Synthesis of (±)-3,3′-diphenyl-2,2′-binaphthol via different routes using Pd and Ni as catalyst respectively

Article abstract of DOI:10.1007/s11696-020-01308-w

3,3′-Biphenyl-2,2′-binaphthols (BINOLs) are precursors of phosphoric acids that are widely used as ligands and catalysts in organic reactions. In this report, two routes for the synthesis of (±)-3,3′-diphenyl BINOLs via (±)-3,3′ bis-halogenated BINOLs int

Full text of DOI:10.1007/s11696-020-01308-w

Chemical Papers
https://doi.org/10.1007/s11696-020-01308-w
SHORT COMMUNICATION
Synthesis of ( ± ±)‑3‑′)diphenyl)232′)binaphthol via diꢀerent routes
using Pd and Ni as catalyst respectively
Zhengjiang Fu1 · Xihan Cao · Guangguo Hao · Quanqing Shi · Hu Cai
1
1
1
1
Received: 15 April 2020 / Accepted: 10 August 2020
©
Institute of Chemistry, Slovak Academy of Sciences 2020
Abstract
,3′-Biphenyl-2,2′-binaphthols (BINOLs) are precursors of phosphoric acids that are widely used as ligands and catalysts
3
in organic reactions. In this report, two routes for the synthesis of (±)-3,3′-diphenyl BINOLs via (±)-3,3′ bis-halogenated
BINOLs intermediates using (±)-BINOL as starting material have been established. Both routes are four-step reactions,
characterized by the use of diꢀerent catalysts in the third step, the total yield of the ꢁrst route is 45%, while overall yield of
the second route is 51% yield.
Keywords BINOLs · (±)-3,3′-Diphenyl BINOL · (±)-3,3′ Bis-halogenated BINOLs · Organic reactions
Due to the chiral auxiliaries and ligands with C2-symme-
try, chiral 3,3′-disubstituted-2,2′-binaphthol derivatives
revealed that the substituents at 3 and 3′ positions of the
BINOLs backbone have considerable electronic and/or steric
inꢂuence on chiral phosphoric acids catalytic performance
through theoretical and experimental methods. According
to this concept, changing the substituent groups at 3 and 3′
positions can, to a large extent, inꢂuence the steric and elec-
tronic properties of the BINOLs framework (Brunel 2005;
Kaupmees et al. 2013; Yang et al. 2013; Bisht et al. 2019).
Therefore, 3,3′ bis-arylated BINOLs are valuable precur-
sors for an array of phosphoric acids organocatalysts that
are applied in catalytic asymmetric reactions.
(
BINOLs) have been widely employed as important ligands
in catalytic asymmetric reactions since the several decades,
additionally, they have also been used as axially chiral back-
bones for the development of phosphoric acids through syn-
thetic sequences (Brunel 2005, 2007; Yamamoto and Futat-
sugi 2005; Luan and Schaus 2012; Zhou et al. 2012; Yu et al.
2
011). In this regard, chiral phosphoric acids derived from
BINOLs have bifunctional catalytic performance, namely
Brønsted acids sites play roles in capturing electrophiles
via hydrogen bonding interactions without formation of
loose ion pair, whereas phosphoryl oxygens act as Lewis
bases sites to capture another component, just as we have
known, phosphoric acids are prevalent organocatalysts that
have attracted increasing attention (Yu et al. 2008; Bartoli
et al. 2010; Mori et al. 2013; Yin and You 2011; Li 2013;
Dong et al. 2017). Furthermore, intensive studies have been
Although many 3,3′ bis-arylated BINOLs are com-
mercial outside, lengthy synthetic sequences and tedious
manipulations lead to high price-to-sales for 3,3′ bis-arylated
BINOLs, and the used 3,3′ bis-arylated BINOLs in most
laboratory are usually synthesized by themselves. Gener-
ally, there are two protocols for synthesis of 3,3′ bis-arylated
BINOLs, one via 3,3′ bis-metalled BINOLs intermediate
(
Simonsen et al. 1998; Wipf et al. 2000; Ahmed and Clark
014) and the other through 3,3′ bis-halogenated BINOLs
intermediate (Cox et al. 1992; Tsang et al. 2001; Ooi et al.
