Organocatalytic Enantioselective Synthesis of Atropisomeric Aryl-p-Quinones: Platform Molecules for Diversity-Oriented Synthesis of Biaryldiols

Article abstract of DOI:10.1002/anie.202004671

Presented here is a class of novel axially chiral aryl-p-quinones as platform molecules for the preparation of non-C₂ symmetric biaryldiols. Two sets of aryl-p-quinone frameworks were synthesized with remarkable enantiocontrol by means of chiral phosphoric acid catalyzed enantioselective arylation of p-quinones by central-to-axial chirality conversion. These aryl-p-quinones were then used to access a wide spectrum of highly functionalized non-C₂ symmetric biaryldiols with excellent retention of the enantiopurity.

Full text of DOI:10.1002/anie.202004671

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Accepted Article
Title: Organocatalytic Enantioselective Synthesis of Atropisomeric Aryl-
p-quinones: Platform Molecules for Diversity-oriented Synthesis
of Biaryldiols
Authors: Bin Tan, Ye-Hui Chen, Heng-Hui Li, Xiao-Hua Xiang, Shaoyu
Li, and Xiao Zhang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202004671
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Organocatalytic Enantioselective Synthesis of Atropisomeric
Aryl-p-quinones: Platform Molecules for Diversity-oriented
Synthesis of Biaryldiols
Ye-Hui Chen,†[a] Heng-Hui Li,†[a] Xiao Zhang,[a] Shao-Hua Xiang,*[a],[b] Shaoyu Li,[a],[b] and Bin Tan*[a]
Dedication ((optional))
[a]
Y.-H. Chen, H.-H. Li, X. Zhang, S.-H. Xiang, S. Li, Prof. Dr. B. Tan
Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis
Southern University of Science and Technology, Shenzhen, 518055, China
E-mail: xiangsh@sustech.edu.cn; tanb@sustech.edu.cn
S.-H. Xiang, S. Li
[b]
Academy for Advanced Interdisciplinary Studies
Southern University of Science and Technology, Shenzhen, 518055, China
These authors contributed equally to this work.
[†]
Supporting information for this article is given via a link at the end of the document.
Abstract: Here we present a class of novel axially chiral aryl-p-
quinones as platform molecules for the preparation of non-C2
symmetric biaryldiols. Two sets of aryl-p-quinone frameworks were
synthesized with remarkable enantiocontrol by means of chiral
phosphoric acid-catalyzed enantioselective arylation of p-quinones
via central-to-axial chirality conversion and a wide spectrum of highly
functionalized non-C2 symmetric biaryldiols were obtained with
excellent enantiopurity retention.
Biaryldiol motifs are prevalent in a wide range of natural
products,[1] bioactive molecules[2] as well as useful chiral ligands
and catalysts.[3] They are also fundamental frameworks to
access an array of privileged atropisomeric biaryls with
significant applications in chemical and material science via
convenient and mature functionalization methods (Figure 1a).[4]
The acquirement of biaryldiols is thus a central issue in axial
chirality and relevant fields. In this regard, great efforts were
devoted to procure structural diversity, establishing various
elegant catalytic enantioselective approaches in the last few
decades.[5] For instance, the transition metal-catalyzed oxidative
couplings of 2-naphthol derivatives constitute substantial source
of C2-symmetric binaphthol derivatives.[6] In the context of non-
C2 symmetric analogues, this strategy is imperiled by insufficient
difference of redox potentials between two coupling partners.[7]
To this end, the groups of Katsuki,[8a] Pappo[8b] and Tu[8c]
auspiciously presented several elegant solutions. In light of the
significant importance of non-C2 symmetric biaryldiols, it remains
highly appealing to develop alternative approaches to access
these scaffolds (Figure 1b).[9]
The robustness of quinone and iminoquinone as phenol
precursors[10] have been harnessed by our group,[11a] Kurti[11b]
and Bella et al.[11c] in constructing enantioenriched non-C2
symmetric biaryldiols by organocatalytic nucleophilic addition
and central-to-axial chirality conversion strategy.[12] Although the
constrained substrate scope with respect to quinone and its
derivatives persists, it holds vast elaboration potential to
encompass broader substrate scope and better functionality
tolerance. Inspired by the above successes, we envisaged an
attainment of non-C2 symmetric biaryldiols[4g,4h,13] from
atropisomeric aryl-p-quinones via direct nucleophilic addition
onto quinone site (Figure 1c). Notably, p-quinone moiety is
Figure 1. Significance of biaryldiols, reported synthetic routes and our design
for synthesis of non-C2 symmetric biaryldiols via aryl-p-quinone atropisomer.
