isolate thermally stable enantiopure dyes is based on increasing the steric hindrance in the bay position. This has been achieved by the synthesis of tetraphenylated OAPPDOs [59], which are configurationally stable at room temperature, and more recently, in the fourfold bay‐alkynylated OAPPDOs [61]. For the latter the enantiomerically pure derivatives were isolated, however, a racemization barrier of 93 kJ mol^−1^ still proved too low for most applications [62].

In this work, we report the successive conformational stabilization of OAPPDO derivatives by initially studying the effect of substituting increasingly bulkier or electron poor phenoxy groups into the bay position. The aim has been to understand how the presence of specific groups influences their reactivity and yield by variation of steric hindrance and nucleophilicity. Subsequently, the introduction of enantiomerically pure bridged phenoxy groups, yielded enantiomerically pure derivatives, in which a mixture of steric bulk and geometrical constraints significantly stabilized the respective enantiomers, thus allowing their isolation and structural and chiroptical characterization, including a first observation of circular polarized luminescence (CPL) for OAPPDO derivatives.

Results and Discussion

2

Synthesis and Structural Characterization of Bay‐Phenolate‐Substituted OAPPDOs

2.1

The previously reported bay‐chlorinated OAPPDO derivatives 1 and 2 [59, 61] were suitable starting materials for the preparation of phenol ether‐functionalized compounds 3–14 via nucleophilic substitution in the bay position (Scheme 1). In all cases, the corresponding phenoxy derivatives were prepared in situ by deprotonation of the phenols and subsequent nucleophilic attack on compounds 1 and 2.

(A) Synthesis of bay‐phenoxy functionalized OAPPDO derivatives; (B) Synthesis of bay‐bridged phenoxy substituted OAPPDO derivatives.

For compounds 3–10, phenol‐substituents in the ortho and para positions were chosen to study the effect and limitations of increasing the steric hindrance on the substitution rate (Scheme 1A). The first approach was to utilize ortho‐substituted phenolates which resulted in compounds 3–5b and 10. By varying the degree of steric bulk at the phenol groups, tetrasubstitution was observed for compounds 3–5b. Tetrasubstitution was also observed for the reaction using para‐substituted and perfluorinated phenols, which led to derivatives 6–8 and 9, respectively. This demonstrates that the use of *para‐*substituted or electron‐poor phenols has no influence on the degree of substitution of 1, while the low nucleophilicity of the perfluorinated phenol resulted in a lower reaction yield for 9. However, the reaction of 1 with 2,6‐diphenylphenol only gave the trans‐disubstituted derivative 10. The trans conformation is favored because the repulsion of the bulky phenoxy groups is minimized.

The structural information obtained by means of X‐ray diffraction of 8 and 10 (Figure 1) established the twisted chiral distortion of the azaperylene core for 8 [torsion angle of 27.06(3)°], comparable to previously reported *bay‐*arylated OAPPDOs, whereas 10 adopts a “meso” conformation with two opposite torsion angles of the bay positions [±32.32(2)°] [59]. Thus, in contrast to the other phenoxy‐substituted OAPPDO, the two diazanaphthyridene units in compound 10 have a quasi‐zero overall twist.

Molecular structures of 8 (top) and 10 (bottom), front and side view. Thermal displacement ellipsoids at 50 % probability level (for simplicity purposes the n‐hexyl chains and H atoms were omitted). Torsion angle = ∡ϕ, is measured between the tetraazaphenalenylone units of one molecule.

A closer inspection of the molecular structure of 10 (Figure 1) suggests that the positioning of one of the ortho‐phenyl groups above and below the tetraazaperylene core (Figure 1, bottom, right) limits further substitution of the available chlorine atoms. Elongated C─C bonds between the two naphthyridine subunits in both 8 (1.462 Å) and 10 (1.461 and 1.472 Å, respectively), indicate a reduced delocalization of the π system between the naphthyridine moieties which is characteristic for related bay‐substituted perylene structures [59, 60, 61, 63] and also higher rylene derivatives [64].

The photophysical properties of OAPPDO derivatives 3–10 were investigated by UV‐VIS and fluorescence spectroscopy (Figure 2). Compounds 3–10 display a hypsochromic shift of the principal absorption band in the visible region, with maxima between 497 and 515 nm in comparison to previously published thioether functionalized OAPPDO derivatives [63]. Fluorescence quantum yields in the range of 52%–78% were found with the emission bands being Stokes‐shifted up to 830 cm^−1^ for the conformationally flexible monophenolate derivatives (3 and 6–8). Additionally, as presented in Table S1, increasing the steric hindrance in either the ortho or para position of the phenoxy substituents led to an expected decrease in the Stokes shift. This is particularly prominent when comparing compounds 3 and 5b, in which there is a decrease from 758 to 260 cm^−1^. Notably, the disubstituted derivative 10 does not follow the trend of the other ortho‐substituted derivatives in displaying a larger Stokes shift of 642 cm^−1^. To further study the effect of steric bulk in the bay position, we attempted to isolate the enantiomers of compounds 3–10, however due to fast interconversion at room temperature isolation of the enantiomers is not possible. Therefore, no chiroptical studies were carried out.

Absorption and emission spectra of compounds 3–14.

