Homogeneous Palladium-Catalyzed Selective Reduction of 2,2′-Biphenols Using HCO 2H as Hydrogen Source

Article abstract of DOI:10.1055/a-1337-5153

An efficient homogeneous palladium-catalyzed selective deoxygenation of 2,2′-biphenols by reduction of aryl triflates with HCO ₂H as the hydrogen source is reported. This protocol complements the current method based on heterogeneous Pd/C-catalyzed hydrogenation with hydrogen gas. This process provided the reduction products in good to excellent yields, which could be readily converted to various synthetically useful molecules, especially ligands for catalytic synthesis.

Full text of DOI:10.1055/a-1337-5153

SYNTHESIS
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart
2021, 53, 1605–1618
paper
1605
de
R. Li et al.
Paper
Synthesis
Homogeneous Palladium-Catalyzed Selective Reduction of
2,2′-Biphenols Using HCO2H as Hydrogen Source
Ruoling Li
Pd(OAc)2 (5 mol%)
DPPF (10 mol%)
R1
R1
R1
OR2
OTf
Chenchen Li
OR2
Et3N, HCO2H
DMF, 80 °C, 15 h
H
Wen Yang*
R1
Wanxiang Zhao*
0
0
0
0
-
0
0
0
2
-
6
3
1
3
-
3
9
9
X
80–99% yield
R1, R2 = H, alkyl, aryl, alkoxy
State Key Laboratory of Chemo/Biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan University,
Changsha 410082, P. R. of China
yangwen@hnu.edu.cn
zhaowanxiang@hnu.edu.cn
OH
H
OH
H
PPh2
PPh2
WSetMaaetaneiCxlYKoizyaerhanrynaegogLsZwaphboaeaonnordx@aiitnhaognrgyuA@.ouehftdhnCuouh.cr.ensemduo./cBniosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
Chiral phosphine ligands
Applications in asymmetric reactions
87%, >99% ee 90%, >99% ee
Gram-scale synthesis
Received: 28.10.2020
Accepted after revision: 15.12.2020
Published online: 15.12.2020
catalyzed reduction reactions of aryl triflates to arenes with
HCO2H have been reported.3l,n But the substrate scope did
not involve 2,2′-biphenol-derived monotriflates. As our
continued interest in synthetic transformations of phenol
derivatives,8 herein we describe a homogeneous palladium-
catalyzed selective deoxygenation of 2,2′-biphenols by re-
duction of aryl triflates with HCO2H (Scheme 1B), which
could complement heterogeneous Pd/C-catalyzed hydroge-
nation with hydrogen gas.
DOI: 10.1055/a-1337-5153; Art ID: ss-2020-g0554-op
Abstract An efficient homogeneous palladium-catalyzed selective
deoxygenation of 2,2′-biphenols by reduction of aryl triflates with
HCO2H as the hydrogen source is reported. This protocol complements
the current method based on heterogeneous Pd/C-catalyzed hydroge-
nation with hydrogen gas. This process provided the reduction products
in good to excellent yields, which could be readily converted to various
synthetically useful molecules, especially ligands for catalytic synthesis.
A) Heterogeneous catalytic hydrogenation with H2
Key words palladium, homogeneous catalysis, 2,2′-biphenols, reduc-
tion, formic acid
Pd/C
OH
H
OH
OTf
i
Pr2NEt, H2
Due to their versatile transformations, phenols and
their derivatives are very important synthetic intermedi-
ates in the preparation of catalysts, drugs, and materials.1
Among various transformations, metal-catalyzed function-
alization and cross-coupling reactions of phenol derivatives
via aryl C–O bond cleavage have attracted great attention in
recent decades, and numerous effective methods have been
established.2 In contrast, the relative defunctionalization by
reduction of C–O bonds has still not been fully explored.3
2,2′-Biphenol is an important member of phenol com-
pounds, and widely present in a large number of natural
products, pharmaceuticals, catalysts, and ligands.4 The se-
lective deoxygenation of 2,2′-biphenols has important ap-
plications in organic synthesis, especially for the prepara-
tion of useful ligands, catalysts, and heterocycles bearing
biphenyl skeleton.5,6 However, there is only one reliable and
commonly used method for binaphthol (Scheme 1A).5k,7
Binaphthol was first converted into monotriflate, and then
was reduced by heterogeneous Pd/C-catalyzed hydrogena-
tion with hydrogen gas. However, this method suffers from
potential safety hazards and poor functional group
tolerance. It is important to point out that the palladium-
B) Homogeneous catalytic hydrogenolysis with HCO2H
this work
R1
R1
OR2
OTf
OR2
H
Pd(OAc)2, DPPF
Et3N, HCO2H
R1
R1
1
2
C) Plausible reaction mechanism
LnPd(0)
ArH
2
[Ar-OTf]
I
1
ArLnPdH
ArLnPdOTf
IV
II
Et3N
HCO2H
HCO2PdLnAr
CO2
Et3N.HOTf
III
Scheme 1 Catalytic reduction of 2,2′-biphenol-based triflates and the
plausible reaction mechanism
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Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

1606
R. Li et al.
Paper
Synthesis
Pd(OAc)2 (5 mol%)
DPPF (10 mol%)
R1
R1
R1
R1
OR2
OTf
OR2
H
Et3N, HCO2H
DMF, 80 °C, 15 h
2
1
MeO
MeO
Ar
Ar
Me
Me
Et
Et
Me
Me
OH
H
OH
OH
H
OH
OH
OH
H
H
H
H
Me
Me
2a (98%)
Ar = Ph
Ar = 4-MeC6H4
2f (86%)
2g (98%)
2b (80%)
2e (83%)
2c (90%)
2d (85%)
Ar = 4-MeOC6H4 2h (99%)
Ar = 3,5-Me2C6H3 2i (99%)
S
O
Ar = 4-FC6H4
2j (99%)
S
Ph
OH
OH
H
OH
OH
H
OH
H
OH
H
H
H
S
O
Ph
S
2n (95%)
2o (92%)
2p (91%)
2k (87%)
2l (91%)
2m (94%)
OH
OBn
OMe
H
OMOM
H
OH
H
OH
H
H
H
2v (97%)
(R)-2r (97%, >99 ee)
2t (87%)
2u (98%)
(S)-2q (96%, >99% ee)
2s (98%)
Scheme 2 Reaction scope. Reagents and conditions: Unless noted otherwise, reactions were performed with 1 (0.30 mmol), Pd(OAc)2 (5 mol%), DPPF
(10 mol%), Et3N (3.0 equiv), HCO2H (2.0 equiv), and DMF (1.5 mL) at 80 °C for 15 h. Reaction temp for 2m,n,q,s,t: 120 °C.
According to the previous report,7f we propose a possi-
ble mechanism for this transformation that would involve
aryl triflates with HCO2H in the presence of a homogeneous
palladium catalyst (Scheme 1C). First, aryl triflate 1 reacts
with Pd(0) catalyst I to generate the species ArLnPdOTf II by
oxidative addition. Then in the presence of formic acid and
triethylamine, it undergoes a ligand exchange process with
the displacement of triflate with formate ion to form the
key intermediate III, which is transformed into intermedi-
ate IV by releasing of carbon dioxide. Finally, reductive
elimination of intermediate IV provides the desired product
2 along with regeneration of the Pd(0) complex.
We began our study with 2′-hydroxy-(1,1′-biphenyl)-2-
yl trifluoromethanesulfonate (1a) as the model substrate
for optimizing the reaction conditions. Key results are
shown in Table 1. In the presence of Pd(OAc)2 and 1,1′-
bis(diphenylphosphino)ferrocene (DPPF), the reduction re-
action with HCO2H as the reductant proceeded cleanly in
DMF at 80 °C for 15 hours to afford the desired product 2a
in 99% yield (98% isolated yield), which was the best result
(Table 1, entry 1). Other phosphine ligands instead of DPPF
were examined (entries 2–5). The use of 1,1′-bis(diphenyl-
phosphino)ethane (DPPE) slightly decreased the yield (en-
try 2), and other ligands, such as xantphos, PCy3, and PPh3,
all provided much lower yields. Lowering or improving the
reaction temperature led to a slight decrease in yield (en-
tries 6, 7). The solvent effect had a limited impact on the ef-
ficiency (entries 8–11). Solvents, such as DMA, 1,4-dioxane,
and toluene, all gave a comparable result, although MeCN
resulted in lower yield. The ratio of Et3N/HCO2H was
screened, and inferior yields were obtained (entries 12, 13).
Notably, the use of Pd/C catalyst instead of Pd(OAc)2 and
DPPF delivered the desired product in lower yield (entry
14).