003; Bartoszek et al. 2008; Klussmann et al. 2010; Albini
2
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11696-020-01308-w) contains
supplementary material, which is available to authorized users.
2
et al. 2014), both 3,3′ bis-metalled BINOLs intermediate
and 3,3′ bis-halogenated BINOLs intermediate could under-
take coupling reactions with aryl sources to furnish 3,3′ bis-
arylated BINOLs (Simonsen et al. 1998; Wipf et al. 2000;
Ahmed and Clark 2014; Cox et al. 1992; Tsang et al. 2001;
Ooi et al. 2003; Bartoszek et al. 2008; Klussmann et al.
*
Zhengjiang Fu
fuzhengjiang@ncu.edu.cn
*
Hu Cai
caihu@ncu.edu.cn
1
College of Chemistry, Nanchang University,
Nanchang 330031, Jiangxi, China
2
010; Albini et al. 2014). Herein, we describe two diꢀerent
Vol.:(0
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Chemical Papers
methodologies for synthesis of ( ±)-3,3′-diphenyl BINOL
higher than that Snieckus reported (Cox et al. 1992). After
treatment of (±)-4 with concentrated HCl in 1,4-dioxane,
94% yield of ( ±)-3,3′-diphenyl(1,1′-binaphthalene)-2,2′-
diol ( ±)-5 was formed, which could be readily converted
to phosphoric acid bearing an axially binaphthyl backbone
with sterically demanding substituents at 3 and 3′ positions.
(±)-1—(±)-6: (±)-BINOL (1 equiv), K CO (3.5 equiv),
(
±)-5 via (±)-3,3′ bis-halogenated BINOLs intermediate.
The presented methods are complementary to previously
established procedures in the aspects of briefness and eꢃ-
ciency (Yang et al. 2016).
(
±)-1—( ±)-2: (i) ( ±)-BINOL (1 equiv), NaH (60%
dispersion in mineral oil, 2.5 equiv), THF, 0 °C, 1 h; (ii)
2
3
MOMCl (2.5 equiv), 0 °C, 5 h. ( ±)-2—( ±)-3: (i) n-BuLi
MeI (4 equiv), anhydrous acetone, reꢂux, 20 h; (±)-6—
(
1.6 M in hexane, 2.5 equiv), − 78 °C—0 °C, THF, 1 h; (ii)
( ±)-7: (i) TMEDA (3.5 equiv), n-BuLi (1.6 M in hexane,
Br /pentane (4 equiv), − 78 °C—rt, 10 h. (±)-3—( ±)-4:
2.5 equiv), ether, 1.5 h, rt; (ii) I /ether (6 equiv), − 78 °C~rt,
2
2
PhB(OH) (2.4 equiv), K PO •3H O (3 equiv), PPh (0.22
10 h; (±)-7—(±)-8: Ni(acac) (0.1 equiv), PhMgBr/ether
2
3
4
2
3
2
equiv), Pd(OAc) (0.05 equiv), THF, 85 °C, 20 h. (±)-4—
(5 equiv), benzene, rt ~ reꢂux, 20 h; ( ±)-8—( ±)-5: BBr
2
3
(
±)-5: conc. HCl, 1,4-dioxane, 50 °C~rt, several minutes.
(1.0 M in CH Cl , 6.5 equiv), 0 °C~rt, 20 h.