Top: Molecular structure of 11, front and side view of compound; Bottom: Molecular structure of 14, front and side view. Thermal displacement ellipsoids at 50 % probability level (for simplicity the n‐hexyl and neopentyl chains and H atoms were omitted). The bisphenol and BINOL bridges are displayed as faded scaffolds in the front views of the molecules for reasons of clarity. Torsion angles are measured between the tetraazaphenalenylone units within the molecules.

Conformationally Stable OAPPDO Derivatives: Bridging the Bay‐Positions with BINOL Units

2.2

Whereas tetrasubstitution is the usual pattern of reactivity for the OAPPDOs [59, 61, 63, 65], compound 10 is a disubstituted system which indicates that the ortho‐diphenyl‐substituted phenol is too bulky for complete substitution of the bay‐chlorine atoms. This led us to employ a bridging diphenol with two adjacent phenoxy groups that are connected directly at the ortho positions through a covalent C−C bond to increase the racemization barrier of our systems.

Reaction 1 with 2,2’‐bisphenol yielded compound 11. Previous reports have indicated that the introduction of bridging bay substituents suppressed the interconversion between the twisted conformers [36, 38, 39]. However, in the case at hand, the enantiomers were not separable due to their fast interconversion at room temperature and therefore chiroptical studies were not performed.

Consequently, enantiomerically constrained (R/S) 5,5’,6,6’,7,7’,8,8’‐octahydro‐1,1’‐[binaphthalene]‐2,2’‐diol (H_8_‐BINOL), and 1,1’‐ bi‐2‐naphthol (BINOL) groups possessing high racemization barriers were employed [66, 67, 68, 69]. Nucleophilic substitution with enantiomerically pure fragments lead to the isolation of enantiomerically pure S and R conformations of 12–14.

The molecular structures of 13 and 14 (Figure 3) indicate that the BINOL unit in the bay position and the OAPPDO have the same absolute configuration, therefore the configuration of these systems can be noted as S,S,S and R,R,R (this nomenclature can be simplified as M and P isomers in the description of the chiroptical properties); considering the stability against racemization of the H_8_‐BINOL and the similar geometry [69, 70, 71], the same nomenclature can be used for 12. The BINOL substitution in the bay position of 13 and 14 results in a twist of the perylene core of approximately 27.2(2) ° and 25.7(4) °, respectively. We note that the molecular structures of 13 and 14 mirror the reported mono‐BINOL substituted benzo[ghi]‐perylene trisimides [36].

As expected and similar to compound 5b, the relatively rigid bridged bisphenol/naphthol derivatives 11–14 were found to have reduced Stokes shifts of 234–313 cm^−1^ (Figure 2 and Table S1, Supporting Information) for their π*→π emission bands.

Circular Dichroism and Circular Polarized Luminescence of the OAPPDO Derivatives 12–14

2.3

The two enantiomers of compounds 12–14 exhibit mirror‐imaged circular dichroic activity (Figure 4, top) with a well‐defined pattern of spectral features. To determine the thermal stability of this new class of chiral emitters, compounds 12 and 13 were subjected to temperature dependent studies of the racemization rate in n‐octane. At 363 K for 140 h and 363 K for 149 h no experimentally significant racemization was observed (see Figures S41 and S42).

Top: CD spectra of 12–14 measured in dichloromethane at 293 K; Bottom: CPL spectra of enantiomers of derivatives 12–14 in dichloromethane at 293 K upon excitation at 407 nm.

CPL had not been observable in previously reported chiral OAPPDO derivatives due to racemization [59, 61]. The remarkable thermal stability and the inter‐ring twist conformation of the H_8_‐BINOL and BINOL substituents of compounds 12–14 now allowed the observation of CPL emissions (Figure 4, bottom). The CPL spectra of all three compounds (recorded in dichloromethane at 293 K upon excitation at 407 nm) are in good agreement with the fluorescence spectra and the enantiomers show inverted signals. The emission dissymmetry factors (g lum) [72] of all three compounds are in the range of 2.2 ± 0.6*10^−4^ (Table 1) and are similar to previously reported related systems [1, 36, 69, 72, 73].

To fully assess the potential as CPL emitters of the chiral OAPPDO derivatives, their brightness (B_CPL_) was calculated following the equation published by Arrico et al [74]. This quantity provides an integrated perspective on the key photophysical parameters (such as absorption extinction coefficient and quantum yields) to determine the amount of CP protons emitted by a compound and therefore allows for a direct comparison between systems. The B_CPL_ values of compounds 12, 13, and 14 are 2.83, 2.13, and 1.17 M^−1^cm^−1^, respectively.

Although similar to polyaromatic molecules previously reported [36, 74], these are rather low B_CPL_ values, which is probably due to the combination of low g lum and extinction coefficients (28064 to 35310 M^−1 ^cm^−1^). The fluorescence kinetics of the enantiomers of derivatives 12–14 were further investigated by tr‐PL spectroscopy (see Figures S44, and S45, Supporting Information). The emission kinetics shows a strong prompt emission that decays mono‐exponentially with a lifetime of 6–7 ns for all samples. No changes in recombination kinetics were found to be induced by the structural variations among the studied molecules.

Conformational Flexibility of the Bridging BINOL Ether Units in Solution

2.4

Given the conformational flexibility of the bridging BINOL units we screened the low energy conformational space of a CH_3_─N truncated structure for 13 by DFT. This led to the identification of two nearly isoenergetic conformers in equilibrium (13’‐CONF1 and 13’‐CONF2), complicating spectral modeling by requiring weighted averaging (Figure 5 and Scheme 2) [75, 76, 77, 78].