Pd(OAc)2 (5 mol%)
DPPF (10 mol%)
Et3N (3.0 equiv)
OH
H
OH
OTf
HCO2H (2.0 equiv)
DMF, 120 °C, 15 h
(S)-2q (1.18 g, 87%, >99% ee)
(R)-1q (5.0 mmol)
Pd(OAc)2 (5 mol%)
DPPF (10 mol%)
Et3N (3.0 equiv)
OH
OH
H
OTf
HCO2H (2.0 equiv)
DMF, 80 °C, 24 h
(R)-2r (1.50 g, 90%, >99% ee)
(S)-1r (6.0 mmol)
Scheme 3 Gram-scale catalytic reactions
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

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R. Li et al.
Paper
Synthesis
Table 1 Optimization of Reaction Conditionsa
To demonstrate the practicability of this protocol, we
carried out gram-scale catalytic reactions and product
transformations. As shown in Scheme 3, the gram-scale
synthesis of chiral (S)-2q and (R)-2r were performed well in
slightly lower yields and without loss of ee values. Impor-
tantly, the representative product 2a could be used as a
‘platform molecule’, and several transformations into other
useful molecules are presented in Scheme 4. For example,
phenol 2a was treated with trifluoromethanesulfonic anhy-
dride to give triflate 3a9 in high yield. Palladium-catalyzed
diphenylphosphonylation of 3a led to diphenylphosphine
oxide 3b10 in good yield, followed by reduction with tri-
chlorosilane to give phosphine ligand 3c11 in high yield.
Palladium-catalyzed cyclization of 3c followed by oxidation
with aqueous H2O2 afforded cyclic phosphine oxide 3d.12
Rhodium-catalyzed dehydrosilylation of 3c with triethylsi-
lane provided the desired silane 3e.13 Phenol 2a was readily
converted into nitrile 3f by cyanation and borate 3g14 by
boronation, respectively.
Pd(OAc)2 (5 mol%)
DPPF (10 mol%)
Et3N (3.0 equiv)
OH
OH
H
OTf
HCO2H (2.0 equiv)
DMF, 80 °C, 15 h
1a
2a
Entry
Change from standard conditions
Yield (%)b
1
2
none
99 (98)c
93
DPPE instead of DPPF
xantphos instead of DPPF
PCy3 instead of DPPF
PPh3 instead of DPPF
70 °C instead of 80 °C
90 °C instead of 80 °C
DMA instead of DMF
1,4-dioxane instead of DMF
toluene instead of DMF
MeCN instead of DMF
Et3N (0.60 mmol)
3
65
4
12
5
50
6
94
7
94
8
92
9
93
NC
OH
10
11
12
13
14
98
F
78
67
3f (70%)
OH
OTf
A
HCO2H (0.30 mmol)
Pd/C instead of Pd(OAc)2 and DPPF
83
OH
O
B
85
G
D
a Standard conditions: 1a (0.30 mmol), Pd(OAc)2 (0.015 mmol), DPPF
(0.030 mmol), Et3N (0.90 mmol), HCO2H (0.60 mmol), DMF (1.5 mL),
80 °C, 15 h.
2a
3a (90%)
3g (98%)
Ph
b Determined by GC analysis with n-dodecane as an internal standard.
c Isolated yield.
B
O
P
With the optimal conditions in hand, we next examined
the generality of aryl triflates. The results are compiled in
Scheme 2. A series of 2,2′-biphenol-derived monotriflates
with different groups proceeded smoothly to afford the de-
sired products 2a–n in good to excellent yields (80–99%).
Furyl and thienyl groups were well incorporated into the
products 2k, 2l, and 2n in high yields. Triflates 1m,n bear-
ing substituents at the ortho-position displayed lower reac-
tivity probably because of the effect of steric hindrance, and
required higher temperature (120 °C) to obtain excellent
yields. Naphthalenediol-derived triflates 1o,p were also via-
ble substrates, providing the desired products 2o,p in high
yields. It is noteworthy that BINOL- and H8 BINOL-, SPINOL-
derived substrates 1q–s worked well to afford the desired
products 2q–s in excellent yields, and no erosion in the en-
antioselectivity was observed for chiral products 2q–r. This
indicated that this useful transformation could be applied
in the preparation of chiral ligands and catalysts. Moreover,
when aryl triflates 1t–v with different protecting groups
(Bn, Me, and MOM) were used as substrates, the corre-
sponding products 2t–v were obtained with high efficiency
(87–97% yield).
O
C
3d (53%)
P
PPh2
Ph
Ph
PPh2
E
3b (73%)
3c (90%)
Et3Si
3e (77%)
Scheme 4 Product transformations. Reagents and conditions: A: Tf2O
(1.0 equiv), iPr2NEt (1.0 equiv), CH2Cl2, 0 °C, rt; B: Ph2P(O)H (2.0 equiv),
Pd(OAc)2 (0.2 equiv), dppb (0.2 equiv), iPr2NEt (3.5 equiv), DMSO, 110
°C, 20 h; C: HSiCl3 (5.0 equiv), Et3N (5.5 equiv), toluene, 110 °C, 14 h;
D: (i) Pd(OAc)2 (5 mol%), toluene, 160 °C, 12 h, (ii) H2O2, rt, 0.5 h; E:
Rh2(OAc)4 (2.5 mol%), HSiEt3 (2.0 equiv), NBE (2.0 equiv), THF, 125 °C,
24 h; F: (i) MeSCN (1.2 equiv), BCl3 (1.2 equiv), AlCl3 (1.0 equiv), DCE,
80 °C, 3 h, (ii) NaOH, 80 °C, 0.5 h; G: (i) BCl3 (1.5 equiv), hexane, rt, 1.5
h, (ii) AlCl3 (4 mol%), 75 °C, 6 h. NBE: Norbornene
To further show the utility of this transformation, we
converted chiral products into ligands and applied them in
asymmetric palladium catalysis. According to the reported
methods,15 enantiopure (S)-2q and (R)-2r were efficiently
converted into chiral phosphine ligands (S)-5q and (R)-5r,
respectively (Scheme 5). It is worth noting that (R)-5r is a
new phosphine ligand, and no erosion in the enantio-
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

1608
R. Li et al.
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Synthesis
This process features high efficiency, broad substrate scope,
and easy gram-scale preparation. The present protocol
complements the current method based on heterogeneous
Pd/C-catalyzed hydrogenation with hydrogen gas. More-
over, the reduction products were readily converted into
various useful molecules. Notably, BINOL- and H8 BINOL-
derived products were transformed into chiral phosphine
ligands, which were successfully used in several palladium-
catalyzed asymmetric reactions.
A
OTf
B
C
PPh2
PPh2
O
(S)-2q
(S)-3q (85%, >99% ee) (S)-4q (>99%, 70% ee)
(63%, 98% ee, recrystallization)
(S)-5q (78%, 98% ee)
OTf
A
PPh2
B
PPh
O
2 C
(R)-2r
Unless otherwise noted, all reactions were conducted in an oven-
dried vial with a magnetic stirrer under N2 atmosphere. All solvents
and reagents were obtained from commercial sources and purified
according to standard procedures. Analytical TLC was performed us-
ing silica gel plates. Visualization was by ultraviolet fluorescence,
and/or KMnO4, and/or potassium molybdate. Flash column chroma-
tography was performed using EM Science (200–300 mesh) silica gel.
1H, 13C, and 31P NMR spectra were recorded on Bruker 400 MHz at 20
°C with CDCl3 as solvent. Chemical shifts (ppm) are given relative to
solvent: references for CDCl3 were 7.26 ppm (1H NMR) and 77.16 ppm
(R)-3r (73%, >99% ee)
(R)-4r (87%, >99% ee) (R)-5r (91%, >99% ee)
Scheme 5 Synthesis of chiral phosphine ligands. Reagents and condi-
tions: A: Tf2O (1.1 equiv), iPr2NEt (1.1 equiv), CH2Cl2, 0 °C, rt; B:
Ph2P(O)H (2.0 equiv), Pd(OAc)2 (0.2 equiv), dppb (0.2 equiv), iPr2NEt
(4.0 equiv), DMSO, 100 °C, 8 h; C: HSiCl3 (4.9 equiv), Et3N (20.1 equiv),
toluene, 110 °C, 16 h.
selectivity was observed during the preparation process.
Enantiopure (S)-5q and (R)-5r were employed as ligands for
several palladium-catalyzed asymmetric reactions, such as
hydrosilylation of styrene (6a) with trichlorosilane, allylic
etherification of 7a with benzyl alcohol, and arylative ring
(
13C NMR). The data are reported as follows: chemical shift (ppm),
multiplicity (standard abbreviations), coupling constant J (Hz), and
integration. High-resolution mass spectra were recorded on a Bruker
Maxis System. IR spectra were collected on a Spectrum BX FTIR from
PerkinElmer and reported in unit of cm–1. The enantiomeric excesses
were determined by chiral HPLC using a Shimadzu Prominence LC-
20A instrument with a Daicel Chiralcel OD-H or OJ-H column or a Dai-
cel Chiralpak AD-H column.
opening
of
1,4-epoxy-1,4-dihydronaphthalene
(8a)
(Scheme 6). In these cases, good or high yields and enantio-
selectivities could be achieved without optimization of con-
ditions.6,16
In summary, we have developed an efficient homoge-
neous palladium-catalyzed selective deoxygenation of 2,2′-
biphenols by reduction of aryl triflates with formic acid.
