Atroposelective Synthesis of Axially Chiral Biaryldiols via Organocatalytic Arylation of 2-Naphthols

Article abstract of DOI:10.1021/jacs.5b10152

The first phosphoric acid-catalyzed asymmetric direct arylative reactions of 2-naphthols with quinone derivatives have been developed, providing efficient access to a class of axially chiral biaryldiols in good yields with excellent enantioselectivities u

Full text of DOI:10.1021/jacs.5b10152

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Communication
Atroposelective Synthesis of Axially Chiral Biaryldiols
via Organocatalytic Arylation of 2-Naphthols
Ye-Hui Chen, Dao-Juan Cheng, Jian Zhang, Yong Wang, Xin-Yuan Liu, and Bin Tan
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b10152 • Publication Date (Web): 11 Nov 2015
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Atroposelective Synthesis of Axially Chiral Biaryldiols via Organo-
catalytic Arylation of 2-Naphthols
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YeꢀHui Chen,a DaoꢀJuan Cheng,a Jian Zhang,a Yong Wang,b XinꢀYuan Liu*a, and Bin Tan*a
a Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055, China
b College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, P. R. China
Supporting Information Placeholder
ABSTRACT: The first phosphoric acidꢀcatalyzed asymmetric
direct arylative reactions of 2ꢀnaphthols with quinone derivatives
have been developed, providing an efficient access to a class of
axially chiral biaryldiols in good yields with excellent enantioseꢀ
lectivities under mild reaction conditions. This approach is highly
convergent and functional group tolerant, providing the rapid
construction of axially chiral compounds from simple, readily
available starting materials. The excellent stereocontrol of the
process stems from the efficient transfer of the stereochemical
information of chiral phosphoric acid into the axis chirality of
biaryldiol products. The preliminary results demonstrated that the
resultant biaryldiols can act as an efficient chiral ligand in asymꢀ
metric transformations.
In this context, there have only been a few synthetic attempts
toward enantioselective synthesis of these axially chiral biaryldiꢀ
ols, which includes direct metalꢀcatalyzed asymmetric oxidative
crossꢀcoupling reactions6 and kinetic resolutions7 (Scheme 1).
Although the oxidative crossꢀcoupling reactions represent a
straightforward way to access nonꢀsymmetric biaryldiols from
achiral precursors, the current catalytic systems can only produce
desired products with certain specific substitution patterns in high
enantioselectivity. Over the past several decades, the kinetic resoꢀ
lution of racemic starting materials has been one of the most powꢀ
erful and reliable strategies for the synthesis of enantiopure comꢀ
pounds in both academia and industry. However, the catalytic
kinetic resolution of these axially chiral biaryldiols has surprisingꢀ
ly underdeveloped8 and accompanied with a limitation of no more
than 50% yield. More recently, Akiyama achieved a significant
breakthrough by using phosphoric acid to enable asymmetric
atroposelective bromination, providing a more useful avenue to
access these types of axially biaryldiol skeleton.9 Despite these
successful results, the development of efficient and highly enantiꢀ
oselective strategy for facile access to axially chiral biaryldiols
would greatly expand the application scope and is still in great
demand.
The axially chiral C2ꢀsymmetric BINOL and their derivatives
have been extensively evaluated as versatile chiral ligꢀ
ands/catalysts in asymmetric transformations.1 In addition, their
wellꢀestablished conversions to the corresponding BINAP2 and
phosphoric acids3 further expand their synthetic utility in various
domains of asymmetric catalysis (Figure 1). As a result, the conꢀ
struction of these scaffolds has attracted considerable attention
and the relatively practical methods have already been achieved.1
Furthermore, recent studies have disclosed that the nonꢀsymmetric
BINOL derivatives (biaryldiols) are also used as efficient chiral
ligands or catalysts.4 Noteworthy is that this motif is a prominent
feature of many biological active natural products5 like the faꢀ
mous Vancomycin, Knipholone and Gossypol (Figure 1). Comꢀ
pared with the successful application and synthesis of C2ꢀ
symmetric BINOLs, the application of these biaryldiols remains
largely underexplored with respect to asymmetric synthesis and
natural products synthesis, which is probably due to lack of reliaꢀ
ble synthetic routes.1a
Scheme 1. The Existing Strategies for Atroposelective Synthe-
sis of Axially Chiral Biaryldiols
Quinones have long served as useful synthetic precursors to
construct densely functionalized aromatic rings.10 Accordingly,
their application in asymmetric organocatalysis has been on the
increase as an expedient means to deliver a range of optically
enriched compounds.11 Motivated by these progresses and the
recent development of synthesis of axial chiral compounds,12 we
envisioned that 2ꢀnaphthols could directly react with quinones to
afford the chiral biarydiols, thus providing the possibility to deꢀ
velop a direct enantioselective arylation strategy to construct axiꢀ
ally chiral nonꢀsymmetric biaryldiols. As shown in Scheme 2, we
postulated that conjugated addition intermediates A could be genꢀ