Experimentally identified low‐energy conformers of compound 13 (front and side view) assigned to well separated aromatic proton resonances in the low‐temperature 1H NMR spectrum (185 K in CD2Cl2), alongside their computed and experimentally derived relative free Gibbs energies. A range was given depending on the level of theory for ΔGDFT.

The thermodynamically favored conformer predicted in silico aligns precisely with the experimentally resolved structure of 13 in crystallo. The presence of the second, slightly less stable conformer (ΔGr2SCAN−3c298K = 2.8 kJ mol^−1^ or ΔGB3LYP298K = 4.4 kJ mol^−1^; see Scheme S1) was confirmed experimentally via low‐temperature ^1^H NMR spectroscopy at 185 K (Figure 5). Integration ratios of both isomers revealed a free Gibbs energy difference of 1.8 kJ mol^−1^, consistent with the theoretical prediction. We note that both identified conformers have the same orientation of the central twisted OAPPDO chromophore, however, the flexibility granted by the bridging ether groups allow for their different spatial positioning.

To probe the conformational space accessible to the BINOL bridges beyond the spectroscopically identified conformers, a systematic scan for further local conformational minima was performed which left the helical chirality of the peripheral BINOL units intact (Scheme 2, for more details see Supporting Information). While conformers 13‐CONF1 and 13‐CONF2 (vide supra) can interconvert directly via one transition state, a nearly isoenergetic alternative route involves a third conformer intermediate (13’‐CONF3) in which partial “unfolding” of one BINOL unit occurs concomitantly with loss of chirality in the OAPPDO core. Subsequent steps involve either a complete unfolding of this BINOL moiety (13‐CONF4) or partial unfolding of the second BINOL unit, leading to 13‐CONF5 with inverted chirality in the OAPPDO core. Both pathways can further proceed to a conformer with unfolded BINOL units on both sides as represented by 13‐CONF7. However, all these additional conformers would be high‐energy species and thus not detectable in solution.

Conformational space of a CH3─N truncated structure for 13 computed on the B3LYP‐GD3(BJ)/Def2‐TZVP level of theory. Relative free Gibbs energies in brackets (below minimum structures; for transition states: next to the arrows) are given in kJ mol−1.

DFT Modeling of Potential Racemization Pathways

2.5

Despite being of high‐energy, these additional conformers may be involved in the racemization mechanism. Therefore, the inversion of BINOL chirality was modeled starting from each of the conformationally distinct species mentioned above (for all transition state energies see Supporting Information). Although BINOL chirality inversion starts with an energetically favored transition state when initiated at 13’‐CONF4, the overall energetically lowest pathway originates from the global enantiomeric minimum structure 13‐CONF1 as illustrated in Figure 6. Here, the rate determining step was found to be the BINOL chirality inversion itself with a computed relative Gibbs free energy of ΔGB3LYP‡ = 178.3 kJ mol^−1^. Using the Eyring–Polanyi equation (κ = 1), this value corresponds to a rate constant of k = 1.710^−13^ s^−1^ at 363 K, predicting negligible racemization after 150 h (99.99998% ee). Furthermore, achieving ∼50% racemization (∼50% ee) necessitates 2.410^7^ days or a temperature of 485 K over 150 h.

Relative Gibbs free energy profile of the lowest‐energy racemization pathway starting at the global minimum structure 13‐CONF1. Only one half of the complete symmetrical inversion mechanism is depicted leading to the achiral intermediate RAC‐INT4. Energies are given in kJ mol−1.

After the completed inversion of one BINOL, the isomer RAC‐INT2 forms, that is structurally related to conformer 13’‐CONF4 but possesses inverted chirality in the now fully unfolded BINOL unit. This isomer can relax into the achiral isomer RAC‐INT4, mirroring the relaxation pathway from 13‐CONF4. Configurational inversion of OAPPDO 13 is completed by reversing this pathway, starting at RAC‐INT4 for the inversion of the second BINOL moiety. This results in an overall symmetrical profile. Notably, a nearly isoenergetic alternative pathway starts from conformer 13’‐CONF2 proceeding to RAC‐INT2 (see Scheme S6).

As is apparent in Figure 6, the computed activation barrier of 178 kJ mol^−1^ for the lowest energy racemization pathway for the BINOL‐decorated OAPPDOs is consistent with the conformational stability of these chiral dye molecules at elevated temperatures in solution. It also explains their stability upon high intensity laser excitation in the CPL experiments.

Conclusion

3

In conclusion, this study establishes a robust platform for designing structurally stabilized chiral fluorophores by introduction of rigid‐bridged phenolate substitutions, such as H_8_‐BINOL and BINOL. This strategy successfully addresses the challenge of achieving thermally stable axial chirality in OAPPDOs derivatives and provides the basis for the further development of this approach. Their thermal stability allowed the observation of CPL of chiral OAPPDO derivatives for the first time.

Theoretical modeling of low‐energy conformers and their interconversion has highlighted the effect of residual conformational flexibility at equilibrium. The racemization barriers of 12 and 13 rival those reported for structurally related benzo[ghi]perylene trisimides substituted with a BINOL unit [36].