2,2′-Biphenol-Derived Monotriflates 1; General Procedure I
According to a reported procedure,17 Tf2O (0.84 mL, 5.0 mmol) was
added dropwise to a solution of the respective (1,1′-biphenyl)-2,2′-
diol derivative (5.0 mmol, 1.0 equiv) and N-ethyldiisopropylamine
(0.82 mL, 5.0 mmol) in CH2Cl2 (15 mL) at 0 °C. The reaction mixture
was slowly warmed up to rt and stirred overnight. The mixture was
poured into H2O (20 mL) and then extracted with CH2Cl2 (3 × 20 mL).
The combined organic layers were washed with brine (20 mL), dried
(anhyd Na2SO4), filtered, and concentrated under reduced pressure.
The residue was purified by column chromatography on silica gel
(PE/EtOAc as eluent) to give the desired product 1.
[PdCl(π-C3H5)]2 (0.1 mol%)
SiCl3
OH
∗
L* (0.2 mol%)
H2O2, KF
K2CO3
∗
Ph
6a
Ph
Me
Ph
Me
HSiCl3
6b
6c
L* = (
L* = (
S
R
)-5q 77%, 92% ee (S)
)-5r 71%, 62% ee (R)
[PdCl(π-C3H5)]2 (2.5 mol%)
OAc
Ph
OBn
2′-Hydroxy-(1,1′-biphenyl)-2-yl Trifluoromethanesulfonate (1a)8c
L* (5.0 mol%)
∗
+
BnOH
Ph
Ph
Ph
The title compound 1a was prepared as a colorless oil in 90% yield
(1.43 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.42 (PE/EtOAc 10:1).
Cs2CO3, CH2Cl2, rt, 4 h
7b
7a
L* = (
L* = (
S)-5q 57%, 24% ee (R)
R
)-5r 80%, 80% ee (S)
1H NMR (400 MHz, CDCl3):  = 7.47–7.40 (m, 3 H), 7.41–7.35 (m, 1 H),
7.27 (t, J = 7.8 Hz, 1 H), 7.20 (d, J = 6.8 Hz, 1 H), 6.99 (t, J = 7.4 Hz, 1 H),
6.87 (d, J = 8.1 Hz, 1 H), 5.28 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 152.9, 147.7, 132.8, 131.5, 131.4,
130.4, 129.8, 128.7, 122.4, 122.0, 121.0, 118.5 (q, J = 320.4 Hz), 116.2.
OH
Ph
catalyst (3 mol%)
*
PhB(OH)2
O
+
*
Cs2CO3, H2O, CHCl3
0 °C, 16 h
8a
8b
cat. 1: 91%, 79% ee (1
cat. 2: 88%, 76% ee (1
R
,2
R
S
)
)
2′-Hydroxy-5,5′-dimethyl-(1,1′-biphenyl)-2-yl Trifluoromethane-
PPh2
Pd
PPh2
Pd
S
,2
sulfonate (1b)8c
OAc
OAc
The title compound 1b was prepared as a colorless oil in 75% yield
(1.30 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.42 (PE/EtOAc 10:1).
cat. 1
cat. 2
Scheme 6 Applications of chiral phosphine ligands in asymmetric pal-
ladium catalysis
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

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R. Li et al.
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Synthesis
1H NMR (400 MHz, CDCl3):  = 7.28–7.20 (m, 3 H), 7.12–7.06 (m, 1 H),
7.00 (s, 1 H), 6.82 (d, J = 8.2 Hz, 1 H), 4.90 (s, 1 H), 2.39 (s, 3 H), 2.30 (s,
3 H).
13C NMR (101 MHz, CDCl3):  = 152.6, 147.1, 142.1, 140.5, 139.1,
134.5, 131.6, 131.4, 130.2, 129.24, 129.18, 128.9, 128.6, 128.4, 127.4,
127.1, 127.0, 122.8, 122.6, 118.6 (d, J = 320.6 Hz), 116.8.
13C NMR (100 MHz, CDCl3):  = 150.7, 145.6, 138.9, 133.1, 131.6,
131.2, 130.8, 130.3, 130.1, 122.3, 121.7, 118.5 (q, J = 320.4 Hz), 116.1,
20.9, 20.4.
6′′-Hydroxy-4,4′′′-dimethyl-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-yl
Trifluoromethanesulfonate (1g)
The title compound 1g was prepared as a colorless solid in 54% yield
(1.35 g, eluent: PE/EtOAc 80:1 to 50:1) following the general proce-
dure I; mp 153.7–154.7 °C; Rf = 0.45 (PE/EtOAc 10:1).
5,5′-Diethyl-2′-hydroxy-(1,1′-biphenyl)-2-yl Trifluoromethane-
sulfonate (1c)8c
The title compound 1c was prepared as a colorless oil in 52% yield
(973.4 mg, eluent: PE/EtOAc 200:1 to 50:1) following the general pro-
cedure I; Rf = 0.45 (PE/EtOAc 5:1).
1H NMR (400 MHz, CDCl3):  = 7.42 (d, J = 8.6 Hz, 1 H), 7.30–7.24 (m, 1
H), 7.18–7.07 (m, 2 H), 6.92 (d, J = 1.9 Hz, 1 H), 6.88 (d, J = 8.3 Hz, 1 H),
4.57 (s, 1 H), 2.61 (q, J = 7.6 Hz, 2 H), 2.51 (d, J = 6.2 Hz, 2 H), 1.23 (t, J =
7.6 Hz, 3 H), 1.08 (t, J = 7.6 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 150.4, 147.7, 144.3, 138.5, 136.7,
130.6, 129.6, 129.2, 125.8, 123.4, 121.2, 118.9 (q, J = 320.8 Hz), 115.7,
28.1, 25.9, 15.9, 15.1.
IR (neat): 1480, 1420, 1247, 1210, 1139, 1105, 897, 865, 810 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.69 (d, J = 2.3 Hz, 1 H), 7.68–7.62 (m, 1
H), 7.56–7.50 (m, 1 H), 7.49–7.42 (m, 6 H), 7.27–7.18 (m, 4 H), 7.00 (d,
J = 8.4 Hz, 1 H), 5.10 (s, 1 H), 2.38 (s, 3 H), 2.37 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 152.4, 146.9, 142.1, 138.4, 137.7,
136.9, 136.3, 134.4, 131.7, 131.2, 130.0, 129.7, 129.1, 128.3, 127.3,
126.9, 122.9, 122.6, 118.7 (q, J = 320.6 Hz), 116.8, 21.34, 21.28.
HRMS (ESI+): m/z [M]+ calcd for C27H21F3O4S: 498.1113; found:
498.1104.
6′′-Hydroxy-4,4′′′-dimethoxy-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-yl
Trifluoromethanesulfonate (1h)
2′-Hydroxy-3,3′,5,5′-tetramethyl-(1,1′-biphenyl)-2-yl Trifluoro-
methanesulfonate (1d)
The title compound 1h was prepared as a colorless solid in 64% yield
(1.70 g, eluent: PE/EtOAc 100:1 to 10:1) following the general proce-
dure I; mp 64.8–65.8 °C; Rf = 0.50 (PE/EtOAc 3:1).
The title compound 1d was prepared as a colorless oil in 34% yield
(636.5 mg, eluent: PE/EtOAc 200:1 to 50:1) following the general pro-
cedure I; Rf = 0.50 (PE/EtOAc 10:1).
IR (neat): 1499, 1482, 1420, 1247, 1213, 1182, 1140, 821 cm–1
.
IR (neat): 1483, 1411, 1207, 1176, 1138, 1089, 860, 636 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.72 (d, J = 1.7 Hz, 1 H), 7.67–7.62 (m, 1
H), 7.58–7.51 (m, 6 H), 7.47 (d, J = 8.6 Hz, 1 H), 7.05–6.99 (m, 5 H),
5.82 (s, 1 H), 3.86 (d, J = 2.9 Hz, 6 H).
13C NMR (100 MHz, CDCl3):  = 159.8, 158.9, 152.2, 146.6, 141.5,
133.8, 133.1, 131.8, 131.5, 130.7, 129.7, 128.6, 128.4, 127.9, 127.7,
122.9, 122.3, 118.6 (q, J = 320.5 Hz), 116.6, 114.5, 114.4, 55.4 (2 C).
1H NMR (400 MHz, CDCl3):  = 7.19 (s, 1 H), 7.14 (s, 1 H), 7.05 (s, 1 H),
6.90 (s, 1 H), 4.83 (s, 1 H), 2.50 (s, 3 H), 2.41 (s, 3 H), 2.33 (s, 6 H).
