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. 2019 Nov 16;22:195–205. doi: 10.1016/j.isci.2019.11.024

Atroposelective Synthesis of Biaryl Diamines and Amino Alcohols via Chiral Phosphoric Acid Catalyzed para-Aminations of Anilines and Phenols

Donglei Wang 1,2,3, Wei Liu 1,2,3, Mengyao Tang 1,2, Na Yu 1, Xiaoyu Yang 1,4,∗
PMCID: PMC6909093  PMID: 31785557

Summary

A versatile method for atroposelective synthesis of chiral biaryl diamines and amino alcohols has been developed via para-amination of anilines and phenols with azodicarboxylates enabled by chiral phosphoric acid catalysis. Meanwhile, highly efficient kinetic resolution of the racemic biaryl anilines has also been realized through these reactions, giving selectivity factor up to 246. The gram-scale reaction and facile derivatizations of the chiral products well demonstrate the potential of these reactions in the development of novel chiral ligands and catalysts.

Subject Areas: Organic Chemistry, Organic Synthesis, Stereochemistry

Graphical Abstract

graphic file with name fx1.jpg

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Highlights

  • •

    Versatile methods for asymmetric synthesis of biaryl diamines and amino alcohols

  • •

    Atroposelective para-aminations of biaryl anilines and phenols

  • •

    Kinetic resolution of racemic biaryl anilines

  • •

    Facile transformations of chiral products

Organic Chemistry; Organic Synthesis; Stereochemistry

Introduction

Biaryl compounds possessing axial chirality are ubiquitous among biologically active natural products and pharmaceuticals (Bringmann et al., 2011, Kozlowski et al., 2009) and have been extensively exploited as chiral ligands/catalysts in asymmetric catalysis (Brunel, 2005, Brunel, 2007, Chen et al., 2003, Kočovský et al., 2003, McCarthy and Guiry, 2001). To this end, their highly efficient and asymmetric catalytic synthesis has drawn increasing research interests, and various elegant methods have been developed in the last two decades (Bencivenni, 2015, Bonne and Rodriguez, 2018, Liao et al., 2019, Ma and Sibi, 2015, Nguyen, 2019, Renzi, 2017, Wang and Tan, 2018, Wencel-Delord et al., 2015, Zilate et al., 2018). However, in contrast to the numerous well-developed methods for asymmetric synthesis of BINOL-type biaryl diols (Chen et al., 2015, Egami et al., 2010, Guo et al., 2007, Jarvo et al., 2001, Jolliffe et al., 2017, Li et al., 2003, Luo et al., 2002, Ma et al., 2014, Moliterno et al., 2016, Moustafa et al., 2018, Narute et al., 2016, Wang et al., 2016, Xu et al., 2017), methods for enantioselective synthesis of other functionalized chiral biaryls are relatively limited. 1,1′-Binaphthyl-2,2′-diamine (BINAM), a representative chiral biaryl diamine, has been widely exploited in the development of chiral ligands and organocatalysts (Galzerano et al., 2009, Tan et al., 2011, Telfer and Kuroda, 2003, Uraguchi et al., 2009, Wang et al., 2005). However, only limited asymmetric catalytic methods (Brown et al., 1985, Chang et al., 2019) have been developed for its enantioselective synthesis, including asymmetric [3,3]-sigmatropic rearrangement (De et al., 2013, Li et al., 2013) and kinetic resolution (Cheng et al., 2014). 2-Amino-2′-hydroxy-1,1′-binaphthyl (NOBIN) (Smrcina et al., 1992, Smrcina et al., 1993), which is considered as the hybrid analogue of BINOL and BINAM, represents one type of privileged biaryl amino alcohol scaffold for constructing chiral ligands (Ding et al., 2005a, Ding et al., 2005b, Kočovský et al., 2003). However, methods for their asymmetric catalytic synthesis was also limited to kinetic resolutions (Lu et al., 2014, Shirakawa et al., 2013) and enantioselective direct arylation of 2-naphthylamines (Chen et al., 2017). Although the aforementioned elegant methods have provided access to enantioenriched biaryl diamines and amino alcohols, respectively, versatile methods for their asymmetric synthesis remain elusive. Recently, Tan and co-workers reported the asymmetric synthesis of BINAM- and NOBIN-type biaryls via enantioselective additions of 2-naphthols and 2-naphthylamines with 2-azonaphthalenes, which represented the first versatile protocol for their asymmetric synthesis, although two different catalytic systems were required (Qi et al., 2019).