ubiquitous in dyes[14] and constitutes the core structure of
numerous biomimetic catalysts for aerobic oxidation of amines
to aldehydes.[15] More importantly, versatile reaction patterns
with an effective aryl-p-quinone platform molecule will enable a
rapid avenue for diversity-oriented synthesis of non-C2
symmetric biaryldiols and largely enrich the library of such
molecules. However, challenges stemming from lower rotation
barriers as compared to biaryls and racemization issue in
oxidation and functionalization processes were perceived. Here
we present an organocatalytic atroposelective solution in
constructing aryl-p-quinones via arylation of p-quinones and the
downstream synthesis of non-C2 symmetric biaryldiols with
excellent enantiopurity retention.
Based on the recent advances[16] and our continuous
understandings[17] on catalytic enantioselective construction of
atropisomeric frameworks, 1,4-benzoquinone 1a and 7-
methoxyl-2-naphthol 2a were chosen as model substrates to
construct aryl-p-quinone structures in the presence of chiral
phosphoric acid[18] catalyst (R)-CPA1. A sacrificial amount of p-
1
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Scheme 1. Substrate generality for enantioselective construction of
atropisomeric aryl-p-quinones.[a]
Figure 2. The axis stability problems and our proposed solutions to approach
the configurationally stable atropisomeric aryl-p-quinone platform molecules.
quinone 1a was used as oxidant but only 8% yield of the desired
product 3 was obtained with 48% enantiomeric excess (ee) in
CH2Cl2 at -78 °C after 24 hours. To address the inadequate
oxidability of p-quinone, exogenous oxidants were included and
the chemical yield was boosted to 85% with DDQ. The
preserved ee value clearly demonstrated an absolute retention
of enantiopurity during the oxidative process. The configurational
stability investigations showed that the stereogenic axis of
compound 3 was labile and the enantioenrichment was lost
completely in i-PrOH at 25 °C after 160 min (Supplementary
Table 2). To enhance axial stability, two solutions were
considered: A) equipping a suitable substituent at C-8 position of
2-naphthol while upholding reactivity; B) replacing the ester
group on p-quinone with a bulkier substituent (Figure 2a). First,
2-naphthol 2b with an iodine atom at C-8 position was employed
and pleasingly, 85% yield and excellent enantioselectivity (96%
ee) were obtained in the presence of (R)-CPA1 and DDQ at -
78 °C. This set of conditions was optimal for this reaction based
on systematic screenings of oxidants and solvents (Figure 2b,
Supplementary Table 4). Alternately, adduct (5a) of chloride-
substituted p-quinone 1b and 2-naphthol 2a possessed a stable
stereogenic axis. Absence of a strong electron-withdrawing
group nonetheless necessitated a room temperature condition
for rapid reaction of the less-reactive 1b, resulting in moderate
yield and atroposelectivity. Upon identification of DCE as
superior solvent and a beneficial low reaction temperature,
target product 5a was afforded in 75% yield with 96% ee (Figure
2c, Supplementary Table 5).
The two sets of optimal conditions established for catalytic
enantioselective construction of atropisomeric aryl-p-quinones
were applied to evaluate substrate generality in both reaction
domains (Scheme 1). Replacing the ethyl moiety on ester in C-8
substituted 2-naphthols with methyl or isopropyl group provided
4b or 4c in similar yields and excellent enantiocontrol, whereas
slightly compromised ee value was observed for butyl ester (4d).