13C NMR (100 MHz, CDCl3):  = 149.0, 144.4, 138.6, 132.6, 132.1,
132.0, 131.6, 130.9, 129.4, 129.0, 124.8, 122.3, 118.3 (q, J = 320.4 Hz),
20.7, 20.3, 17.2, 16.0.
HRMS (ESI+): m/z [M]+ calcd for C17H17F3O4S: 374.0800; found:
374.0792.
HRMS (ESI+): m/z [M]+ calcd for C27H21F3O6S: 530.1011; found:
530.1007.
2′-Hydroxy-5,5′-dimethoxy-(1,1′-biphenyl)-2-yl Trifluorometh-
anesulfonate (1e)
6′′-Hydroxy-3,3′′′,5,5'''-tetramethyl-(1,1′:3′,1′′:3′′,1′′′-quater-
phenyl)-4′-yl Trifluoromethanesulfonate (1i)8c
The title compound 1e was prepared as a colorless oil in 77% yield
(1.46 mg, eluent: PE/EtOAc 80:1 to 10:1) following the general proce-
dure I; Rf = 0.68 (PE/EtOAc 5:2).
The title compound 1i was prepared as a white solid in 60% yield
(1.58 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.45 (PE/EtOAc 10:1).
1H NMR (400 MHz, CDCl3):  = 7.75 (d, J = 2.1 Hz, 1 H), 7.73–7.68 (m, 1
H), 7.61–7.56 (m, 1 H), 7.53 (d, J = 2.0 Hz, 1 H), 7.49 (d, J = 8.5 Hz, 1 H),
7.24 (d, J = 8.2 Hz, 4 H), 7.09–7.03 (m, 2 H), 7.00 (s, 1 H), 5.16 (s, 1 H),
2.41 (d, J = 3.6 Hz, 12 H).
IR (neat): 1486, 1415, 1247, 1201, 1136, 1031, 872, 813, 616 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.25 (t, J = 8.9 Hz, 1 H), 6.94 (d, J = 3.0
Hz, 1 H), 6.93–6.88 (m, 1 H), 6.87–6.80 (m, 2 H), 6.78 (t, J = 3.9 Hz, 1
H), 5.55 (s, 1 H), 3.77 (s, 3 H), 3.74 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 159.0, 153.4, 147.0, 141.0, 132.7,
123.1, 122.9, 118.5 (q, J = 320.5 Hz), 117.2, 116.2, 114.8, 56.0, 55.8.
HRMS (ESI+): m/z [M]+ calcd for C15H13F3O6S: 378.0385; found:
13C NMR (100 MHz, CDCl3):  = 152.4, 146.9, 142.3, 140.4, 139.1,
138.8, 138.4, 134.6, 131.6, 131.4, 130.1, 123.0, 129.2, 128.7, 128.4,
125.3, 124.8, 122.7, 122.4, 118.6 (q, J = 320.5 Hz), 116.6, 21.52 (2 C),
21.48 (2 C).
378.0378.
4,4′′′-Difluoro-6′′-hydroxy-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-yl
Trifluoromethanesulfonate (1j)
6′′-Hydroxy-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-yl Trifluorometh-
anesulfonate (1f)8c
The title compound 1j was prepared as a colorless oil in 78% yield
(1.97 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.42 (PE/EtOAc 5:1).
The title compound 1f was prepared as a colorless oil in 48% yield
(1.13 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.42 (PE/EtOAc 10:1).
IR (neat): 1498, 1481, 1419, 1211, 1162, 1137, 1105, 897, 866, 819
1H NMR (400 MHz, CDCl3):  = 7.74 (d, J = 2.3 Hz, 1 H), 7.72–7.68 (m, 1
H), 7.63–7.55 (m, 5 H), 7.53–7.44 (m, 4 H), 7.43–7.37 (m, 3 H), 7.32 (t,
J = 7.3 Hz, 1 H), 7.06 (d, J = 8.4 Hz, 1 H), 5.10 (s, 1 H).
cm–1
.
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1H NMR (400 MHz, CDCl3):  = 7.69 (d, J = 2.3 Hz, 1 H), 7.68–7.62 (m, 1
H), 7.59–7.46 (m, 7 H), 7.20–7.08 (m, 4 H), 7.03 (d, J = 8.4 Hz, 1 H),
5.25 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 163.1 (d, J = 248.1 Hz), 162.4 (d, J =
246.0 Hz), 152.5, 147.0, 141.1, 136.5 (d, J = 3.1 Hz), 135.2 (d, J = 3.3
Hz), 133.5, 131.8, 131.2, 130.0, 129.1, 129.0 (d, J = 8.3 Hz), 128.5 (d, J =
8.0 Hz), 128.4, 122.8, 122.5, 118.6 (q, J = 320.6 Hz), 116.8, 116.1 (d, J =
21.6 Hz), 115.8 (d, J = 21.4 Hz).
2′-Hydroxy-3,3′-di(thiophen-3-yl)-(1,1′-biphenyl)-2-yl Trifluoro-
methanesulfonate (1n)
The title compound 1n was prepared as a colorless solid in 76% yield
(1.83 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; mp 114.5–115.8 °C; Rf = 0.50 (PE/EtOAc 5:1).
IR (neat): 1416, 1202, 1135, 1069, 877, 777, 748, 625, 599 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.58–7.53 (m, 3 H), 7.52–7.47 (m, 3 H),
7.47–7.42 (m, 2 H), 7.38–7.31 (m, 3 H), 7.11 (t, J = 7.6 Hz, 1 H), 5.55 (s,
1 H).
13C NMR (100 MHz, CDCl3):  = 150.2, 145.2, 137.3, 136.3, 133.1,
131.54, 131.53, 131.3, 131.2, 130.6, 128.6, 128.5, 128.4, 127.1, 126.1,
125.1, 124.0, 123.59, 123.55, 120.8, 118.0 (q, J = 320.5 Hz).
HRMS (ESI+): m/z [M]+ calcd for C25H15F5O4S: 506.0611; found:
506.0603.
5,5′-Di(furan-3-yl)-2′-hydroxy-(1,1′-biphenyl)-2-yl Trifluorometh-
anesulfonate (1k)
HRMS (ESI+): m/z [M + H]+ calcd for C21H14F3O4S3: 483.0001; found:
482.9998.
The title compound 1k was prepared as a colorless oil in 51% yield
(1.15 g, eluent: PE/EtOAc 80:1 to 50:1) following the general proce-
dure I; Rf = 0.48 (PE/EtOAc 5:1).
Hydroxynaphthalen-1-yl Trifluoromethanesulfonate (1o)8c
IR (neat): 1416, 1206, 1162, 1135, 886, 874, 785, 613, 596 cm–1
.
The title compound 1o was prepared as a colorless solid in 82% yield
(1.20 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.42 (PE/EtOAc 10:1).
1H NMR (400 MHz, CDCl3):  = 7.82 (d, J = 8.3 Hz, 1 H), 7.49 (d, J = 8.2
Hz, 1 H), 7.48–7.37 (m, 2 H), 7.33 (d, J = 7.7 Hz, 1 H), 6.93 (d, J = 7.5 Hz,
1 H), 6.04 (s, 1 H).
1H NMR (400 MHz, CDCl3):  = 7.77 (s, 1 H), 7.71 (s, 1 H), 7.63 (d, J =
2.1 Hz, 1 H), 7.62–7.55 (m, 1 H), 7.49 (d, J = 9.0 Hz, 2 H), 7.49–7.41 (m,
3 H), 6.96 (d, J = 8.1 Hz, 1 H), 6.70 (d, J = 3.5 Hz, 2 H), 5.58 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 152.1, 146.3, 144.2, 143.7, 139.4,
138.0, 133.4, 131.8, 129.7, 128.7, 128.0, 127.0, 125.8, 125.6, 124.8,
122.8, 122.4, 118.5 (q, J = 320.6 Hz), 116.7, 108.9, 108.7.
13C NMR (100 MHz, CDCl3):  = 150.5, 145.3, 137.2, 128.9, 127.6,
125.4, 120.9, 118.9 (q, J = 321.1 Hz), 118.7, 117.5, 112.4.
HRMS (ESI+): m/z [M + H]+ calcd for C21H14F3O6S: 451.0458; found:
451.0456.
Hydroxynaphthalen-2-yl Trifluoromethanesulfonate (1p)8c
2′-Hydroxy-5,5′-di(thiophen-3-yl)-(1,1′-biphenyl)-2-yl Trifluoro-
methanesulfonate (1l)
The title compound 1p was prepared as a colorless solid in 81% yield
(1.18 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.43 (PE/EtOAc 10:1).
1H NMR (400 MHz, CDCl3):  = 7.78 (d, J = 8.2 Hz, 1 H), 7.74 (s, 1 H),
7.71 (d, J = 8.3 Hz, 1 H), 7.51 (t, J = 7.6 Hz, 1 H), 7.43 (t, J = 7.5 Hz, 1 H),
7.36 (s, 1 H), 5.53 (s, 1 H).