2
2
As shown in Scheme 1, the first route to synthe-
C o n s i d e r i n g
t h e
b r o m i n a t i o n
o f
size ( ±)-5 started with the commercially available
(±)-2,2′-bis(methoxymethyl)-1,1′-binaphthalene (±)-2 pro-
vided desired (±)-3,3′-dibromo-2,2′-bis(methoxymethyl)-
1,1′-binaphthalene ( ±)-3 in moderate yield in the
Scheme 1, another methodology was highly desirable to
handle this unsatisꢁed result. As illustrated in Scheme 2,
the starting synthetic sequence was based on the use of
( ±)-2,2′-dimethoxy-1,1′-binaphthalene ( ±)-6, which was
ꢁrst obtained from the nearly complete conversion of the
corresponding (±)-BINOL (±)-1 in the presence of stoichi-
ometric amounts of potassium carbonate and methyl iodide
in anhydrous acetone under reꢂux conditions. Afterwards,
dilithiation of (±)-2,2′-dimethoxy-1,1′-binaphthalene (±)-6
was done with tetramethylethylenediamine and n-butyllith-
ium in low temperature for an hour, followed by diiodi-
nation with iodine in ether to aꢀord (±)-3,3′-diiodo-2,2′-
dimethoxy-1,1′-binaphthalene (±)-7 in 87% yield. The yield
of diiodination in our route is higher than those in literatures
(Zheng et al. 2012; Ðorđević et al. 2015). Although Pd-cata-
lyzed reactions have occupied a central role for forming new
C–C bonds, Ni-catalyzed transformations have witnessed
(
±)-BINOL. First, the ( ±)-BINOL ( ±)-1 was treated
with stoichiometric amounts of sodium hydride (NaH)
and chloromethyl methyl ether (MOMCl) in THF to
give 83% yield of ( ±)-2,2′-bis(methoxymethyl)-1,1′-
binaphthalene ( ±)-2. Based on known literatures (Ooi
et al. 2003; Xu et al. 2005; Osorio-Planes et al. 2014), the
(
±)-2,2′-bis(methoxymethyl)-1,1′-binaphthalene ( ±)-2
was then carried out with n-butyllithium in low tempera-
ture for half an hour, followed by dibromination with the
solution of bromine in pentane to aꢀord (±)-3,3′-dibromo-
2
,2′-bis(methoxymethyl)-1,1′-binaphthalene (±)-3 in 63%
yield along with some monobromination byproduct at
room temperature (rt). Subsequently, a Suzuki coupling
transformation of dibromo functional groups of (±)-3 was
accomplished with stoichiometric amounts of phenylbo-
ronic acid and potassium phosphate tribasic trihydrate in
THF via palladium acetate/triphenylphosphine catalyst
system to give (±)-3,3′-diphenyl-2,2′-bis(methoxymethyl)-
1
,1′-binaphthalene ( ±)-4 in 92% yield, which was much
Scheme 1 The ꢁrst route to synthesize (±)-3,3′-diphenyl BINOL (±)-5
Scheme 2 The second route to synthesize (±)-3,3′-diphenyl BINOL (±)-5
1
3

Chemical Papers
considerable development and become one of the most
promising synthetic tools, partially due to the nonprecious
and earth-abundant nature of nickel versus its noble counter-
part palladium. Thereafter, the subsequent approach involved
Ni-catalyzed Kumada transformation of the (±)-3,3′-diiodo-
ꢁltered through a pad of celite and then washed with EtOAc.
The combined organic phase was washed with brine, dried
over Na SO , ꢁltered and concentrated in vacuo. The resi-
2
4
due was then puriꢁed by ꢂash chromatography on silica gel
(15% ether in hexane) to aꢀord 1.42 g (83%) corresponding
product as a white solid.
2
3
8
,2′-dimethoxy-1,1′-binaphthalene ( ±)-7 into desired
,3′-diphenyl-2,2′-dimethoxy-1,1′-binaphthalene ( ±)-8 in
6% yield with stoichiometric amounts of phenylmagnesium
bromide in mixed solvents, and the obtained yield was supe-
rior to previous reports (Cram et al. 1981; Wipf et al. 2000).