Apart from iodine, bromine atom aptly exerted sufficient steric
congestion to invoke configurational stability in 4e which was
formed in remarkable efficiency and enantioselectivity under
condition A. Subsequently, p-quinones 1 with different halide
substituents were investigated against 7-methoxyl-2-naphthol 2a
as the nucleophile under condition B. Undoubtedly, p-quinone
possessing bromine or iodine atom undertook this chemistry to
afford 5b and 5c in 97% and 96% ee respectively. While the C-7
[a] Condition A: 1 (0.2 mmol), 2 (0.2 mmol) and (R)-CPA1 (10 mol%) in CH2Cl2
(4 mL) at -78 °C for 48 h. Then DDQ (0.2 mmol) was added in one portion and
reacted for 1 h. Condition B: 1 (0.2 mmol), 2 (0.24 mmol) and (R)-CPA1 (10
mol%) in ClCH2CH2Cl (4 mL) at -32 °C for 72 h. Then DDQ (0.24 mmol) was
added in one portion and reacted for 0.5 h. Isolated yields were provided and
the ee values were determined by HPLC analysis on a chiral stationary phase.
substituents on naphthalene ring of 2-naphthol imposed
negligible influence on the reaction (5d-5g), unsubstituted 2-
naphthol provided 5h in only 89% ee. Further assessment
revealed that all tested 2-naphthols with varied alkyl group and
substitution pattern underwent effective transformations to
furnish 5i-5m. The absolute configuration of 5a was deduced as
(R), by reference to the oxidation product of a (R)-biaryldiol
reported in our previous work.[11a] Those of other products were
assigned by analogy in accordance with the corresponding
absolute configuration of CPAs.
A gram-scale reaction delivered 5a in analogous yield and
enantioselectivity, demonstrating scalability of this method in
preparing aryl-p-quinone atropisomer (Figure 3a). With good
amount of 5a in hand, the endeavours to build structurally
diverse non-C2 symmetric biaryldiols from this platform molecule
commenced with nucleophilic addition of thiophenol (Figure 3b).
Biaryldiols 6 bearing different substituents and substitution
pattern on the upper aromatic ring were generated in moderate
to good yields whilst preserving the atropo-enantioenrichment
(6a-6e, 96% ee). Diarylphosphine oxides reacted to give highly
functionalized Michael addition-type adducts (7) in satisfactory
yields (55-77%) without ee erosion (Figure 3c). Moreover,
ketoester was substantiated as competent C-nucleophile,
reacting at alternate reactive sites on quinone to produce
cyclization product 8 in 41% yield with subtle ee decrement
(92% ee, Figure 3d).
2
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The good compatibility of indole nucleophiles prompted us to
assemble indole-p-quinone atropisomers through established
pathway for more diversified heteroaryl-p-quinone structures.
Considering the lower rotation barrier and hence configurational
instability of indole-p-quinones due to five-membered N-
heterocycle ring,[20] indole 9d possessing a bulky tert-butyl group
at C-2 position was reacted with 2-chloro-1,4-naphthoquinone
11 in a model reaction (Supplementary Table 6). Optimization
studies including parallel screenings of CPA, solvent, substrate
loading ratio and reaction temperature provided the optimal
conditions used to examine indole substrates carrying different
rotation-restricting groups in Scheme 3. While transformations
proceeded in good efficiencies, appendant tert-amyl enhanced
the enantioselectivity to 94% ee (12b) but a moderate 88% ee
was obtained for 1-adamantyl group (12c). An evaluation
focused on the substitution effect on the indole ring concluded
that all examined substrates delivered corresponding adducts in
moderate yields with excellent enantiocontrol. These results
highlighted the high efficiency of current methodology in
assembling axially chiral heteroaryl-p-quinone molecules.