Experimental Section

4

All starting materials and solvents were purchased from commercial sources and used without further purification. Deuterated solvents were bought from Sigma–Aldrich. The ^1^H and ^13^C NMR spectra were recorded with a Bruker Avance II 400 or 600 spectrometer and are referenced to the residual signal of CDCl_3_ (^1^H: 7.26 ppm; ^13^C: 77.16 ppm), CD_2_Cl_2_ (^1^H: 5.32 ppm; ^13^C: 53.84 ppm), THF‐d_8_ (^1^H: 1.72 and 3.58 ppm; ^13^C: 25.31 and 67.21 ppm), TCE‐d_2_ (^1^H: 5.98 ppm; ^13^C: 74.05 ppm) [79]. The following abbreviations were used to describe the multiplicities: s = singlet, bs = broad singlet, d = doublet, m = multiplet, t = triplet. MALDI mass spectra were measured on a Bruker ApexQe hybrid 9.4 T FT‐ICR by the department of Organic Chemistry of Heidelberg University under the direction of Dr. J. Gross. The UV‐Vis absorption spectra were recorded on a Cary 5000 UV‐Vis spectrometer and were baseline and solvent corrected. The fluorescence spectra were recorded on a Varian Cary Eclipse Fluorescence spectrophotometer and emission quantum yields (Φ) were measured on a JASCO spectrofluorometer FP‐8500 equipped with an ILF‐835j100 mm integrating sphere. Circular dichroism spectra were recorded with a Jasco J‐1700 Circular Dichroism Spectrophotometer in dichloromethane and n‐octane; path length: 1 cm. IR‐spectra were measured with a Bruker ALPHA‐FT‐IR (diamond ATR‐crystal). Single crystal X‐ray diffraction analyses were performed by Dr. Joachim Ballmann in the X‐ray laboratory of the department of Inorganic Chemistry at Heidelberg University with an Agilent Supernova E diffractometer. Unless otherwise stated, all preparative work was performed under inert gas atmosphere using standard Schlenk glassware, which was flame dried prior to use. An oil bath was used as a heat source for all reactions that required heating. OAPPDO 1 and 2 were synthesized according to a procedure reported in the literature [59, 61].

General Procedure 1: Following a modified literature procedure [63], OAPPDO 1, K_2_CO_3_ and corresponding phenol were dissolved in DMF, the mixture was stirred for 24 h at 145 °C. The mixture was cooled to room temperature, poured into distilled water and extracted with dichloromethane. The organic phase was collected and dried under vacuum. The crude product was purified by flash column chromatography.

General Procedure 2: Following a modified literature procedure [36, 39], OAPPDO 1 or 2, K_2_CO_3_ and the corresponding bridged biphenoxy group (enantiomer S or R), were dissolved in DMF and the mixture was stirred for 7 days at 140 °C. The mixture was cooled to room temperature, poured into distilled water and extracted with dichloromethane. The organic phase was collected and dried under vacuum. The crude product was purified by flash column chromatography.

Compound 3: According to GP1 compound 1 (100 mg, 119 µmol, 1 equiv.), phenol (56 mg, 593 µmol, 5 equiv.) and K_2_CO_3_ (66 mg, 475 µmol, 5 equiv.) were dissolved in 10 of DMF and stirred for 24 h at 145°C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure, and the residue was purified using flash column chromatography (SiO_2_, PE/EE 7:1). The product was isolated as a yellow‐orange solid (100 mg, 93 µmol, 79%). ^1^H NMR (600.13 MHz, CDCl_3_, 295 K): δ [ppm] = 7.22 (t, 3 𝐽_H─H_ = 7.71 Hz, CH, 4H), 7.05 (t, 3 𝐽_H─H_ = 7.24 Hz, CH, 8H), 6.97 (d, 3 𝐽_H─H_ = 7.24 Hz, CH, 8H), 3.79–3.77 (m, CH_2_, 8H), 1.45–1.40 (m, CH_2_, 8H), 1.23–1.17 (m, CH_2_, 8H), 1.12–1.08 (m, CH_2_, 8H), 1.05–1.00 (m, CH_2_, 8H), 0.83 (t, 3 𝐽_H─H_ = 7.31 Hz, CH_3_, 12H). ^13^C NMR (150.92 MHz, CDCl_3_, 295 K): δ [ppm] = 157.9 (Cq), 154.6 (Cq), 150.9 (Cq), 149.3 (Cq), 147.5 (Cq), 128.9 (CH), 123.9 (CH), 121.4 (CH), 101.0 (Cq), 99.0 (Cq), 42.6 (CH_2_), 31.6 (CH_2_), 27.3 (CH_2_), 26.5 (CH_2_), 22.8 (CH_2_), 14.2 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_66_H_72_N_8_O_6_]^+^: 1072.5569, found 1072.5576.