Finally, quantities of boron tribromide were slowly added
into the solution of (±)-3,3′-diphenyl-2,2′-dimethoxy-1,1′-
binaphthalene (±)-8 in anhydrous dichloromethane, which
aꢀorded ( ±)-3,3′-diphenyl(1,1′-binaphthalene)-2,2′-diol
Preparation of ( ± ±‑3,3′‑dibromo‑2,2′‑bis(m
ethoxymethyl±‑1,1′‑binaphthalene [( ± ±‑3,
in ꢀcheme 1]
50-mL, one-necked, round-bottomed ꢂask equipped with a
stir bar was charged with (±)-2,2′-bis(methoxymethyl)-1,1′-
binaphthalene (1.42 g, 4.2 mmol, 1 equiv) and THF (20 mL).
The mixture was cooled to -78 °C with stirring, and n-butyl-
lithium (n-BuLi) (6.6 mL, 1.6 M in hexane, 10.5 mmol, 2.5
equiv) was slowly added via syringe at this temperature.
Then, the reaction mixture was allowed to warm to 0 °C and
stirred for 1 h. After 1 h, the reaction mixture was re-cooled
(
±)-5 in 72% yield.
In summary, we have reported two diꢀerent methods to
furnish (±)-3,3′-diphenyl BINOL via (±)-3,3′ bis-halogen-
ated BINOL intermediates using ( ±)-BINOL as starting
material in this paper. Additionally, the described protocols
to synthesize ( ±)-3,3′-diphenyl BINOL here are likely to
provide access to several varieties of phosphoric acids which
can be used in the development of ligands and catalysts pre-
cursors for organic catalytic reactions.
to -78 °C, and the solution of bromine (Br ) (0.43 mL,
2
16.8 mmol, 4 equiv) in pentane (5 mL) was slowly added
in to reaction mixture via syringe. Subsequently, the reac-
tion mixture was allowed to warm to room temperature and
stirred for 10 h. Then, the reaction mixture was diluted with
saturated aqueous Na SO , ꢁltered through a pad of celite
Experimental
2
3
and then washed with EtOAc. The combined organic phase
was washed with brine, dried over Na SO , ꢁltered and con-
Chloromethyl methyl ether (Amato et al. 1979) and phe-
nylmagnesium bromide (Gülak et al. 2012) were prepared
following literature procedures. All other reagents were
commercially available. All reactions were performed under
nitrogen atmosphere unless otherwise noted. Column chro-
2
4
centrated in vacuo. The residue was then puriꢁed by ꢂash
chromatography on silica gel (3% ether in hexane) to aꢀord
1.33 g (63%) dibromination product as a white solid and
0.19 g (11%) monobromination byproduct as a white solid.
1
matography was performed on silica gel 300–400 mesh. H
1
3
and C NMR spectra were recorded at 400 and 100 MHz
with CDCl as solvent, respectively, and all coupling con-
Preparation of ( ± ±‑3,3′‑diphenyl‑2,2′‑bis(m
ethoxymethyl±‑1,1′‑binaphthalene [( ± ±‑ꢁ,
in ꢀcheme 1]
3
stants (J values) were reported in Hertz (Hz). Elemental
analyses were performed by Comprehensive Laboratory
Center of College of Chemistry.
A 50-mL, one-necked, round-bottomed ꢂask equipped with
a stir bar was charged with phenylboronic acid (PhB(OH) )
2
Preparation of ( ± ±‑2,2′‑bis(methoxymethyl±‑
(0.79 g, 6.5 mmol, 2.4 equiv), potassium phosphate triba-
1
,1′‑binaphthalene [( ± ±‑2, in ꢀcheme 1]
sic trihydrate (K PO •3H O) (2.16 g, 8.1 mmol, 3 equiv),
3
4
2
triphenylphosphine (PPh ) (0.16 g, 0.6 mmol, 0.22 equiv),
3
1
00-mL, one-necked, round-bottomed ꢂask equipped with
a stir bar was charged with sodium hydride (NaH) (0.5 g,
0% dispersion in mineral oil, 12.5 mmol, 2.5 equiv), (±)-
palladium acetate (Pd(OAc) ) (0.030 g, 8.1 mmol, 0.05
2
equiv), ( ±)-3,3′-dibromo-2,2′-bis(methoxymethyl)-1,1′-
binaphthalene (1.33 g, 2.7 mmol, 1 equiv) and THF (20 mL).