Scheme 3. Substrate generality for enantioselective construction of
atropisomeric indole-p-quinones.[a]
Figure 3. Gram-scale reaction, diverse construction of optical active non-C2
symmetric biaryldiols with platform molecule 5a.
Indoles[19] as representative C-nucleophiles gave rise to a pair of
products following addition onto both reactive sites in the
presence of Sc(OTf)3. Furthermore, rapid oxidation upon air
exposure hindered the isolation of biaryldiols. Implementing a re-
oxidation event with DDQ aided to generate highly functionalized
indole-aryl-p-quinone atropisomers in useful yields without
conspicuous ee deterioration (10a-1~10c-2). While all products
were isolable, iterative nucleophilic additions were unsuccessful,
plausibly due to unfavorable steric effect (Scheme 2).
Scheme 2. The construction of enantioenriched indole-p-quinones with 5a and
indoles.[a]
[a] Conditions: 11 (0.10 mmol) and (S)-CPA1 (10 mol%) were dissolved in
CCl4 (1 mL). A solution of 9 (0.20 mmol) in CCl4 (1 mL) was added dropwise.
The reaction was stirred at 10 °C for 96 h. Isolated yields were provided and
ee values were determined by HPLC analysis on a chiral stationary phase.
In summary, enantioselective construction of structurally novel
axially chiral (hetero)aryl-p-quinone frameworks was efficiently
accomplished through the assembly of p-quinones and
naphthols or indoles. This transformation accommodates broad
range of substrates with excellent enantiocontrol. Delivered aryl-
p-quinones serve as versatile platform molecules for
enantioretentive diversity-oriented synthesis of non-C2
symmetric biaryldiols via nucleophilic addition with a series of S-,
P- and C-nucleophiles. Iterative oxidation and nucleophilic
addition toward multi-substituted atropisomeric aryl-p-quinones
as well as the application potential of the obtained biaryldiol as
chiral catalysts are under survey in our laboratory.
[a] Conditions: 5a (0.2 mmol), 9 (0.4 mmol) and Sc(OTf)3 (20 mol%) in toluene
(4 mL) at r.t. for 5 h. Then DDQ (0.4 mmol) was added in one portion at -30 °C
and the reaction proceeded for another 1 h. Isolated yields were provided and
ee values were determined by HPLC analysis on a chiral stationary phase.
Acknowledgements
3
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[9]
a) T. Temma, S. Habaue, Tetrahedron Lett. 2005, 46, 5655-5657; b) P.
Yan, Y. Sugiyama, Y. Takahashi, H. Kinemuchi, T. Temma, S. Habaue,
Tetrahedron 2008, 64, 4325-4331; c) A. Grandbois, M. È. Mayer, M.
Bédard, S. K. Collins, T. Michel, Chem. Eur. J. 2009, 15, 9655-9659; d)
M. Holtz-Mulholland, M. de Léséleuc, S. K. Collins, Chem. Commun.
2013, 49, 1835-1838.
We are grateful for financial support from the National Natural
Science Foundation of China (Nos. 21772081, 21825105,
21901103 and 21901105), Shenzhen Nobel Prize Scientists
Laboratory Project (C17213101), and Shenzhen Special Funds
for the Development of Biomedicine, Internet, New Energy, and
New Material Industries (JCYJ20170412151701379). This work
was sponsored by Guangdong Provincial Key Laboratory of
Catalysis (No. 2020B121201002) and Guangdong Province
(2019BT02Y335).
[10] a) D. Magdziak, S. J. Meek, T. R. R. Pettus, Chem. Rev. 2004, 104,
1383-1429; b) J. Alemán, B. Richter, K. A. Jørgensen, Angew. Chem.
Int. Ed. 2007, 46, 5515-5519; Angew. Chem. 2007, 119, 5611-5615; c)
J. Alemán, S. Cabrera, E. Maerten, J. Overgaard, K. A. Jørgensen,
Angew. Chem. Int. Ed. 2007, 46, 5520-5523; Angew. Chem. 2007, 119,
5616-5619; d) B. Hosamani, M. F. Ribeiro, E. N. da Silva Júnior, I. N. N.