Compound 4: According to GP1 compound 1 (200 mg, 237.3 µmol, 1 equiv.), 2,6‐dimethylphenol (145 mg, 1.19 mol, 5 equiv.) and K_2_CO_3_ (131 mg, 949 µmol, 5 equiv.) were dissolved in 20 of DMF and stirred for 24 h at 145°C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure, and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 1:1). The product was isolated as a yellow‐orange solid (68 mg, 58 µmol, 24%). ^1^H NMR (600.13 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 7.04 – 6.98 (m, CH, 12H,), 3.60 (s, CH_2_, 7H), 1.31 – 1.21 (m, CH_2_,16H), 1.13 – 1.08 (m, CH_2_, 8H), 0.95 – 0.90 (m, CH_2_, 8H), 0.87 (t, J = 7.4 Hz, CH_3_, 12H). ^13^C NMR (150.92 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 157.1 (Cq), 151.0 (Cq), 150.6 (Cq), 149.8 (Cq), 147.6 (Cq), 131.3 (Cq), 128.2 (CH), 124.7 (CH), 98.9 (Cq), 98.1 (Cq), 42.5 (CH_2_), 31.8 (CH_2_), 27.3 (CH_2_), 26.5 (CH_2_), 22.8 (CH_2_), 16.4 (CH_3_), 14.0 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_74_H_88_N_8_O_6_]^+^: 1184.6827, found in 1184.6832

Compound 5a: According to GP1 compound 1 (100 mg, 119 µmol, 1 equiv.), 2‐(iso‐propyl)phenol (0.11 mL, 831 mmol, 7 equiv.) and K_2_CO_3_ (66 mg, 475 µmol, 5 equiv.) were dissolved in 10 of DMF and stirred for 24 h at 145 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure, and the residue was purified using flash column chromatography (SiO_2_, PE/EE 50:1). The product was isolated as a yellow‐ solid (127 mg, 102 µmol, 86 %). ^1^H NMR (600.18 MHz, THF‐d_8_, 295 K): δ [ppm] = 7.27 (dd, 3 𝐽_H─H_ = 7.65/1.71 Hz, CH, 4H), 7.07–7.01 (m, CH, 8H), 6.91 (dd, 3 𝐽_H─H_ = 7.91/1.41 Hz, CH, 4H), 3.71–3.69 (m, CH_2_, 8H), 3.24 (sept, 3 𝐽_H─H_ = 6.88 Hz, CH, 4H), 1.36–1.31 (m, CH_2_, 8H), 1.25–1.19 (m, CH_2_, 8H), 1.12–1.07 (m, CH_2_, 8H), 1.08 (d, 3 𝐽_H─H_ = 6.83 Hz, CH_3_, 24H), 0.98–0.93 (m, CH_2_, 8H), 0.86 (t, 3 𝐽_H─H_ = 7.35 Hz, CH_3_, 12H). ^13^C NMR(150.92 MHz, THF‐d_8_, 295 K): δ [ppm] = 159.4 (Cq), 153.0 (Cq), 150.9 (Cq), 150.0 (Cq,), 148.4 (Cq), 141.4 (Cq), 126.9 (CH), 126.8 (CH), 125.4 (CH), 123.1 (CH), 100.8 (Cq), 99.0 (Cq), 42.9 (CH_2_), 32.3 (CH_2_), 27.7 (CH_2_), 27.7 (CH_2_), 27.1 (CH), 23.4 (CH_3_), 23.4 (CH_2_), 14.3 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_78_H_96_N_8_O_6_]^+^: 1240.7447, found 1240.7454.

Compound 5b: According to GP1 compound 1 (200 mg, 237.3 µmol, 1 equiv.), 2,6‐diisopropylphenol (0.22 mL, 1.19 mmol, 5 equiv.) and K_2_CO_3_ (131 mg, 949 µmol, 5 equiv.) were dissolved in 20 of DMF and stirred for 24 h at 145°C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure, and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 1:1). The product was isolated as a bright orange solid (79 mg, 56 µmol, 24 %). ^1^H NMR (600.13 MHz, TCE‐d_2_, 410 K): δ [ppm] = 7.20 – 7.10 (m, 12H, CH), 3.23 (p, J = 7.0 Hz, 8H, CH_2_), 1.37 – 1.24 (m, 18H, CH2), 1.16 – 1.12 (m, 8H, CH_2_), 1.11 (d, J = 6.9 Hz, 24H, CH_3_), 0.99 (t, J = 7.6 Hz, 12H, CH_2_), 0.95 – 0.93 (m, 24H, CH_3_), 0.91 (t, J = 7.3 Hz, 12H, CH_3_). ^13^C NMR (150.92 MHz, TCE‐d_2_, 410 K): δ [ppm] = 158.5 (Cq), 149.4 (Cq), 147.4 (Cq), 141.5 (Cq), 125.6 (CH), 123.9 (CH), 99.9 (Cq), 98.0 (Cq), 42.7 (Cq), 31.4 (CH_2_), 27.1 (CH_2_/CH), 26.4 (CH_2_), 23.6 (CH_3_), 23.3 (CH_3_), 22.5 (CH_2_), 13.8 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_90_H_120_N_8_O_6_]^+^: 1408.9331, found in 1409.9364.