With stirring, the reaction mixtures were heated at 85 °C
for 20 h, and then cooled down to room temperature. The
reaction mixtures were diluted with deionized water, ꢁltered
through a pad of celite and then washed with EtOAc. The
combined organic phase was washed with brine, dried over
Na SO , ꢁltered and concentrated in vacuo. The residue was
6
BINOL (1.43 g, 5 mmol, 1 equiv) and THF (30 mL). The
mixture was stirred at 0 °C for 1 h, and then chloromethyl
methyl ether (MOMCl) (0.95 mL, 12.5 mmol, 2.5 equiv)
was slowly added via syringe at this temperature. After the
addition, the reaction mixture was stirred at 0 °C for 5 h.
Subsequently, the reaction mixture was warmed to room
2
4
temperature and diluted with saturated aqueous NH Cl,
then puriꢁed by ꢂash chromatography on silica gel (6% ether
4
1
3

Chemical Papers
in hexane) to aꢀord 1.21 g (92%) corresponding product as
a white solid.
to room temperature and stirred for 10 h. Then, the reaction
mixture was diluted with saturated aqueous Na SO , ꢁltered
2
3
through a pad of celite and then washed with EtOAc. The
combined organic phase was washed with brine, dried over
Na SO , ꢁltered and concentrated in vacuo. The residue was
ꢀ
ynthesis of ( ± ±‑3,3′‑diphenyl(1,1′‑binaphth
2
4
alene±‑2,2′‑diol [( ± ±‑ꢂ, in ꢀcheme 1]
then puriꢁed by ꢂash chromatography on silica gel (8% ether
in hexane) to aꢀord 2.34 g (87%) corresponding product as
a yellow solid.
A 50-mL, one-necked, round-bottomed flask equipped
with a stir bar was charged with ( ±)-3,3′-diphenyl-2,2′-
bis(methoxymethyl)-1,1′-binaphthalene (1.30 g, 2.6 mmol,
1
equiv), concentrated HCl solution (10 mL) and 1,4-diox-
ane (20 mL). With stirring, the reaction mixture was heated
at 50 °C for several minutes, and then cooled down to room
temperature. The reaction mixtures were diluted with deion-
ized water and washed with EtOAc. The combined organic
phase was washed with brine, dried over Na SO , ꢁltered
Preparation of ( ± ±‑3,3′‑diphenyl‑2,2′‑dimeth
oxy‑1,1′‑binaphthalene [( ± ±‑ꢅ, in ꢀcheme 2]
A 50-mL, one-necked, round-bottomed flask equipped
with a stir bar was charged with nickel (II) acetylacetonate
2
4
and concentrated in vacuo. The residue was then puriꢁed by
ꢂash chromatography on silica gel (6% ether in hexane) to
aꢀord 1.01 g (94%) corresponding product as a white solid.
(Ni(acac) ) (0.11 g, 0.43 mmol, 0.1 equiv), (±)-3,3′-diiodo-
2
2,2′-dimethoxy-1,1′-binaphthalene (2.45 g, 4.3 mmol, 1
equiv) and benzene (10 mL). With stirring, the solution of
phenylmagnesium bromide (PhMgBr) (3.90 g, 21.5 mmol,
5
equiv) in ether was slowly added via syringe at room
Preparation of ( ± ±‑2,2′‑dimethoxy‑1,1′‑bina
phthalene [( ± ±‑ꢃ, in ꢀcheme 2]
temperature. After the addition, the reaction mixture was
stirred for 0.5 h at room temperature, and then heated for
2
0 h under reꢂux conditions. After 20 h, the reaction mixture
A 100-mL, one-necked, round-bottomed ꢂask equipped with
a stir bar was charged with potassium carbonate (K CO )
was slowly diluted with saturated aqueous NH Cl (20 mL),
4
ꢁltered through a pad of celite and then washed with EtOAc.