Asymmetric Friedel-Crafts aminations of naphthols and naphthylamines with azodicarboxylates have been well employed in asymmetric synthesis of N-containing chiral scaffolds. For instance, Jørgensen group (Brandes et al., 2006a, Brandes et al., 2006b) and Zhang group (Bai et al., 2019) developed asymmetric construction of C-N axial chirality by chiral amine and phosphoric acid-catalyzed ortho-amination of 2-naphthols and 2-naphthyl amines, respectively (Scheme 1A). You group (Wang et al., 2015, Xia et al., 2019) and Luan group (Nan et al., 2015) reported asymmetric dearomatization of naphthols via direct aminations of naphthols with azodicarboxylates enabled by chiral Brønsted/Lewis acid catalysis, constructing N-containing chiral quaternary centers (Scheme 1B). Nevertheless, most of these methods are still limited to ortho-aminations of naphthols and naphthylamines; asymmetric reactions involving para-aminations of common anilines and phenols (Leblanc and Boudreault, 1995, Tang et al., 2017, Yadav et al., 2002, Zaltsgendler et al., 1993) are still elusive. Herein, we report a versatile protocol for atroposelective synthesis of biaryl diamines and amino alcohols via para-aminations of anilines and phenols (Diener et al., 2015, Gustafson et al., 2010, Miyaji et al., 2015, Miyaji et al., 2017, Mori et al., 2013a, Mori et al., 2013b) with azodicarboxylates via chiral phosphoric acid catalysis (Akiyama, 2007, Akiyama et al., 2004, Akiyama and Mori, 2015, Li and Song, 2018, Parmar et al., 2014, Terada, 2010, Uraguchi and Terada, 2004) (Scheme 1C).

Scheme 1.

Scheme 1

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Asymmetric Friedel-Crafts Amination with Azodicarboxylates

(A) construction of C-N axial chirality, (B) construction of N-containing chiral quaternary centers, and (C) atroposelective synthesis of biaryl diamines and amino alcohols.

Results and Discussion

Optimization of Reaction Conditions

Our study commenced with using biaryl aniline 1a as substrate and dibenzyl azodicarboxylate 2 as amination reagent under the catalysis of CPA catalysts (Table 1). Interestingly, in the presence of CPA catalyst A1 (10 mol %), the amination reaction between 1a and azodicarboxylate 2 (1.1 equiv.) in toluene (with 5 Å molecular sieves) proceeded smoothly at ambient temperature to afford the triazane 4a (Egger et al., 1983, Tang et al., 2017) as the major product (60% yield), whereas the desired para-amination product 3a was obtained only in 13% yield with 47% enantiomeric excess (ee) (entry 1). Next, a variety of BINOL-derived chiral phosphoric acid catalysts were examined (entries 2–7), and encouragingly the TCYP catalyst (cat A7) provided the desired product 3a in 80% yield with 98% ee, with the undesired N-amination product 4a and diamination product 5a isolated in <10% yield (entry 7). Next, a range of solvents were also investigated (entries 8–10), and CHCl3 turned out to be the optimal one, in which the desired product 3a was produced in 91% yield with 98% ee (entry 9). The role of the molecular sieves was also demonstrated; in the absence of 5-Å molecular sieves, the axially chiral biaryl 3a was obtained only in 66% yield (entry 11). The reduction of catalyst loading was also studied; however, decreasing the catalyst loading to 5 mol % at room temperature led to a diminished yield (entry 12). Interestingly, conducting this reaction with 5 mol % catalyst at 40°C gave product 3a in 87% yield with the same ee (entry 13). The axially chiral biaryl product 3a has high configurational stability, whose ee was retained after storing on bench for more than 2 months at ambient temperature and heating at 100°C in toluene for 36 h.

Table 1.