Namboothiri, Org. Biomol. Chem. 2016, 14, 6913-6931; e) X. Zhang, Y.-
H. Chen, B. Tan, Tetrahedron Lett. 2018, 59, 473-486.
Conflict of interest
The authors declare that they have no conflict of interest.
[11] a) Y.-H. Chen, D.-J. Cheng, J. Zhang, Y. Wang, X.-Y. Liu, B. Tan, J. Am.
Chem. Soc. 2015, 137, 15062-15065; b) J.-Z. Wang, J. Zhou, C. Xu, H.
Sun, L. Kürti, Q.-L. Xu, J. Am. Chem. Soc. 2016, 138, 5202-5205; c) M.
Moliterno, R. Cari, A. Puglisi, A. Antenucci, C. Sperandio, E. Moretti, A.
Di Sabato, R. Salvio, M. Bella, Angew. Chem. Int. Ed. 2016, 55, 6525-
6529; Angew. Chem. 2016, 128, 6635-6639.
Keywords: chiral phosphoric acid • enantioselective catalysis •
aryl-p-quinones • platform molecules • biaryldiols
[1]
For typical reviews, see: a) G. Bringmann, A. J. P. Mortimer, P. A.
Keller, M. J. Gresser, J. Garner, M. Breuning, Angew. Chem. Int. Ed.
2005, 44, 5384-5427; Angew. Chem. 2005, 117, 5518-5563; b) M. C.
Kozlowski, B. J. Morgan, E. C. Linton, Chem. Soc. Rev. 2009, 38,
3193-3207; c) G. Bringmann, T. Gulder, T. A. M. Gulder, M. Breuning,
Chem. Rev. 2011, 111, 563-639.
[12] For typical central‐to‐axial chirality transfer examples, see: a) O.
Quinonero, M. Jean, N. Vanthuyne, C. Roussel, D. Bonne, T.
Constantieux, C. Bressy, X. Bugaut, J. Rodriguez, Angew. Chem. Int.
Ed. 2016, 55, 1401-1405; Angew. Chem. 2016, 128, 1423-1427; b) V.
S. Raut, M. Jean, N. Vanthuyne, C. Roussel, T. Constantieux, C.
Bressy, X. Bugaut, D. Bonne, J. Rodriguez, J. Am. Chem. Soc. 2017,
139, 2140-2143; c) A. Link, C. Sparr, Angew. Chem. Int. Ed. 2018, 57,
7136-7139; Angew. Chem. 2018, 130, 7254-7257.
[2]
[3]
[4]
S. R. LaPlante, L. D. Fader, K. R. Fandrick, D. R. Fandrick, O. Hucke,
R. Kemper, S. P. F. Miller, P. J. Edwards, J. Med. Chem. 2011, 54,
7005-7022.
[13] a) T. Yoshida, H. Morimoto, N. Kumagai, S. Matsunaga, M. Shibasaki,
M. Shibasaki, Angew. Chem. Int. Ed. 2005, 44, 3470-3474; Angew.
Chem. 2005, 117, 3536-3540; b) M. T. Reetz, J.-A. Ma, R. Coddard,
Angew. Chem. Int. Ed. 2005, 44, 412-415; Angew. Chem. 2005, 117,
416-419; c) X.-B. Yang, J. Feng, J. Zhang, N. Wang, L. Wang, J.-L. Liu,
X.-Q. Yu, Org. Lett. 2008, 10, 1299-1302; d) B. M. Trost, D. A. Bringley,
S. M. Silverman, J. Am. Chem. Soc. 2011, 133, 7664-7667; e) K. Endo,
S. Yakeishi, D. Hamada, T. Shibata, Chem. Lett. 2013, 42, 547-549; f)
S.-Y. Yan, Y.-Q. Han, Q.-J. Yao, X.-L. Nie, L. Liu, B.-F. Shi, Angew.
Chem. Int. Ed. 2018, 57, 9093-9097; Angew. Chem. 2018, 130, 9231-
9235.