erated from 2ꢀnaphthols and quinones, and subsequently aromaꢀ
tized with efficient central to axial chirality exchange6e,12l,13 as a
result of the restricted rotation to yield the final axial chiral comꢀ
pounds. In this scenario, several challenges had to be encountered:
Figure 1. Selected natural products and ligands/catalysts involvꢀ
ing axially chiral biaryldiols
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(1) the selection of reasonable catalyst to increase the reactivity,
ing has a negative effect on the results while the higher loading
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to efficiently control C/O chemoselectivity of the 2ꢀnaphthols; (2)
the choice of chiral catalyst to efficiently induce stereocontrol in
the conjugated addition step; (3) the use of mild reaction condiꢀ
tions to transfer the chirality and obviate the axial rotation. As
part of our continued interest for asymmetric synthesis of axially
chiral compounds14 and phosphoric acid catalysis,15 herein, we
describe the novel chiral phosphoric acidꢀcatalyzed highly enantiꢀ
oselective direct arylative reactions of 2ꢀnaphthols and quinone
derivatives, providing a new synthetic route toward axially chiral
biaryldiols bearing multiple substituent patterns; such structural
motifs are important components of various biologically active
natural products5 and should have the potential application for
asymmetric catalysis.4
does not improve the chemical yield and stereoselectivity (Table
1, entries 17, 18). The reaction concentration has a fairly influence
on the chemical yield and enantioselectivity. When more or less
concentrated solution was employed, the chemical yield and ee of
the product decreased (Table 1, entry 19, 20).
Table 1. Optimization of the Reaction Conditionsa
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Scheme 2. Our Strategy for Atroposelctive Synthesis of Axial-
ly Chiral Biaryldiols via Direct Arylation of 2-Naphthols
entry catalyst solvent
T (oC)
yield
(%)b
90
ee (%)c
We initiated our studies by evaluating the reaction between
quinone 1a and 2ꢀnaphthol 2a in toluene at room temperature in
the presence of the typically used phosphoric acid catalyst (CPA)
C1 (Scheme 3). To our delight, the reaction proceeded smoothly
and afforded the desired axially chiral biaryldiol 3a in good yield,
albeit with poor enantioselectivity (23% ee). However, after makꢀ
ing great efforts on optimization of the reaction conditions, we
could not improve the enantioselectivity by using the current
model reaction.
1
2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DCM
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0
57
3
C1
C2
C3
C4
C5
C6
C7
C8
C9
C1
C1
C1
C1
C1
C1
C1
C1
C1
C1
C1
85
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92
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0
6
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ꢀ41
ꢀ4
ꢀ7
72
65
70
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80
85
93
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88
93
8
Scheme 3. Initial Results for Direct Synthesis of Biaryldiols
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17d
18e
19f
20g
DCE
CHCl3
EtOAc
DCM
DCM
ꢀ40
ꢀ78
ꢀ78
ꢀ78
ꢀ78
ꢀ78
To improve reaction results, we modified the design of the
quinone substrate to provide its potential interaction for hydrogen
bonding formation with catalysts. Specifically, we installed an
ester group into quinone skeleton to facilitate access of the cataꢀ
lyst to the ketoneꢀester moiety16 for multiple hydrogenꢀbonding,
thus enabling the simultaneous activation of a nucleophile and an
electrophile in a suitable spatial configuration. The quinone derivꢀ
ative 1b was tested for this reaction, using CPA C1 as a catalyst,
the enantioselectivity was improved up to 57% ee (Table 1, entry
1). Encouraged by this promising result, a detailed optimization
study was first done with different CPAs (C1ꢀC9). Several
BINOL, SPINOL, and VAPOLꢀderived catalysts were investigatꢀ
ed, which displayed remarkable effects on the outcome of the
reaction (Table 1, entries 1ꢀ9). The results clearly demonstrated
that CPA with a very bulky substituted group in the 3,3’ꢀposition
gave rise to good enantiocontrol. It should be noted that almost no
ee of product 4a was obtained with VAPOLꢀderived phosphoric
acid C6 as the catalyst, which is most likely due to the less steric
hindrance with the starting material. Of the solvents tested for the
reaction catalyzed by C1 (Table 1, entries 10ꢀ13), dichloroꢀ
methane (DCM) proved optimal with respect to the enantioselecꢀ
tivity (Table 1, entry 10). Attempts to optimize the reaction by
conducting it in different temperature succeeded to provide the
desired improvement in enantioselectivity and found the best
results can be obtained with up to 90% yield in 93% ee at the
temperature of ꢀ78 oC (Table 1, entry 16). The lower catalyst loadꢀ
DCM
DCM
DCM
DCM
DCM
a
The reaction was carried out with 2ꢀmethoxycarbonylꢀ1,4ꢀ
benzoquinone 1b (0.10 mmol), 7ꢀmethoxylꢀ2ꢀnaphthol 2a (0.12
mmol) and catalyst (5 mol %) in 2 mL of solvent for 24 h under
b
Ar. Isolated yield based on 1b. c ee values were determined by
d
HPLC analysis using a chiral stationary phase. . 2.5 mol % of
e
C1 was employed. 10 mol % of C1 was employed. f 1 mL of
DCM was employed. g 3 mL of DCM was employed for 48 h.