The title compound 1l was prepared as a colorless solid in 21% yield
(506.6 mg, eluent: PE/EtOAc 100:1 to 20:1) following the general pro-
cedure I; mp 60.3–61.7 °C; Rf = 0.36 (PE/EtOAc 5:1).
IR (neat): 1418, 1247, 1208, 1163, 1137, 1106, 886, 780 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.73 (d, J = 2.0 Hz, 1 H), 7.73–7.67 (m, 1
H), 7.60–7.55 (m, 1 H), 7.53–7.50 (m, 2 H), 7.46 (d, J = 8.5 Hz, 1 H),
7.44–7.34 (m, 5 H), 6.99 (d, J = 8.4 Hz, 1 H), 5.34 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 145.4, 138.3, 133.4, 128.3, 127.9,
127.8, 126.5, 125.3, 120.9, 118.9 (q, J = 320.6 Hz), 113.2.
13C NMR (100 MHz, CDCl3):  = 152.2, 146.5, 141.5, 140.1, 136.6,
131.7, 130.4, 129.4, 129.2, 128.6, 127.7, 127.1, 126.4, 126.3, 126.2,
122.7, 122.5, 121.9, 119.6, 118.5 (q, J = 320.5 Hz), 116.7.
HRMS (ESI+): m/z [M + H]+ calcd for C21H14F3O4S3: 483.0001; found:
482.9998.
(R)-2′-Hydroxy-(1,1′-binaphthalen)-2-yl Trifluoromethanesulfon-
ate [(R)-1q]8c
The title compound (R)-1q was prepared as a colorless oil in 78% yield
(1.63 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.45 (PE/EtOAc 10:1); []D30.9 +19.80 (c 0.55, CHCl3); >99%
ee.
1H NMR (400 MHz, CDCl3):  = 7.87 (d, J = 8.5 Hz, 1 H), 7.83–7.68 (m, 3
H), 7.48 (d, J = 8.5 Hz, 1 H), 7.36 (d, J = 7.2 Hz, 2 H), 7.25–7.08 (m, 4 H),
7.07–6.92 (m, 1 H), 5.30 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 151.9, 146.2, 133.41, 133.36, 132.9,
131.5, 131.4, 129.2, 128.5, 128.3, 128.2, 127.5, 127.1, 126.5, 125.5,
124.3, 123.8, 119.7, 118.4 (q, J = 320.3 Hz), 117.9, 112.2.
2′′-Hydroxy-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-2′-yl Trifluorometh-
anesulfonate (1m)
The title compound 1m was prepared as a white solid in 73% yield
(1.72 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; mp 101.8–103.2 °C; Rf = 0.43 (PE/EtOAc 10:1).
IR (neat): 1416, 1245, 1206, 1138, 1069, 882, 762, 700, 633 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.61–7.42 (m, 13 H), 7.40–7.32 (m, 2
H), 7.13 (t, J = 7.6 Hz, 1 H), 5.45 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 150.0, 145.2, 137.0, 136.5, 136.4,
133.3, 131.6, 131.5, 131.1, 129.8, 129.5, 129.4, 129.1, 128.6, 128.5,
128.4, 128.2, 123.6, 120.9, 117.9 (q, J = 320.6 Hz).
(S)-2′-Hydroxy-5,5′,6,6′,7,7′,8,8′-octahydro-(1,1′-binaphthalen)-2-
yl Trifluoromethanesulfonate [(S)-1r]
The title compound (S)-1r was prepared as a colorless oil in 87% yield
(1.86 g, eluent: PE/EtOAc 200:1 to 50:1) following the general proce-
dure I; Rf = 0.45 (PE/EtOAc 10:1); []D30.9 –40.61 (c 0.67, CHCl3), >99%
ee.
HRMS (ESI+): m/z [M]+ Calcd for C25H17F3O4S: 470.0800; found:
470.0792.
IR (neat): 1416, 1202, 1135, 1069, 877, 777, 748, 625, 599 cm–1
.
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

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1H NMR (400 MHz, CDCl3):  = 7.25–7.07 (m, 2 H), 7.01 (d, J = 8.3 Hz, 1
H), 6.74 (d, J = 8.3 Hz, 1 H), 4.73 (s, 1 H), 2.81 (t, J = 6.0 Hz, 2 H), 2.78–
2.65 (m, 2 H), 2.54–2.44 (m, 1 H), 2.38–2.28 (m, 1 H), 2.29–2.19 (m, 1
H), 2.09–1.99 (m, 1 H), 1.84–1.60 (m, 8 H).
13C NMR (100 MHz, CDCl3):  = 150.6, 145.7, 139.9, 138.7, 136.0,
130.70, 130.68, 129.9, 129.1, 120.2, 118.5, 118.4 (q, J = 320.1 Hz),
113.6, 29.7, 29.2, 27.4, 27.3, 23.1, 23.0, 22.6, 22.4.
1H NMR (400 MHz, CDCl3):  = 7.45–7.40 (m, 3 H), 7.40–7.33 (m, 2 H),
7.27–7.21 (m, 2 H), 7.12–7.05 (m, 1 H), 5.12 (s, 2 H), 3.37 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 154.8, 147.8, 132.72, 132.67, 131.6,
130.3, 129.2, 128.2, 125.5, 121.9, 121.5, 118.5 (q, J = 320.4 Hz), 114.8,
95.0, 56.1.
HRMS (ESI+): m/z [M + Na]+ calcd for C15H13F3O5SNa: 385.0328; found:
385.0326.
HRMS (ESI+): m/z [M + H]+ calcd for C21H22F3O4S: 427.1186; found:
427.1183.
Phenol Derivatives 2; General Procedure II
7′-Hydroxy-2,2′,3,3′-tetrahydro-1,1′-spirobi(inden)-7-yl Trifluoro-
To a 10 mL tube were added 1 (0.3 mmol, 1.0 equiv), Pd(OAc)2 (0.015
mmol, 2.4 mg), and DPPF (0.03 mmol, 16.7 mg) in a N2-filled glovebox.
The tube was capped with a rubber plug and removed from the glove-
box. A solution of HCO2H (0.6 mmol, 23 L, 88% wt) and Et3N (0.9
mmol, 125 L) in DMF (1.5 mL) was added via syringe. The reaction
mixture was heated to 80 °C or 120 °C in an oil bath and stirred vigor-
ously for 15 h. Upon completion, the mixture was slowly cooled to rt,
poured into H2O (10 mL), and extracted with EtOAc (3 × 10 mL). The
combined organic layers were washed with brine (15 mL), dried (an-
hyd Na2SO4), filtered, and concentrated under reduced pressure. The
residue was purified by silica gel column chromatography to afford
the desired product 2.
methanesulfonate (1s)8c
The title compound 1s was prepared as a colorless solid in 81% yield
(1.56 g, eluent: PE/EtOAc 100:1 to 30:1) following the general proce-
dure I; Rf = 0.50 (PE/EtOAc 5:1).
1H NMR (400 MHz, CDCl3):  = 7.33–7.27 (m, 2 H), 7.17–7.08 (m, 2 H),
6.87 (d, J = 7.4 Hz, 1 H), 6.56 (d, J = 7.9 Hz, 1 H), 4.33 (s, 1 H), 3.26–2.79
(m, 4 H), 2.75–1.97 (m, 4 H).
13C NMR (100 MHz, CDCl3):  = 152.2, 148.1, 146.3, 145.7, 139.7,
132.2, 129.3, 129.0, 124.7, 118.7, 118.2 (q, J = 319.8 Hz), 117.4, 114.0,
59.1, 38.4, 38.3, 31.5, 31.2.
(1,1′-Biphenyl)-2-ol (2a)20
2′-(Benzyloxy)-(1,1′-biphenyl)-2-yl Trifluoromethanesulfonate
(1t)17
The title compound 2a was prepared from 1a (95.5 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless oil; yield: 50.0
mg (98%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.62 (PE/EtOAc 5:1).
1H NMR (400 MHz, CDCl3):  = 7.55–7.43 (m, 4 H), 7.41–7.33 (m, 1 H),
7.24 (t, J = 7.6 Hz, 2 H), 6.98 (t, J = 7.9 Hz, 2 H), 5.27 (d, J = 5.5 Hz, 1 H).
13C NMR (100 MHz, CDCl3):  = 152.6, 137.2, 130.4, 129.4, 129.3,
129.2, 128.3, 128.0, 121.0, 116.0.
The title compound 1t was prepared from 2′-(benzyloxy)-(1,1′-biphe-
nyl)-2-ol (1.38 g, 5.0 mmol) as a colorless solid in 36% yield (735.1 mg,
eluent: PE/CH2Cl2 50:1 to 5:1); mp 58.7–59.7 °C; Rf = 0.50 (PE/CH2Cl2
2:1).