Compound 6: According to GP1 compound 1 (100 mg, 119 µmol, 1 equiv.), 4‐(tert‐butyl)phenol (100 µl, 593 µmol, 5 equiv.) and K_2_CO_3_ (66 mg, 475 µmol, 5 equiv.) were dissolved in 10 of DMF and stirred for 24 h at 145 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, PE/EE 7:1). The product was isolated as a yellow solid (131 mg, 101 µmol, 85 %). ^1^H NMR (600.13 MHz, CDCl_3_, 295 K): δ [ppm] = 7.22 (d, 3 𝐽_H─H_ = 8.59 Hz, CH, 8H), 6.85 (d, 3 𝐽_H─H_ = 8.85 Hz, CH, 8H), 3.82–3.79 (m, CH_2_, 8H), 1.48–1.42 (m, CH_2_, 8H), 1.27 (bs, CH_3_, 36H), 1.24–1.12 (m, CH_2_, 16H,), 1.08–1.03 (m, CH_2_, 8H), 0.83 (t, 3 𝐽_H─H_ = 8.59 Hz, CH_3_, 12H). ^13^C NMR (150.92 MHz, CDCl_3_, 295 K): δ [ppm] = 157.8 (Cq), 152.2 (Cq), 151.0 (Cq), 149.4 (Cq), 147.4 (Cq), 146.4 (Cq), 125.6 (CH), 120.5 (CH), 101.1 (Cq), 99.0 (Cq), 42.6 (CH_2_), 34.4 (Cq), 31.7 (CH_3_), 31.7 (CH_3_), 27.3 (CH_2_), 26.5 (CH_2_), 22.7 (CH_2_), 14.2 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_82_H_104_N_8_O_6_]^+^: 1296.8074, found 1296.8070

Compound 7: According to GP1 compound 1 (200 mg, 237.3 µmol, 1 equiv.), n‐octylphenol (244.83 mg, 1.19 mmol, 5 equiv.) and K_2_CO_3_ (131 mg, 1.19 mmol, 5 equiv.) were dissolved in 10 of DMF and stirred for 24 h at 145 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 1:1). The product was isolated as a bright orange solid (180 mg, 116.29 µmol, 49 %). ^1^H NMR (600.13 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 7.21 (d, J = 8.6 Hz, CH, 8H), 6.86 (d, J = 8.3 Hz, CH, 8H), 5.31 – 5.30 (m, CH_2_, 4H), 3.77 (s, CH_2_, 8H), 1.72 (s, CH_2_, 8H), 1.45 (p, J = 7.6 Hz, CH_2_, 8H), 1.32 (s, CH_3_, 24H), 1.27 – 1.15 (m, CH_2_, 18H), 1.09 (q, J = 7.9 Hz, CH_2_,8H), 0.84 (t, J = 7.2 Hz, CH3,12H), 0.73 (s, CH_3_, 36H). ^13^C NMR (150.92 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = δ 158.0 (Cq), 152.3 (Cq), 150.9 (Cq), 149.5 (Cq), 147.8 (Cq), 145.8 (Cq), 126.8 (CH), 120.7 (CH), 101.0 (Cq), 99.1 (Cq), 57.2 (CH_2_), 42.4 (CH_2_), 38.5 (Cq), 32.6 (CH_2_), 32.0 (CH_3_), 31.9 (CH_3_), 27.6 (CH_2_), 26.8 (CH_2_), 22.9 (CH_2_), 14.3 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_98_H_136_N_8_O_6_]^+^:1522.0616 found, 1522.0665.

Compound 8: According to GP1 compound 1 (200 mg, 237.3 µmol, 1 equiv.), 4‐fluorophenol (133 mg, 1.19 mmol, 5 equiv.) and K_2_CO_3_ (164 mg, 1.19 mmol, 5 equiv.) were dissolved in 20 of DMF and stirred for 24 h at 145 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure, and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 1:1). The product was isolated as an orange solid (156 mg, 136 µmol, 57 %). ^1^H NMR (600.13 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 6.95 (d, CH, 16H), 3.80 – 3.75 (m, CH_2_, 8H), 1.42 (p, J = 7.7 Hz, CH_2_, 8H), 1.22 (p, J = 7.6 Hz, CH_2_, 8H), 1.15 – 1.09 (m, CH_2_, 8H), 1.06 (q, J = 7.9 Hz, CH_2_, 8H), 0.85 (t, J = 7.3 Hz, CH_3_, 12H). ^13^C NMR (150.92 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 159.9 (Cq), 158.3 (Cq), 157.7 (Cq), 150.4 (Cq), 150.4 (Cq), 150.4 (Cq), 149.0 (Cq), 147.5 (Cq), 122.4 (CH), 122.4 (CH), 115.4 (CH), 115.3 (CH), 100.5 (Cq), 98.8 (Cq), 42.4 (CH_2_), 31.4 (CH_2_), 27.0 (CH_2_), 26.4 (CH_2_), 22.6 (CH_2_), 13.8 (CH_3_). ^19^F‐NMR (150.92 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = −120.36 (p, J = 6.4 Hz). HRMS‐(MALDI^+^): calcd. for [C_66_H_68_F_4_N_8_O_6_]^+^: 1144.5198, found 1144.5237.

Compound 9: According to GP1 compound 1 (200 mg, 237.3 µmol, 1 equiv.), 2,3,4,5,6‐pentafluorophenol (218 mg, 1.19 mmol, 5 equiv.) and K_2_CO_3_ (131 mg, 1.19 mmol, 5 equiv.) were dissolved in 20 of DMF and stirred for 24 h at 145°C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 1:2). The product was isolated as a yellow solid (42 mg, 289 µmol, 12 %). ^1^H NMR (600.13 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 3.81 (t, J = 7.7 Hz, CH_2_, 8H), 1.47 (p, J = 7.7 Hz, CH_2_, 8H), 1.31 – 1.23 (m, CH_2_, 8H), 1.21 – 1.15 (m, CH_2_,8H), 1.15 – 1.08 (m, CH_2_, 8H), 0.87 (t, J = 7.3 Hz, CH_3_, 12H). ^13^C NMR (150.92 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 155.81 (C_q_), 149.85 (C_q_), 149.20 (C_q_), 148.13 (C_q_), 142.6 (C_q_), 140.9 (C_q_), 139.7 (C_q_), 138.7 (C_q_), 138.0 (C_q_), 137.1 (C_q_), 128.10 (C_q_), 99.86 (C_q_), 98.90 (C_q_), 53.78 (CH_2_), 42.95 (CH_2_), 31.47 (CH_2_), 26.93 (CH_2_), 26.67 (CH_2_), 22.57 (CH_2_), 13.63 (CH_3_). ^19^F NMR (565 MHz, CD_2_Cl_2_): δ [ppm] = −154.02 (d, J = 18.4 Hz), −160.50 (t, J = 21.6 Hz), −163.71 (t, J = 19.8 Hz). HRMS‐(MALDI^+^): calcd. for [C_66_H_44_F_20_N_8_O_10_]^+^: 1432.3690, found 1432.3726