After the optimal reaction conditions being established, we set
out to explore the substrate scope with respect to various quinones
and 2ꢀnaphthols as reactants (Table 2). As regarding to the quiꢀ
none derivatives, the phosphoric acidꢀcatalyzed direct arylation
reaction proceeded smoothly with a variety of quinone esters to
afford the desired products under mild reaction condition. All of
the investigated reactions were complete within 24 hours and gave
products (4aꢀ4i) in good yields (70ꢀ90%) and with excellent enanꢀ
tioselectivities (92ꢀ99% ee). For the use of 2ꢀnaphthols, the posiꢀ
tion and the electronic properties of the substituents on the aroꢀ
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matic ring appeared to have a very limited effect on stereoselecꢀ
Based on the experimental results, a possible reaction process
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tivity. Regardless of the type of substituents on the aromatic rings,
bearing electronꢀwithdrawing (Table 2, products 4n-4s), electronꢀ
donating (Table 2, product 4j), or neutral (4k-4m) groups at the
different positions, the reactions of these 2ꢀnaphthols gave the
axially chiral biaryldiols with very high stereoselectivities and
good reactivity. It is noteworthy that the use of a steric hindrance
8ꢀsubstituted naphthanol, also afforded the desired product 4q in
excellent stereocontrol (97% ee) under the standard reaction conꢀ
ditions, demonstrating that the substrate scope could not be only
limited to less bulky 2ꢀnaphthols. It should be noted that changing
the ester group to the more useful halogen group, such as Cl or Br
at the quinone moiety, has almost no influence on the reaction
efficiency and stereoselectivity with excellent results (4t, 4u),
which is very important for chiral ligands or catalysts design beꢀ
cause halides are very reactive for further modifications in many
transition metalꢀcatalyzed reactions.17
is illustrated in Scheme 5. The chiral phosphoric acid C1 perꢀ
formed as a bifunctional organocatalyst to simultaneously activate
2ꢀnaphthols and quinone derivatives by multiple hydrogenꢀ
bonding activation and promote the first step of enantioselective
conjugated addition to form the intermediate A. The following
step is just to transfer its central chirality information into its axial
chirality and affords the final chiral biaryldiol.6e,12l,13 The ester
moiety or halogen in the 2ꢀposition of the quinone might play a
very important role to control the stereoinduction via additional
interactions. In addition, these groups could help to increase the
stablity of the obtained products. However, the exact role of these
moieties remains unclear and deserves further investigations. In
order to confirm the absolute configuration (AC) of compounds 4,
the ECD spectra were calculated by the TDꢀDFT method, which
has been proven to be useful in predicting ECD spectra and asꢀ
signing the AC of organic molecules. The R configuration could
be reliably assigned to compound 4b (For details, see Supporting
Information Figure S1).
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Table 2. Substrates Scope of the Direct Arylation Reactiona,b,c
HO
O
Scheme 5. Proposed Reaction Process
R
OH
catalyst C1 (5 mol %)
R
OH
OH
R'
DCM, -78 oC,
24 h
R'
O
1
2
4
HO
Br
4a, R = Me, 90%, 93% ee
4b, R = Et, 90%, 96% ee
OH
4c, R = Pr, 87%, 99% ee
R =
Br
RO2C
Br
MeO
OH 4d, R = i-Pr, 85%, 97% ee
4e, R = Bu, 82%, 95% ee
4f, R = Bn, 75%, 92% ee
4g
77% yield
98% ee
4i
4h
70% yield
99% ee
76% yield
98% ee
HO
HO
HO
HO
An indication for the configurational stability of the product
EtO2C
OH
OH
EtO2C
OH
OH
EtO2C
OH
EtO2C
OH
OH
o
was obtained by heating a solution of 4b in DCE at 80 C for 24
OH
Ph
hours. HPLC analysis showed an unaffected enantiomeric exess.