The combined organic phase was washed with brine, dried
over Na SO , ꢁltered and concentrated in vacuo. The resi-
2
3
(
(
2.42 g, 17.5 mmol, 3.5 equiv), methyl iodide (MeI)
1.25 mL, 20 mmol, 4 equiv), (±)-BINOL (1.43 g, 5 mmol,
2
4
1
equiv) and anhydrous acetone (40 mL). With stirring, the
due was then puriꢁed by ꢂash chromatography on silica gel
(8% ether in hexane) to aꢀord 1.66 g (86%) corresponding
product as a yellow solid.
reaction mixture was heated for 20 h under reꢂux conditions,
and then cooled down to room temperature. The reaction
mixtures were diluted with deionized water and washed with
EtOAc. The combined organic phase was washed with brine,
dried over Na SO , ꢁltered and concentrated in vacuo to
2
4
aꢀord 1.49 g (95%) corresponding product as a pale yellow
solid.
Preparation of ( ± ±‑3,3′‑diphenyl(1,1′‑binaph
thalene±‑2,2′‑diol [( ± ±‑ꢂ, in ꢀcheme 2]
A 100-mL, one-necked, round-bottomed ꢂask equipped
with a stir bar was charged with ( ±)-3,3′-diphenyl-2,2′-
dimethoxy-1,1′-binaphthalene (1.71 g, 3.7 mmol, 1 equiv)
and dichloromethane (30 mL). Then the mixture was cooled
Preparation of ( ± ±‑3,3′‑diiodo‑2,2′‑dimethox
y‑1,1′‑binaphthalene [( ± ±‑ꢄ, in ꢀcheme 2]
A 250-mL, one-necked, round-bottomed ꢂask equipped
with a stir bar was charged with tetramethylethylenedi-
amine (TMEDA) (2.6 mL, 17.5 mmol, 3.5 equiv) and ether
to 0 °C by ice bath with stirring, boron tribromide (BBr )
3
(24 mL, 1.0 M in CH Cl , 24 mmol, 6.5 equiv) was slowly
2
2
added via syringe at 0 °C and the mixture was stirred for
20 h at room temperature. Then, the mixture was re-cooled
to 0 °C again via ice bath, the reaction mixture was diluted
with deionized water with stirring and washed with EtOAc.
The combined organic phase was washed with brine, dried
over Na SO , ꢁltered and concentrated in vacuo. The resi-
(
70 mL), n-butyllithium (n-BuLi) (7.8 mL, 1.6 M in hex-
ane, 12.5 mmol, 2.5 equiv) was slowly added via syringe
at room temperature and the mixture stirred for 0.5 h. Then
(
±)-2,2′-dimethoxy-1,1′-binaphthalene (1.56 g, 5 mmol, 1
equiv) was added and the mixture was stirred for another 1 h.
2
4
After 1 h, the mixture was cooled to -78 °C with stirring,
due was then puriꢁed by ꢂash chromatography on silica gel
(20% ether in hexane) to aꢀord 1.12 g (72%) corresponding
product as a white solid.
the solution of iodine (I ) (7.6 g, 30 mmol, 6 equiv) in ether
2
(
10 mL) was slowly added via syringe for several minutes.
After the addition, the reaction mixture was allowed to warm
1
3

Chemical Papers
Acknowledgements Financial support from the National Natural Sci-
ence Foundation of China (NSFC) (21761021 and 21861026), pro-
ject of teaching reform in colleges and universities of Jiangxi Prov-
ince (JXJG-18-1-56), innovative special funds project for graduate
sudents of Nanchang University (CX2019061) and scientiꢁc research
and training program of Nanchang University (3664) is gratefully
acknowledged.
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Compliance with ethical standards
Conflict of interest The authors declare no competing ꢁnancial inter-
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