For typical reviews, see: a) Y. Chen, S. Yekta, A. K. Yudin, Chem. Rev.
2003, 103, 3155-3211; b) J. M. Brunel, Chem. Rev. 2007, 107, PR1-
PR45.
a) P. Lin, Chem. Rev. 1998, 98, 2405-2494; b) P. Lin, Acc. Chem. Res.
2012, 45, 150-163; c) R. Noyori, H. Takaya, Acc. Chem. Res. 1990, 23,
345-350; d) M. Berthod, G. Mignani, G. Woodward, M. Lemaire, Chem.
Rev. 2005, 105, 1801-1836; e) T. Akiyama, Chem. Rev. 2007, 107,
5744-5758; f) M. Terada, Chem. Commun. 2008, 4097-4112; g) M.
Rueping, A. Kuenkel, I. Atodiresei, Chem. Soc. Rev. 2011, 40, 4539-
4549; h) D. Parmar, E. Sugiono, S. Raja, M. Rueping, Chem. Rev.
2014, 114, 9047-9153; i) P. Kočovský, Š. Vyskočil, M. Smrčina, Chem.
Rev. 2003, 103, 3213-3245; j) M. Shibasaki, S. Matsunaga, Chem. Soc.
Rev. 2006, 35, 269-279.
[14] O. J. X. Morel, R. M. Christie, Chem. Rev. 2011, 111, 2537-2561.
[15] a) S. M. Janes, D. Mu, D. Wemmer, A. J. Smith, S. Kaur, D. Maltby, A.
L. Burlingame, J. P. Klinman, Science 1990, 248, 981-987; b) M. Mure,
Acc. Chem. Res. 2004, 37, 131-139; c) M. Largeron, M. B. Fleury,
Science, 2013, 339, 43-44; d) J. P. Klinman, F. Bonnot, Chem. Rev.
2014, 114, 4343-4365; e) A. E. Wendlandt, S. S. Stahl, Angew. Chem.
Int. Ed. 2015, 54, 14638-14658; Angew. Chem. 2015, 127, 14848-
14868; f) M. Largeron, Org. Biomol. Chem. 2017, 15, 4722-4730.
[16] For typical reviews, see: a) E. Kumarasamy, R. Raghunathan, M. P.
Sibi, J. Sivaguru, Chem. Rev. 2015, 115, 11239-11300; For selected
examples: a) J. L. Gustafson, D. Lim, S. J. Miller, Science 2010, 328,
1251-1255; b) K. Mori, Y. Ichikawa, M. Kobayashi, Y. Shibata, M.
Yamanaka, T. Akiyama, J. Am. Chem. Soc. 2013, 135, 3964-3970; c) K.
T. Barrett, A. J. Metrano, P. R. Rablen, S. J. Miller, Nature 2014, 509,
71-75; d) Y.-H. Chen, L.-W. Qi, F. Fang, B. Tan, Angew. Chem. Int. Ed.
2017, 56, 16308-16312; Angew. Chem. 2017, 129, 16526-16530; e) H.-
H. Zhang, C.-S. Wang, C. Li, G.-J. Mei, Y. Li, F. Shi, Angew. Chem. Int.
Ed. 2017, 56, 116-121; Angew. Chem. 2017, 129, 122-127; f) J. D.
Jolliffe, R. J. Armstrong, M. D. Smith, Nat. Chem. 2017, 9, 558-562; g)
K. Zhao, L. Duan, S. Xu, J. Jiang, Y. Fu, Z. Gu, Chem 2018, 4, 599-612;
h) V. Hornillos, J. A. Carmona, A. Ros, J. Iglesias-Sigüenza, J. López-
Serrano, R. Fernández, J. M. Lassaletta, Angew. Chem. Int. Ed. 2018,
57, 3777-3781; Angew. Chem. 2018, 130, 3839-3843; i) S. Jia, Z.
Chen, N. Zhang, Y. Tan, Y. Liu, J. Deng, H. Yan, J. Am. Chem. Soc.