Optimization of the Reaction Conditions

Inline graphic
Entrya Cat. Sol. 4a Yieldb (%) 5a Yieldb (%) 3a Yieldb (%) 3a eec (%)
1 A1 Tol 60 16 13 47
2 A2 Tol 35 22 19 81
3 A3 Tol 58 22 5 46
4 A4 Tol 20 22 28 94
5 A5 Tol 48 17 5 85
6 A6 Tol 7 17 54 98
7 A7 Tol 9 6 80 98
8 A7 DCM 14 22 56 98
9 A7 CHCl3 – – 91 98
10 A7 Et2O 44 22 16 96
11d A7 CHCl3 – 17 66 97
12e A7 CHCl3 7 18 74 98
13e,f A7 CHCl3 – – 87 98
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a

Unless otherwise noted, reactions were performed with 1a (0.1 mmol), 2 (0.11 mmol), CPA catalyst (0.01 mmol), and 5 Å MS (30 mg) in solvents (0.5 mL) for 16 h at ambient temperature.

b

Yield was isolated yield.

c

Enantiomeric excess (ee) was determined by HPLC analysis on a chiral stationary phase.

d

Reaction was performed without 5 Å MS.

e

Reaction was performed with 5 mol % catalyst.

f

Reaction was performed at 40°C.

Substrate Scope

With the optimal conditions in hand, we next sought to explore the compatibility of substrate scope of this reaction (Scheme 2). A range of substituted 2-naphthylamine moieties could be well tolerated in the biaryl aniline substrates, affording the axially chiral amination products with high enantioselectivities (3b-3d). A series of substitutions at the ortho- and meta-positions of the aniline moieties in substrates was also compatible with the optimal conditions (3f-3h). It is worth mentioning that the direct amination of substrates 1g and 1h afforded products as inseparable diastereomer mixtures due to the presence of extra C-N axial chirality; therefore, these products were directly converted into –NH2-containing product 3g and 3h by catalytic hydrogenations. The absolute configurations of the axially chiral products 3 were assigned as (S) by analogy to product 3g, whose structure was unambiguously confirmed by X-ray crystallography (see Supplemental Information). The 2-naphthylamine scaffold in the substrates could also be switched to 3-substituted anilines (3i-3k), which also produced the biaryl amination products with high enantioselectivities under the standard conditions. Switching the N-protecting group from -Boc to –Cbz was also well tolerated with the optimal conditions, which produced product 3l with excellent enantioselectivity. However, using the N-protecting group-free biaryl aniline as substrates provided the triazane product as the major product.

Scheme 2.

Scheme 2

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Substrate Scope for Asymmetric Synthesis of Biaryl Diamines via Para-aminations of Anilines

Reactions were performed with 1 (0.1 mmol), 2 (0.11 mmol), (R)-cat A7 (0.005 mmol), and 5 Å MS (30 mg) in CHCl3 (0.5 mL) at 40°C overnight. Yield was isolated yield. Ee was determined by HPLC analysis on a chiral stationary phase.

aThe amination products were subjected into catalytic hydrogenation (1 atm) with Pd/C (10 mol %) as catalyst to afford 3g and 3h.

With the excellent performance of constructing chiral biaryl diamines via asymmetric para-amination reactions, we envisioned that these reactions could also be adopted in the kinetic resolution of racemic biaryl anilines. Thus, a variety of 2-substituted biaryl anilines possessing axial chirality were synthesized and their kinetic resolution via para-amination reactions with azodicarboxylate 2 (0.6 equiv.) was investigated (Scheme 3). Under the catalysis of (R)-TRIP catalyst (cat A6, 10 mol %) in DCM at room temperature, the kinetic resolutions of these substrates proceeded with high efficiencies to afford both recovered aniline substrates and para-amination products with high enantioselectivities (with s factor up to 246, 3m-3p). The absolute configurations of the axially chiral products and recovered starting materials were assigned by analogy to recovered 1m, whose structure was unambiguously confirmed by X-ray crystallography (see Supplemental Information).

Scheme 3.

Scheme 3

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Substrate Scope for Kinetic Resolution of Biaryl Anilines by Para-aminations

Reactions were performed with 1 (0.1 mmol), 2 (0.06 mmol), (R)-cat A6 (0.01 mmol), and 5 Å MS (30 mg) in CH2Cl2 (0.5 mL) at room temperature overnight. Yield was isolated yield. Ee was determined by HPLC analysis on a chiral stationary phase.