IR (neat): 1418, 1246, 1204, 1138, 1094, 887, 751, 594 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.47–7.31 (m, 5 H), 7.31–7.20 (m, 6 H),
7.08–6.97 (m, 2 H), 5.07 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 156.0, 147.8, 137.2, 132.7, 131.7,
130.2, 129.1, 128.5, 128.2, 127.7, 126.9, 125.2, 121.4, 121.0, 118.5 (q, J
= 320.4 Hz), 112.8, 70.4.
3′,5-Dimethyl-(1,1′-biphenyl)-2-ol (2b)
The title compound 2b was prepared from 1b (103.9 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless oil; yield: 47.6
mg (80%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.62 (PE/EtOAc 5:1).
HRMS (ESI+): m/z [M + Na]+ calcd for C20H15F3O4SNa: 431.0535; found:
431.0535.
IR (neat): 1498, 1268, 1211, 1183, 1128, 815, 793, 761, 702 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.34 (t, J = 7.5 Hz, 1 H), 7.29–7.14 (m, 3
H), 7.03 (d, J = 6.4 Hz, 2 H), 6.86 (d, J = 8.7 Hz, 1 H), 4.92 (s, 1 H), 2.39
(s, 3 H), 2.30 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 150.3, 139.1, 137.3, 130.7, 130.0,
129.9, 129.6, 129.2, 128.6, 128.1, 126.1, 115.7, 21.6, 20.6.
2′-Methoxy-(1,1′-biphenyl)-2-yl Trifluoromethanesulfonate (1u)18
The title compound 1u was prepared from 2′-(methoxy)-(1,1′-biphe-
nyl)-2-ol (1.59 g, 5.0 mmol) as a colorless oil in 86% yield (1.43 g, elu-
ent: PE/EtOAc 100:1 to 20:1); Rf = 0.60 (PE/EtOAc 5:1).
IR (neat): 1417, 1247, 1203, 1138, 1094, 887, 753, 592, 517 cm–1
.
HRMS (ESI+): m/z [M + Na]+ calcd for C14H14ONa: 221.0937; found:
221.0936.
1H NMR (400 MHz, CDCl3):  = 7.53–7.39 (m, 5 H), 7.35–7.29 (m, 1 H),
7.11 (t, J = 7.5 Hz, 1 H), 7.05 (d, J = 8.3 Hz, 1 H), 3.84 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 156.8, 147.9, 132.7, 132.6, 131.4,
130.3, 129.1, 128.2, 124.8, 121.3, 120.7, 118.5 (q, J = 320.1 Hz), 111.0,
55.5.
3′,5-Diethyl-(1,1′-biphenyl)-2-ol (2c)
The title compound 2c was prepared from 1c (112.3 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless oil; yield: 61.1
mg (90%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.62 (PE/EtOAc 5:1).
HRMS (ESI+): m/z [M + Na]+ calcd for C14H11F3O4SNa: 355.0222; found:
355.0222.
IR (neat): 2965, 2931, 2872, 1497, 1483, 1457, 1229, 1187, 825 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.35 (d, J = 3.7 Hz, 2 H), 7.30–7.23 (m, 1
H), 7.21 (d, J = 7.4 Hz, 1 H), 7.10 (d, J = 8.0 Hz, 1 H), 6.94 (s, 1 H), 6.89
(d, J = 8.2 Hz, 1 H), 4.66 (s, 1 H), 2.65–2.57 (m, 2 H), 2.56–2.42 (m, 2
H), 1.22 (t, J = 7.6 Hz, 3 H), 1.07 (t, J = 7.5 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 150.6, 143.7, 136.1, 135.6, 130.8,
129.7, 129.2, 128.8, 128.5, 127.4, 126.5, 115.1, 28.1, 26.3, 15.9, 15.4.
2′-(Methoxymethoxy)-(1,1′-biphenyl)-2-yl Trifluoromethane-
sulfonate (1v)19
The title compound 1v was prepared from 2′-(methoxymethoxy)-
(1,1′-biphenyl)-2-ol (1.15 g, 5.0 mmol) as a colorless oil in 21% yield
(380.4 mg, eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.62 (PE/EtOAc 5:2).
IR (neat): 1419, 1202, 1138, 1122, 1081, 988, 886, 756, 593 cm–1
.
HRMS (ESI+): m/z [M]+ calcd for C16H18O: 226.1358; found: 226.1351.
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3,3′,5,5′-Tetramethyl-(1,1′-biphenyl)-2-ol (2d)
4,4′′′-Dimethoxy-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-ol (2h)
The title compound 2d was prepared from 1d (112.3 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless solid; yield: 57.7
mg (85%) (eluent: PE/EtOAc 100:1 to 20:1); mp 126.3–127.8 °C; Rf =
0.62 (PE/EtOAc 5:1).
The title compound 2h was prepared from 1h (159.2 mg, 0.3 mmol) at
80 °C according to the general procedure II; white solid; yield: 113.6
mg (99%) (eluent: PE/EtOAc 50:1 to 10:1); mp 149.8–151.2 °C; Rf =
0.52 (PE/EtOAc 3:1).
IR (neat): 3517, 2921, 2856, 1599, 1483, 1203, 1114, 852, 706 cm–1
.
IR (neat): 1608, 1515, 1496, 1476, 1241, 1179, 1035, 819, 794 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.11 (s, 2 H), 7.08 (s, 1 H), 6.99 (s, 1 H),
6.92 (s, 1 H), 5.27 (s, 1 H), 2.42 (s, 6 H), 2.33 (s, 6 H).
1H NMR (400 MHz, CDCl3):  = 7.78 (s, 1 H), 7.67–7.46 (m, 9 H), 7.10
(d, J = 8.3 Hz, 1 H), 7.02 (t, J = 7.9 Hz, 4 H), 5.60 (s, 1 H), 3.87 (s, 6 H).
13C NMR (100 MHz, CDCl3):  = 148.5, 139.1, 137.5, 131.1, 129.5,
129.2, 128.0, 127.7, 126.9, 124.4, 21.5, 20.6, 16.3.
HRMS (ESI+): m/z [M]+ calcd for C16H18O: 226.1358; found: 226.1351.
13C NMR (100 MHz, CDCl3):  = 159.5, 158.8, 151.8, 141.9, 137.8,
133.8, 133.3, 133.2, 129.7, 128.7, 128.6, 128.3, 127.8, 127.6, 127.5,
127.4, 126.3, 116.4, 114.4, 114.3, 55.4 (2 C).
HRMS (ESI+): m/z [M]+ calcd for C26H22O3: 382.1569; found: 382.1561.
3′,5-Dimethoxy-(1,1′-biphenyl)-2-ol (2e)
3,3′′′,5,5′′′-Tetramethyl-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-ol (2i)
The title compound 2e was prepared from 1e (113.5 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless solid; yield: 57.3
mg (83%) (eluent: PE/EtOAc 100:1 to 10:1); mp 94.6–95.8 °C; Rf = 0.56
(PE/EtOAc 2:1).
The title compound 2i was prepared from 1i (158.0 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless oil; yield: 112.4
mg (99%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.52 (PE/EtOAc 5:1).
IR (neat): 1577, 1482, 1409, 1269, 1204, 1165, 1029, 759 cm–1
.
IR (neat): 1600, 1501, 1470, 1173, 850, 823, 798, 703 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.40 (t, J = 7.9 Hz, 1 H), 7.06 (d, J = 7.6
Hz, 1 H), 7.01 (s, 1 H), 6.98–6.90 (m, 2 H), 6.86–6.79 (m, 2 H), 5.12 (s, 1
H), 3.84 (s, 3 H), 3.80 (s, 3 H).
1H NMR (400 MHz, CDCl3):  = 7.85 (s, 1 H), 7.73 (d, J = 7.6 Hz, 1 H),
7.69–7.52 (m, 4 H), 7.37 (s, 2 H), 7.33 (s, 2 H), 7.18–7.10 (m, 2 H), 7.07
(s, 1 H), 5.50 (s, 1 H), 2.48 (d, J = 6.2 Hz, 12 H).
13C NMR (100 MHz, CDCl3):  = 160.3, 153.6, 146.5, 138.7, 130.4,
128.6, 121.2, 116.7, 115.2, 114.8, 114.6, 113.7, 55.9, 55.4.
HRMS (ESI+): m/z [M]+ calcd for C14H14O3: 230.0943; found: 230.0937.
13C NMR (100 MHz, CDCl3):  = 152.1, 142.7, 140.74, 140.70, 138.5,
138.4, 137.6, 134.4, 129.7, 129.4, 129.1, 128.6, 128.5, 128.1, 128.0,
127.8, 126.8, 125.2, 124.8, 116.3, 21.5 (4 C).
HRMS (ESI+): m/z [M]+ calcd for C28H26O: 378.1984; found: 378.1977.