Compound 10: According to GP1 compound 1 (200 mg, 237.3 µmol, 1 equiv.), 2,6‐diphenylphenol (292.2 mg, 1.19 mmol, 5 equiv.) and K_2_CO_3_ (131 mg, 1.19 mmol, 5 equiv.) were dissolved in 20 of DMF and stirred for 24 h at 145 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 1:1). The product was isolated as a bright orange solid (97 mg, 58 µmol, 24 %). ^1^H NMR (600.13 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 7.38 (s, CH, 6H), 7.30 (d, J = 7.6 Hz, CH, 8H), 6.92 (t, J = 7.6 Hz, CH, 8H), 6.83 (t, J = 7.5 Hz, CH, 4H), 4.16 – 4.11 (m, CH_2_, 4H), 3.87 (t, J = 7.6 Hz, CH_2_, 4H), 1.72 (p, J = 7.3 Hz, CH_2_, 4H), 1.46 – 1.29 (m, CH_2_, 16H), 1.26 (p, J = 7.2 Hz, CH_2_, 4H), 1.21 – 1.14 (m, CH_2_, 4H), 1.12 – 1.05 (m, CH_2_, 4H), 0.88 (t, J = 7.2 Hz, CH_3_, 12H). ^13^C NMR (150.92 MHz, CD_2_Cl_2_, 295 K): δ [ppm] = 158.3 (Cq), 150.4 (Cq), 148.7 (Cq), 147.9 (Cq), 147.1 (Cq), 146.8 (Cq), 145.8 (Cq), 138.6 (Cq), 136.9 (Cq), 130.4 (CH), 129.2 (CH), 127.8 (CH), 127.1 (CH), 125.8 (CH), 112.4 (Cq), 100.8 (Cq), 98.7 (Cq), 42.9 (CH_2_), 42.5 (CH_2_), 31.8 (CH_2_), 31.6 (CH_2_), 27.3 (CH_2_), 27.3 (CH_2_), 26.6 (CH_2_), 26.6 (CH_2_), 22.8 (CH_2_), 22.8 (CH_2_), 14.0 (CH_3_), 13.9 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_78_H_78_Cl_2_N_8_O_4_]^+^: 1260.5523, found 1260.5535.

Compound 11: According to GP2 compound 1 (400 mg, 474.65 µmol, 1 equiv.), [1,1′‐Biphenyl]‐2,2′‐diol (203.28 mg, 1.09 mmol, 2.3 equiv.) and K_2_CO_3_ (164 mg, 1.19 mmol, 2.5 equiv.) were dissolved in 20 of DMF and stirred for 7 days at 140°C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 5:1). The product was isolated as a bright orange solid (182.72 mg, 170.87 µmol, 36 %). ^1^H NMR (600.13 MHz, TCE‐d_2_, 366 K): δ 7.41 – 7.34 (m, CH, 4H), 7.25 (t, J = 7.9 Hz, CH, 4H), 7.19 (t, J = 7.5 Hz, CH, 4H), 6.91 (d, J = 8.0 Hz, CH, 4H), 4.05 (t, J = 7.3 Hz, CH_2_, 8H), 1.66 – 1.55 (m, CH_2_, 8H), 1.34 – 1.23 (m, CH_2_, 24H), 0.91 (t, J = 6.4 Hz, CH_3_, 12H). ^13^C NMR (150.90 MHz, TCE‐d_2_, 366 K): δ = 158.5 (Cq), 151.9 (Cq), 150.7 (Cq), 148.3 (Cq), 147.3 (Cq), 130.9 (CH), 129.3 (CH), 129.1 (Cq), 125.1 (CH), 120.2 (CH), 102.3 (Cq), 99.7 (Cq), 42.7 (CH_2_), 31.5 (CH_2_), 27.2 (CH_2_), 26.5 (CH_2_), 22.6 (CH_2_), 13.9 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_66_H_68_N_8_O_6_]^+^: 1068.5262, found 1068.5256.