To achieve enantioselective synthesis of biaryl amino alcohols, the 2-naphthylamine moieties in the substrates were switched to 2-naphthol moieties. However, the amination reactions of the corresponding biaryl anilines 6′ provided only N-amination triazane products 7’ (Scheme 4). Interestingly, the desired biaryl amino alcohols were obtained while phenols 6 were employed as electron-rich arenes instead of anilines. Under the catalysis of (R)-C8-TRIP catalyst (cat A8) in CHCl3 at ambient temperature, the para-amination of biaryl phenol 6a with azodicarboxylate 2 afforded the biaryl amino alcohol 7a in 56% yield with 86% ee (for further details, see Table S1 in the Supplemental Information). Switching the protecting group from O-Me to O-MOM was compatible with the optimal conditions, providing the axially chiral amination product with comparable stereoselectivity (7b). The substrate scope for the 2-naphthol moieties in the substrates were explored under the standard conditions, which showed that a range of substituted 2-naphthol scaffolds (with various substitutions at the 4-, 6-, and 7-positions) could be accommodated, affording biaryl amino alcohols in good yields and high enantioselectivities (7c–7g). The absolute configurations of these biaryl amino alcohols 7 were assigned by analogy to product 7c, whose structure was also confirmed by X-ray crystallography (Supplemental Information). It is worth mentioning that biaryl phenol substrate without O-Me protecting group afforded the para-amination product with diminished enantioselectivity under the optimal conditions.

Scheme 4.

Scheme 4

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Substrate Scope for Asymmetric Synthesis of Biaryl Amino Alcohols via Para-amination of Phenols

Reactions were performed with 6 (0.1 mmol), 2 (0.3 mmol), (R)-cat A8 (0.01 mmol), and 5 Å MS (30 mg) in CHCl3 (0.5 mL) at ambient temperature for 36 h. Yield was isolated yield. Ees was determined by HPLC analysis on a chiral stationary phase.

aReaction was performed with 2 (0.15 mmol).

Mechanistic Discussion

To gain more insight into the reaction mechanism, several control experiments were performed (Scheme 5). The amination reaction of N-Me biaryl aniline substrate 1q proceeded smoothly under the standard conditions to give the desired para-amination product 3q in 56% yield with 92% ee. However, applying the same conditions on N,N-dimethyl aniline substrate 1r provided only the para-amination product 3r in 25% yield with 5% ee (with the N-amination product as the major by-product), which indicated that the potential hydrogen bonding between CPA catalyst and the aniline N-H group played a key role in controlling both chemoselectivity and stereoselectivity in this reaction (Scheme 5A). Interestingly, subjection of the N-amination triazane product 4a into the optimal conditions without adding azodicarboxylate 2 also gave the para-amination product 3a in 58% yield with 98% ee after 16 h, with the aniline substrate 1a isolated in 28% yield, which suggested the reversible nature of the triazane formation step (Scheme 5B). Based on the above-mentioned experimental study and previous work (Bai et al., 2019, Drouet et al., 2011, Dumoulin et al., 2015), a plausible reaction mechanism is proposed, in which bifunctional activation (Parmar et al., 2014, Simón and Goodman, 2008, Yamanaka et al., 2007) of both the aniline substrate and azodicarboxylate via dual hydrogen-bonding interaction with the CPA catalyst is postulated (Scheme 5C). Under the catalysis of CPA catalyst, there are two alternative reaction pathways between aniline substrates and azodicarboxylates: (1) direct nucleophilic addition of the –NH2 group to the azodicarboxylate facilitated the generation of the triazane products (path a), which is also reversible under these conditions; and (2) the para-selective amination of aniline substrates would give the dearomatized addition product INT A, possessing a chiral center (path b). On subsequent aromatization, INT A underwent the central-to-axial chirality transfer (Qi et al., 2017, Raut et al., 2017) to provide the axial biaryl diamine products.

Scheme 5.