(1,1′:3′,1′′:3′′,1′′′-Quaterphenyl)-4′-ol (2f)
4,4′′′-Difluoro-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-ol (2j)
The title compound 2f was prepared from 1f (141.2 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless solid; yield: 83.2
mg (86%) (eluent: PE/EtOAc 100:1 to 30:1); mp 98.6–100.2 °C; Rf =
0.56 (PE/EtOAc 5:1).
The title compound 2j was prepared from 1j (151.9 mg, 0.3 mmol) at
80 °C according to the general procedure II; white solid; yield: 105.3
mg (98%) (eluent: PE/EtOAc 100:1 to 30:1); mp 150.6–151.7 °C; Rf =
0.52 (PE/EtOAc 5:1).
IR (neat): 1512, 1494, 1476, 1221, 1159, 838, 821, 799, 527 cm–1
1H NMR (400 MHz, CDCl3):  = 7.71 (s, 1 H), 7.66–7.39 (m, 9 H), 7.23–
IR (neat): 1599, 1487, 1475, 1265, 1221, 1173, 761, 732, 699 cm–1
.
.
1H NMR (400 MHz, CDCl3):  = 7.84 (s, 1 H), 7.74–7.62 (m, 7 H), 7.61–
7.55 (m, 2 H), 7.56–7.44 (m, 5 H), 7.43–7.36 (m, 1 H), 7.15 (d, J = 8.3
Hz, 1 H), 5.50 (s, 1 H).
6.96 (m, 5 H), 5.36 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 152.2, 142.4, 140.70, 140.66, 137.7,
134.2, 129.8, 129.1, 129.0, 128.9, 128.5, 128.1, 128.00, 127.97, 127.8,
127.3, 126.92, 126.86, 126.8, 116.5.
13C NMR (100 MHz, CDCl3):  = 162.8 (d, J = 246.9 Hz), 162.3 (d, J =
245.8 Hz), 152.2, 141.5, 137.7, 136.84 (d, J = 3.3 Hz), 136.79 (d, J = 3.3
Hz), 133.4, 129.9, 129.0, 128.9 (d, J = 8.1 Hz), 128.5, 128.4 (d, J = 7.9
Hz), 128.0, 127.9, 126.8, 116.6, 115.9 (d, J = 19.8 Hz), 115.7 (d, J = 19.6
Hz).
HRMS (ESI+): m/z [M]+ calcd for C24H18O: 322.1358; found: 322.1351.
HRMS (ESI+): m/z [M]+ calcd for C24H16F2O: 358.1169; found:
358.1162.
4,4′′′-Dimethyl-(1,1′:3′,1′′:3′′,1′′′-quaterphenyl)-4′-ol (2g)
The title compound 2g was prepared from 1g (149.6 mg, 0.3 mmol) at
80 °C according to the general procedure II, colorless solid; yield:
103.0 mg (98%) (eluent: PE/EtOAc 100:1 to 30:1); mp 114.9–116.3 °C;
Rf = 0.56 (PE/EtOAc 5:1).
3′,5-Di(furan-3-yl)-(1,1′-biphenyl)-2-ol (2k)
The title compound 2k was prepared from 1k (135.1 mg, 0.3 mmol) at
80 °C following the general procedure II; colorless oil; yield: 78.9 mg
(87%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.56 (PE/EtOAc 5:1).
IR (neat): 1493, 1476, 1277, 1262, 1222, 1173, 810, 794, 709 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.83 (s, 1 H), 7.70 (d, J = 7.5 Hz, 1 H),
7.68–7.51 (m, 8 H), 7.37–7.29 (m, 4 H), 7.14 (d, J = 8.3 Hz, 1 H), 5.48 (s,
1 H), 2.48 (d, J = 6.4 Hz, 6 H).
13C NMR (100 MHz, CDCl3):  = 152.0, 142.2, 137.9, 137.8, 137.7,
137.6, 136.6, 134.1, 129.74, 129.71, 129.6, 128.9, 128.5, 127.9, 127.8,
127.7, 127.1, 126.7, 126.6, 116.4, 21.22, 21.16.
IR (neat): 1511, 1233, 1162, 1057, 1017, 874, 782, 596 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.80 (s, 1 H), 7.71 (s, 1 H), 7.64 (s, 1 H),
7.59–7.46 (m, 4 H), 7.45–7.38 (m, 3 H), 7.10–6.93 (m, 1 H), 7.06–7.02
(m, 1 H), 6.78–6.69 (m, 1 H), 5.33 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 151.8, 144.0, 143.7, 139.0, 137.9,
137.6, 133.7, 129.9, 128.5, 127.8, 127.7, 127.0, 126.7, 126.1, 126.0,
125.6, 125.5, 116.5, 109.0, 108.9.
HRMS (ESI+): m/z [M]+ calcd for C26H22O: 350.1671; found: 350.1663.
HRMS (ESI+): m/z [M + H]+ calcd for C20H15O3: 303.1016; found:
303.1015.
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3′,5-Di(thiophen-3-yl)-(1,1′-biphenyl)-2-ol (2l)
1H NMR (400 MHz, CDCl3):  = 7.83–7.75 (m, 2 H), 7.69 (d, J = 8.2 Hz, 1
H), 7.46 (t, J = 7.4 Hz, 1 H), 7.37 (t, J = 7.4 Hz, 1 H), 7.19–7.12 (m, 2 H),
5.71 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 153.4, 134.7, 130.0, 129.1, 127.9,
126.7, 126.5, 123.8, 117.9, 109.7.
The title compound 2l was prepared from 1l (144.8 mg, 0.3 mmol) at
80 °C following the general procedure II; colorless solid; yield: 91.3
mg (91%) (eluent: PE/EtOAc 100:1 to 20:1); mp 51.2–52.3 °C; Rf = 0.45
(PE/EtOAc 5:1).
IR (neat): 1559, 1541, 1507, 1496, 1270, 1223, 1173, 777, 678 cm–1
.
(S)-(1,1′-Binaphthalen)-2-ol [(S)-2q]23
1H NMR (400 MHz, CDCl3):  = 7.78 (s, 1 H), 7.67 (d, J = 7.8 Hz, 1 H),
7.59–7.51 (m, 4 H), 7.48–7.41 (m, 3 H), 7.40 (s, 3 H), 7.06 (d, J = 8.3 Hz,
1 H), 5.42 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 151.9, 141.9, 141.8, 137.6, 137.0,
129.9, 129.2, 128.42, 128.40, 127.8, 127.5, 127.3, 126.6, 126.4, 126.33,
126.29, 126.2, 121.0, 119.3, 116.4.
The title compound (S)-2q was prepared from (R)-1q (125.5 mg, 0.3
mmol) at 120 °C according to the general procedure II; white solid;
yield: 77.8 mg (96%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.60
(PE/EtOAc 5:1); []D30.9 –99.62 (c 0.27, CHCl3); >99% ee.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OD-H, n-hexane/i-PrOH (95:5), flow rate = 0.5 mL/min,  = 254 nm],
tmin = 8.9 min, tmax = 17.9 min; >99% ee.
1H NMR (400 MHz, CDCl3):  = 7.95–7.79 (m, 4 H), 7.60–7.53 (m, 1 H),
7.50–7.42 (m, 2 H), 7.36 (d, J = 8.4 Hz, 1 H), 7.33–7.24 (m, 3 H), 7.21–
7.13 (m, 1 H), 7.07 (d, J = 8.4 Hz, 1 H), 4.95 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 151.1, 134.3, 134.0, 132.9, 131.6,
130.0, 129.8, 129.3, 129.1, 128.6, 128.1, 127.0, 126.7, 126.1, 125.9,
125.1, 123.5, 118.9, 117.6.
HRMS (ESI+): m/z [M]+ calcd for C20H14OS2: 334.0486; found:
334.0479.
(1,1′:3′,1′′:3′′,1′′′-Quaterphenyl)-2′-ol (2m)
The title compound 2m was prepared from 1m (141.1 mg, 0.3 mmol)
at 120 °C according to the general procedure II; colorless solid; yield:
90.8 mg (94%) (eluent: PE/EtOAc 100:1 to 30:1); mp 96.2–97.9 °C; Rf =
0.52 (PE/EtOAc 10:1).
IR (neat): 3535, 1598, 1458, 1431, 1401, 1221, 757, 700, 614 cm–1
.
(R)-5,5′,6,6′,7,7′,8,8′-Octahydro-(1,1′-binaphthalen)-2-ol [(R)-2r]
1H NMR (400 MHz, CDCl3):  = 7.91 (s, 1 H), 7.75–7.69 (m, 3 H), 7.68–
7.61(m, 4 H), 7.58–7.51 (m, 4 H), 7.50–7.34 (m, 4 H), 7.17 (t, J = 7.6 Hz,
1 H), 5.56 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 149.5, 141.9, 141.0, 138.2, 137.6,
130.2, 130.1, 129.5, 129.3, 129.0, 128.93, 128.90, 128.8, 128.4, 128.3,
127.8, 127.6, 127.3, 126.5, 120.9.