Compound 12 (S or R): According to GP2 compound 1 (300 mg, 355.99 µmol, 1 equiv.), (S or R) H_8_‐BINOL (241.04 mg, 818.77 µmol, 2.3 equiv.) and K_2_CO_3_ (123 mg, 889.96 µmol, 2.5 equiv.) were dissolved in 20 of DMF and stirred for 7 days at 140 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 10:1). The product was isolated as a bright orange solid (151.04 mg, 117.48 µmol, 33 %). ^1^H NMR (600 MHz, TCE‐d_2_ 398 K): δ 6.93 (d, J = 8.3 Hz, CH, 4H), 6.61 (d, J = 8.3 Hz, CH, 4H), 4.21 – 4.09 (m, CH_2_, 8H), 2.82 – 2.76 (m, CH_2_, 4H), 2.67 – 2.52 (m, CH_2_, 8H), 2.37 – 2.29 (m, CH_2_, 4H), 1.85 – 1.69 (m, CH_2_, 20H), 1.55 – 1.47 (m, CH_2_, 4H), 1.47 – 1.31 (m, CH_2_, 26H), 0.92 (t, CH_3_, 12H). ^13^C NMR (150.90 MHz, TCE‐d_2_ 398 K): δ 160.0 (C_q_), 150.8 (C_q_), 150.4 (C_q_), 148.1 (C_q_), 147.8 (C_q_), 137.7 (C_q_), 133.7 (C_q_), 129.5 (CH), 126.4 (C_q_), 117.5 (CH), 102.5 (C_q_), 98.8 (C_q_), 42.5 (CH_2_), 31.4 (CH_2_), 29.3 (CH_2_), 27.5 (CH_2_), 27.3 (CH_2_), 26.4 (CH_2_), 22.9 (CH_2_), 22.8 (CH_2_), 22.4, 13.8 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_82_H_92_N_8_O_6_] +: 1284.7140, found 1284.7100.

Compound 13 (S or R): According to GP2 compound 1 (400 mg, 474.65 µmol, 1 equiv.), (S or R) BINOL (312.58 mg, 1.09 mmol, 2.3 equiv.), and K_2_CO_3_ (164 mg, 1.19 mmol, 2.5 equiv.) were dissolved in 20 of DMF and stirred for 7 days at 140 °C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 10:1). The product was isolated as a bright orange solid (241 mg, 189.86 µmol, 40 %). ^1^H NMR (600 MHz, TCE‐d_2_, 390 K): δ 7.83 (t, J = 8.7 Hz, CH, 8H), 7.43 – 7.39 (m, CH, 4H), 7.30 – 7.24 (m, CH, 8H), 7.11 (d, J = 9.0 Hz, CH, 4H), 4.04 – 3.80 (m, CH_2_, 8H), 1.67 – 1.53 (m, CH_2_, 8H), 1.35 – 1.21 (m, CH_2_, 24H), 0.87 (t, CH_3_, 12H). ^13^C NMR (150.90 MHz, TCE‐d_2_, 390 K): δ 159.1 (Cq), 150.5 (Cq), 149.9 (Cq), 148.2 (Cq), 147.2 (Cq), 133.0 (Cq), 131.0 (Cq), 130.2 (CH_2_), 128.1 (CH_2_), 126.7 (CH_2_), 126.7 (CH_2_), 125.1 (CH_2_), 120.8 (Cq), 119.8 (CH_2_), 102.5 (Cq), 99.0 (Cq), 42.7 (CH_2_), 31.3 (CH_2_), 27.1 (CH_2_), 26.4 (CH_2_), 22.4 (CH_2_), 13.7 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_82_H_76_N_8_O_6_]^+^: 1268.5888, found 1268.5866.

Compound 14 (S or R): According to GP2 compound 2 (150 mg, 190.69 µmol, 1 equiv.), (S or R) BINOL (125.58 mg, 438.58 µmol, 2.3 equiv.) and K_2_CO_3_ (65.89 mg, 476.72 µmol, 2.5 equiv.) were dissolved in 20 of DMF and stirred for 7 days at 140°C. The mixture was cooled to room temperature, poured into distilled water (20 mL) and extracted with dichloromethane (50 mL). The organic phase was collected, and the solvent was removed under reduced pressure and the residue was purified using flash column chromatography (SiO_2_, DCM/n‐hexane 10:1). The product was isolated as a bright orange solid (140 mg, 116.32 µmol, 61 %). ^1^H (600 MHz, TCE‐d_2_, 410K) δ = 7.81 (t, J = 8.8 Hz, CH, 8H), 7.42 – 7.37 (m, CH, 4H), 7.29 – 7.25 (m, CH, 8H), 7.04 (d, J = 9.2 Hz, CH, 4H), 3.88 (s, CH_2_, 8H), 0.94 (s, CH_3_, 36H). ^13^C NMR (150.90 MHz, TCE, 410K): δ = 158.9 (C_q_), 151.9 (C_q_), 150.2 (C_q_), 148.9 (C_q_), 147.5 (C_q_), 133.0 (C_q_), 130.9 (C_q_), 130.0 (CH), 128.1 (CH), 126.7 (CH), 126.7 (CH), 125.1 (CH), 121.1 (C_q_), 119.9 (CH), 102.5 (C_q_), 98.5 (C_q_), 52.1 (CH_2_), 33.9 (C_q_), 29.1 (CH_3_). HRMS‐(MALDI^+^): calcd. for [C_78_H_68_N_8_O_6_] +: 1212.5262, found 1212.525

Deposition Numbers 2443149 (for 3), 2443147 (for 8), 2443148 (for 10), 2443144 (for 11), 2443145 (for 13), 2443146 (for 14) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures Services.

Conflicts of Interest

The authors declare no conflict of interest.

Supporting information

Supporting File 1: chem70481‐sup‐0001‐SuppMat.docx.

Supporting File 2: chem70481‐sup‐0002‐DataFile.zip.