2018, 140, 7056-7060; j) S.-C. Zheng, Q. Wang, J. Zhu, Angew. Chem.
Int. Ed. 2019, 58, 1494-1498; Angew. Chem. 2019, 131, 1508-1512; k)
J. Luo, T. Zhang, L. Wang, G. Liao, Q.-J. Yao, Y.-J. Wu, B.-B. Zhan, Y.
Lan, X.-F. Lin, B.-F. Shi, Angew. Chem. Int. Ed. 2019, 58, 6708-6712;
Angew. Chem. 2019, 131, 6780-6784; l) G. Liao, H.-M. Chen, Y.-N. Xia,
B. Li, Q.-J. Yao, B.-F. Shi, Angew. Chem. Int. Ed. 2019, 58, 11464-
[5]
[6]
a) O. Baudoin, Eur. J. Org. Chem. 2005, 2005, 4223-4229; b) J.
Wencel-Delord, A. Panossian, F. R. Leroux, F. Colobert, Chem. Soc.
Rev. 2015, 44, 3418-3430; c) P. Loxq, E. Manoury, R. Poli, E. Deydier,
A. Labande, Coord. Chem. Rev. 2016, 308, 131-190; d) B. Zilate, A.
Castrogiovanni, C. Sparr, ACS Catal. 2018, 8, 2981-2988.
a) M. Nakajima, I. Miyoshi, K. Kanayama, S. Hashimoto, M. Noji, K.
Koga, J. Org. Chem. 1999, 64, 2264-2271; b) J. Gao, J. H. Reibenspies,
A. E. Martell, Angew. Chem. Int. Ed. 2003, 42, 6008-6010; Angew.
Chem. 2003, 115, 6190-6194; c) J. B. Hewgley, S. S. Stahl, M. C.
Kozlowski, J. Am. Chem. Soc. 2008, 130, 12232-12233; d) S. K.
Alamsetti, E. Poonguzhali, D. Ganapathy, G. Sekar, Adv. Synth. Catal.
2013, 355, 2803-2808; e) C.-Y. Chu, D.-R. Hwang, S.-K. Wang, B.-J.
Uang, Chem. Commun. 2001, 980-981; f) N. B. Barhate, C.-T. Chen,
Org. Lett. 2002, 4, 2529-2532; g) Z. Luo, Q. Liu, L. Gong, X. Cui, A. Mi,
Y. Jiang, Angew. Chem. Int. Ed. 2002, 41, 4532-4535; Angew. Chem.
2002, 114, 4714-4717; h) Q.-X. Guo, Z.-J. Wu, Z.-B. Luo, Q.-Z. Liu, J.-
L. Ye, S.-W. Luo, L.-F. Cun, L.-Z. Gong, J. Am. Chem. Soc. 2007, 129,
13927-13938; i) S. Takizawa, T. Katayama, H. Sasai, Chem. Commun.
2008, 4113-4122; j) H. Egami, T. Katsuki, J. Am. Chem. Soc. 2009, 131,
6082-6083; k) R. Irie, K. Masutani, T. Katsuki, Synlett 2000, 1433-1436.
M. Smrčina, Š. Vyskočil, B. Máca, M. Polášek, T. A. Claxton, A. P.
Abbott, P. Kočovský, J. Org. Chem. 1994, 59, 2156-2163.
[7]
[8]
a) H. Egami, K. Matsumoto, T. Oguma, T. Kunisu, T. Katsuki, J. Am.
Chem. Soc. 2010, 132, 13633-13635; b) S. Narute, R. Parnes, F. D.
Toste, D. Pappo, J. Am. Chem. Soc. 2016, 138, 16553-16560; c) J.-M.
Tian, A.-F. Wang, J.-S. Yang, X.-J. Zhao, Y.-Q, Tu, S.-Y. Zhang, Z.-M.
Chen, Angew. Chem. Int. Ed. 2019, 58, 11023-11027; Angew. Chem.