Therefore, the obtained axially chiral compounds may have
potential applications as asymmetric organocatalysts/ligands. To
further investigate the utility of the obtained chiral biaryldiols, the
efficiency of (R)ꢀ4 as ligands for enantioselective addition of diꢀ
ethylzinc to aldehydes was verified, which is one of the most
reliable methods to prepare chiral secꢀalcohols and also a standard
reaction to test the reactivity and enantioselectivity of newly deꢀ
signed chiral ligands.18 As shown in the Table 3, the mixture preꢀ
pared by allowing a toluene solution of 4b or 4p and titanium
MeO
Ph
4j
4k
4ld
4me
88% yield
91% ee
88% yield
99% ee
84% yield
92% ee
85% yield
92% ee
HO
HO
EtO2C
HO
EtO2C
HO
EtO2C
MeO2C
OH
OH
OH
OH
OH
OH
EtO2C
Br
OH
OH
Br
NC
4nf
4o
4p
4q
82% yield
91% ee
84% yield
93% ee
80% yield
97% ee
60% yield
90% ee
HO
HO
HO
HO
o
tetraisopropoxide to stand at ꢀ5 C gave excellent chemical yields
EtO2C
OH
OH
BnO2C
OH
OH
OH
OH
OH
OH
Cl
Br
and enantiomeric excesses (96% or 99% ee). It should be noted
that the enantioselectivity for this model reaction was just 89% ee
with (S)ꢀBINOL as chiral ligand under the same reaction condiꢀ
tions, further demonstrating the useful utility of the obtained nonꢀ
symmetrical biaryldiols.
MeO
MeO
MeO2C
Br
4rg
82% yield
90% ee
4th (from 1j)
75% yield
95% ee
4uh (from 1k)
72% yield
96% ee
4s
71% yield
90% ee
a The reaction was carried out with quinone esters 1 (0.10 mmol),
2ꢀnaphthol 2 (0.12 mmol) and catalyst C1 (5 mol %) in 2 mL of
Table 3. Preliminary Application in Addition of Diethylzinc to
Aldehydea,b,c
b
DCM at ꢀ78oC for 24 h under Ar. Isolated yields based on quiꢀ
none esters. c ee values were determined by HPLC analysis using
e
a chiral stationary phase. d Reaction at ꢀ20 °C for 72 h. Reaction
f
at ꢀ78 °C for 48 h. Reaction at ꢀ25 °C with 10 mol % of C1 for
60 h. g Reaction at ꢀ10 °C with 10 mol% of C1 for 48 h. h Reaction
at ꢀ40 °C for 24 h.
To demonstrate the utility of the direct arylative reaction,
preparative scale synthesis of product 4b and 4t was carried out.
As displayed in Scheme 4, there was almost no change in reactiviꢀ
ty and stereoselectivity, suggesting that this method should have
the potential for largeꢀscale chemical production.
Scheme 4. Preparative Synthesis of 4b and 4t.
a
b
Reaction conditions, see supporting information.
Isolated
c
yields. ee values were determined by HPLC analysis using a
chiral stationary phase.
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(j) Burns, N. Z.; Krylova, I. N.; Hannoush, R. N.; Baran, P. S. J. Am.
chem. Soc. 2009, 131, 9172.
In summary, we have successfully developed the first phosꢀ
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phoric acidꢀcatalyzed asymmetric direct arylative reactions of 2ꢀ
naphthols with quinone derivatives, giving an efficient access to a
class of axially chiral biaryldiols in good yields with excellent
enantioselectivities under mild reaction conditions. This new apꢀ
proach is highly convergent and functional group tolerant, which
allows for the rapid construction of axially chiral compounds from
simple, readily available starting materials. The excellent stereꢀ
ocontrol of the process stems from the efficient transfer of the
stereochemical information of chiral phosphoric acid into the axis
chirality of biaryldiol products. The application of this strategy to
other substrate classes and mechanistic investigations addressing
the intricacies of the chirality transfer are currently underway in
our laboratory and will be reported in due course.
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ASSOCIATED CONTENT
Supporting Information
Experimental procedures, characterization of all new compounds,
Figure S1. This information is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
tanb@sustc.edu.cn
liuxy3@sustc.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Financial support from the National Natural Science Foundation
of China (Nos. 21572096, 21572095), and South University of
Science and Technology of China (FRGꢀSUSTC1501Aꢀ16) is
greatly appreciated. B.T. thanks the Thousand Young Talents
Program for financial support.
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