Scheme 5

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Preliminary Mechanistic Study and Proposed Mechanism

Transformations of Products

To evaluate the practicability of these reactions, a gram-scale amination reaction of 1a was performed, which provided the axially chiral biaryl 3a in 70% yield with 99% ee, with reduced catalyst loading (2 mol %, Scheme 6A). The derivatizations of the chiral products were also studied to prove the value of these reactions. By means of the Sandmeyer reaction, the directing –NH2 group was transformed into an iodide group via diazotization of 3a with NaNO2 followed by treatment with NaI to afford 8a, which could be further employed in Suzuki coupling with phenylboronic acid to give product 9a in 81% yield (Scheme 6B). Notably, the ee of chiral biaryl product was retained through these steps of transformations, including the Suzuki coupling step (105°C, overnight), again demonstrating the high configurational stability of these atropisomeric products. The catalytic hydrogenation of 7a using Pd/C as catalyst facilely reduced the substituted hydrazine moiety to give the biaryl product 10a in 90% yield (Scheme 6C). A two-step procedure of catalytic hydrogenation followed by deprotection of the N-Boc group converted chiral product 3n into biaryl diamine 11n in 82% yield, without erosion of the enantioselectivity (Scheme 6D). Finally, a primary-amine/thiourea bifunctional catalyst 13a was straightforwardly synthesized from the chiral product 3a within 4 steps, with complete retention of the enantiomeric purity (Scheme 6E). The application of this bifunctional catalyst was preliminarily demonstrated in an asymmetric Michael reaction of 3-methyl oxindole 14 with cinnamaldehyde 15 (Galzerano et al., 2009), which readily provided the product 16 (after reduction) in 53% yield with 6:1 d.r. and 73% ee without optimization (Scheme 6F).

Scheme 6.

Scheme 6

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Gram-Scale Synthesis of 3a and Derivatizations of the Chiral Products

Conclusion

We have disclosed a versatile method for asymmetric synthesis of biaryl diamines and amino alcohols, which was realized through chiral phosphoric acid catalyzed enantioselective para-aminations of biaryl anilines and phenols with azodicarboxylates. These reactions are also well employed in the highly efficient kinetic resolution of racemic biaryl anilines, which give s factor up to 246. Preliminary mechanistic studies were performed to elucidate the reaction mechanism, in which a dual hydrogen-bonding activation mode was proposed in the key chirality induction step. The facile transformations of chiral products into atropisomeric biaryl diamine and amino alcohol derivatives with novel and diversified scaffolds well demonstrate the value of these reactions, especially in the field of developments of novel chiral catalysts and ligands.

Limitations of the Study

The synthesis of the substrates usually needs multiple steps. Different directing groups are required in the synthesis of biaryl diamines and biaryl amino alcohols.

There are also some limitations of the substrate scope (Scheme 7): (1) electron-donating groups were required at the 2-position of the naphthyl moiety; substrates with alkyl groups at this position barely provided the para-amination products (S1a and S1b); (2) kinetic resolution of racemic biaryl phenol substrate did not provide good kinetic resolution performance (S1c); (3) substitutions at the 2-position of the phenol moiety and 3-position of the naphthol moiety were not compatible in the asymmetric para-amination reactions of biaryl phenols (S1d and S1e).

Scheme 7.

Scheme 7

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Incompatible Substrates

Methods

All methods can be found in the accompanying Transparent Methods supplemental file.

Acknowledgments

We gratefully acknowledge NSFC (Grant No. 21702138), “Thousand Talents Plan” Youth Program, and ShanghaiTech University start-up funding for financial support. We thank the Analytical Instrumentation Centre of ShanghaiTech for facilities and services of characterization of compounds.

Author Contributions

D.W., W.L., and M.T. performed the experiments. N.Y. performed the crystallographic studies. X.Y. conceived the concept, directed the project, and wrote the paper.

Declaration of Interests

The authors declare no competing interests.

Published: December 20, 2019

Footnotes

Supplemental Information can be found online at https://doi.org/10.1016/j.isci.2019.11.024.

Data and Code Availability

The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under accession number CCDC: 1923360 (3g), 1938295 (7c), and 1923362 ((S)-1m). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Supplemental Information

Document S1. Transparent Methods, Figures S1–S216, and Tables S1–S4
mmc1.pdf (10.6MB, pdf)

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Document S1. Transparent Methods, Figures S1–S216, and Tables S1–S4
mmc1.pdf (10.6MB, pdf)

Data Availability Statement

The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under accession number CCDC: 1923360 (3g), 1938295 (7c), and 1923362 ((S)-1m). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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