2019, 131, 11139-11143.
4
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11468; Angew. Chem. 2019, 131, 11586-11590; m) F. Jiang, K.-W.
Chen, P. Wu, Y.-C. Zhang, Y. Jiao, F. Shi, Angew. Chem. Int. Ed. 2019,
58, 15104-15110; Angew. Chem. 2019, 131, 15248-15254; n) Y.-B.
Wang, Q.-H. Wu, Z.-P. Zhou, S.-H. Xiang, Y. Cui, P. Yu, B. Tan, Angew.
Chem. Int. Ed. 2019, 58, 13443-13447; Angew. Chem. 2019, 131,
13577-13581; o) X. Chen, D. Gao, D. Wang, T. Xu, W. Liu, P. Tian, X.
Tong, Angew. Chem. Int. Ed. 2019, 58, 15334-15338; Angew. Chem.
2019, 131, 15478-15482; p) K. Xu, W. Li, S. Zhu, T. Zhu, Angew. Chem.
Int. Ed. 2019, 58, 17625-17630; Angew. Chem. 2019, 131, 17789-
17794; q) R. Deng, J. Xi, Q. Li, Z. Gu, Chem 2019, 5, 1834-1846; r) D.
Shen, Y. Xu, S.-L. Shi, J. Am. Chem. Soc. 2019, 141, 14938-14945; s)
R. M. Witzig, V. C. Fäseke, D. Häussinger, C. Sparr, Nat. Catal. 2019,
2, 925-930; t) L.-W. Qi, S. Li, S.-H. Xiang, J. Wang, B. Tan, Nat. Catal.
2019, 2, 314-323; u) S. Lu, S. V. H. Ng, K. Lovato, J.-Y. Ong, S. B. Poh,
X. Q. Ng, L. Kürti, Y. Zhao, Nat. Commun. 2019, 10, 3061; v) S. Lu, J.-
Y. Ong, H. Yang, S. B. Poh, X. Liew, C. S. D. Seow, M. W. Wong, Y.
Zhao, J. Am. Chem. Soc. 2019, 141, 17062-17067; w) M. Tian, D. Bai,
G. Zheng, J. Chang, X. Li, J. Am. Chem. Soc. 2019, 141, 9527-9532; x)
Q. Wang, Z.-J. Cai, C.-X. Liu, Q. Gu, S.-L. You, J. Am. Chem. Soc.
2019, 141, 9504-9510.
[17] Y.-B. Wang, B. Tan, Acc. Chem. Res. 2018, 51, 534-547.
[18] For pioneering studies, see: a) T. Akiyama, J. Itoh, K. Yokota, K.
Fuchibe, Angew. Chem. Int. Ed. 2004, 43, 1566-1568; Angew. Chem.
2004, 116, 1592-1594; b) D. Uraguchi, M. Terada, J. Am. Chem. Soc.
2004, 126, 5356-5357.
[19] a) M. Bandini, A. Melloni, A. Umani-Ronchi, Angew. Chem. Int. Ed.
2004, 43, 550-556; Angew. Chem. 2004, 116, 560-566; b) M. Bandini,
A. Eichholzer, Angew. Chem. Int. Ed. 2009, 48, 9608-9644; Angew.
Chem. 2009, 121, 9786-9824; c) M. Zeng, S.-L. You, Synlett 2010,
1289-1301.
[20] a) D. Bonne, J. Rodriguez, Chem. Commun. 2017, 53, 12385-12393; b)
D. Bonne, J. Rodriguez, Eur. J. Org. Chem. 2018, 2417-2431.
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Entry for the Table of Contents
A class of atropisomeric aryl-p-quinones were efficiently assembled by means of chiral phosphoric acid catalyzed enantioselective
arylation of p-quinones via central-to-axial chirality transfer process. This novel axially chiral framework was able to serve as platform
molecule for diversity-oriented synthesis of a wide range of highly functionalized non-C2 symmetric biaryldiols with highly preserved
chiral integrity.
6
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