The title compound (R)-2r was prepared from (S)-1r (127.9 mg, 0.3
mmol) at 80 °C according to the general procedure II; colorless oil;
yield: 81.0 mg (97%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.66
(PE/EtOAc 10:1); []D30.9 +20.08 (c 0.19, CHCl3); >99% ee.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OJ-H, n-hexane/i-PrOH (99:1), flow rate = 0.5 mL/min,  = 220 nm],
tmin = 10.2 min, tmax = 18.2 min; >99% ee.
HRMS (ESI+): m/z [M + H]+ calcd for C24H19O: 323.1431; found:
323.1429.
IR (neat): 2927, 2856, 1976, 1476, 1457, 1021, 800, 473 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.22 (t, J = 7.5 Hz, 1 H), 7.15 (d, J = 7.5
Hz, 1 H), 7.02 (d, J = 8.3 Hz, 1 H), 6.96 (d, J = 7.2 Hz, 1 H), 6.80 (d, J = 8.3
Hz, 1 H), 4.42 (s, 1 H), 2.85 (t, J = 6.0 Hz, 2 H), 2.77 (t, J = 6.0 Hz, 2 H),
2.47–2.20 (m, 3 H), 2.16–2.06 (m, 1 H), 1.90–1.61 (m, 8 H).
13C NMR (100 MHz, CDCl3):  = 150.3, 138.7, 136.9, 135.7, 134.5,
129.6, 129.4, 129.2, 127.9, 126.8, 126.4, 112.4, 30.1, 29.4, 28.0, 26.9,
23.32, 23.29, 23.2, 23.0.
3,3′-Di(thiophen-3-yl)-(1,1′-biphenyl)-2-ol (2n)
The title compound 2n was prepared from 1n (144.8 mg, 0.3 mmol) at
120 °C according to the general procedure II; colorless solid; yield:
95.3 mg (95%) (eluent: PE/EtOAc 100:1 to 20:1); mp 95.6–96.9 °C; Rf =
0.66 (PE/EtOAc 5:1).
IR (neat): 3524, 1448, 1325, 1224, 1195, 865, 837, 773 cm–1
1H NMR (400 MHz, CDCl3):  = 7.82 (s, 1 H), 7.70–7.63 (m, 2 H), 7.58–
.
HRMS (ESI+): m/z [M]+ calcd for C20H22O: 278.1671; found: 278.1664.
7.41 (m, 8 H), 7.35–7.28 (m, 1 H), 7.13–7.07 (m, 1 H), 5.67 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 149.6, 141.9, 138.0, 137.8, 136.7,
129.7, 129.6, 129.5, 128.9, 128.5, 128.1, 127.5, 126.5, 126.4, 125.99,
125.96, 123.6, 123.5, 120.9, 120.8.
HRMS (ESI+): m/z [M + H]+ calcd for C20H15OS2: 335.0559; found:
335.0557.
2,2′,3,3′-Tetrahydro-1,1′-spirobi(inden)-7-ol (2s)
The title compound 2s was prepared from 1s (115.3 mg, 0.3 mmol) at
120 °C according to the general procedure II; colorless oil; yield: 69.5
mg (98%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.70 (PE/EtOAc 5:1).
IR (neat): 3530, 2943, 1589, 1474, 1463, 1237, 776, 760, 734 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.40–7.04 (m, 5 H), 6.85 (d, J = 7.2 Hz, 1
H), 6.64 (d, J = 7.9 Hz, 1 H), 4.34 (s, 1 H), 3.17–2.80 (m, 4 H), 2.40–2.25
(m, 2 H), 2.24–2.13 (m, 1 H), 2.09–1.98 (m, 1 H).
13C NMR (100 MHz, CDCl3):  = 152.5, 147.5, 146.1, 144.1, 133.4,
129.0, 127.9, 127.6, 125.4, 123.5, 117.1, 114.5, 59.6, 41.2, 37.4, 31.5,
31.0.
Naphthalen-1-ol (2o)21
The title compound 2o was prepared from 1o (87.7 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless solid; yield: 39.7
mg (92%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.66 (PE/EtOAc 5:1).
1H NMR (400 MHz, CDCl3):  = 8.17 (s, 1 H), 7.79 (s, 1 H), 7.45 (s, 3 H),
7.26 (s, 1 H), 6.76 (s, 1 H), 5.73 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 151.4, 134.8, 127.8, 126.5, 126.0,
HRMS (ESI+): m/z [M + H]+ calcd for C17H17O: 237.1274; found:
237.1273.
125.4, 124.5, 121.6, 120.8, 108.8.
2-(Benzyloxy)-1,1′-biphenyl (2t)24
Naphthalen-2-ol (2p)22
The title compound 2t was prepared from 1t (122.5 mg, 0.3 mmol) at
120 °C according to the general procedure II; colorless oil; yield: 67.9
mg (87%) (eluent: PE/EtOAc 200:1 to 50:1); Rf = 0.60 (PE/EtOAc 20:1).
The title compound 2p was prepared from 1p (87.7 mg, 0.3 mmol) at
80 °C according to the general procedure II; white solid; yield: 39.3
mg (91%) (eluent: PE/EtOAc 100:1 to 30:1); Rf = 0.66 (PE/EtOAc 5:1).
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

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Synthesis
1H NMR (400 MHz, CDCl3):  = 7.71 (d, J = 7.8 Hz, 2 H), 7.56–7.28 (m,
Product Transformations and Applications
10 H), 7.19–7.09 (m, 2 H), 5.17 (s, 2 H).
(1,1′-Biphenyl)-2-yl Trifluoromethanesulfonate (3a)9
13C NMR (100 MHz, CDCl3):  = 155.7, 138.7, 137.4, 131.5, 131.1,
129.8, 128.7, 128.5, 128.0, 127.7, 127.0, 126.9, 121.5, 113.6, 70.6.
The title compound 3a was prepared from 2a (1.70 g, 10.0 mmol) as a
colorless oil in 90% yield (2.72 g, eluent: PE/EtOAc 100:1 to 20:1); Rf =
0.25 (PE).
2-Methoxy-1,1′-biphenyl (2u)25
The title compound 2u was prepared from 1u (99.7 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless oil; yield: 54.1
mg (98%) (eluent: PE/EtOAc 100:1 to 20:1); Rf = 0.60 (PE/EtOAc 10:1).
1H NMR (400 MHz, CDCl3):  = 7.61 (d, J = 8.0 Hz, 2 H), 7.48 (t, J = 7.5
Hz, 2 H), 7.39 (t, J = 7.3 Hz, 3 H), 7.10 (t, J = 7.4 Hz, 1 H), 7.05 (d, J = 8.5
Hz, 1 H), 3.86 (s, 3 H).
1H NMR (400 MHz, CDCl3):  = 7.54–7.38 (m, 9 H).
13C NMR (100 MHz, CDCl3):  = 147.0, 135.7, 132.1, 129.5, 129.1,
128.7, 128.6, 128.5, 123.3, 122.2, 120.1, 118.5 (q, J = 320.5 Hz), 116.9,
113.7.
(1,1′-Biphenyl)-2-yldiphenylphosphine Oxide (3b)10
13C NMR (100 MHz, CDCl3):  = 156.6, 138.7, 131.0, 130.9, 129.7,
128.7, 128.1, 127.0, 120.9, 111.4, 55.7.
The title compound 3b was prepared from 3a (997.6 mg, 3.3 mmol) as
a white solid in 73% yield (835.7 mg, eluent: PE/EtOAc 50:1 to 3:1);
Rf = 0.36 (PE/EtOAc 1:1).
1H NMR (400 MHz, CDCl3):  = 7.60–7.50 (m, 5 H), 7.46–7.25 (m, 9 H),
2-(Methoxymethoxy)-1,1′-biphenyl (2v)26
The title compound 2v was prepared from 1v (108.7 mg, 0.3 mmol) at
80 °C according to the general procedure II; colorless oil; yield: 62.3
mg (97%) (eluent: PE/EtOAc 200:1 to 30:1); Rf = 0.60 (PE/EtOAc 10:1).
1H NMR (400 MHz, CDCl3):  = 7.55–7.50 (m, 2 H), 7.43–7.36 (m, 2 H),
7.34–7.24 (m, 3 H), 7.23–7.18 (m, 1 H), 7.11–7.04 (m, 1 H), 5.09 (s, 2
H), 3.36 (s, 3 H).
7.24–7.19 (m, 2 H), 7.10–6.99 (m, 3 H).
13C NMR (100 MHz, CDCl3):  = 147.8 (d, J = 8.6 Hz), 140.4 (d, J = 4.1
Hz), 134.1 (d, J = 12.2 Hz), 133.2 (d, J = 104.4 Hz), 132.1 (d, J = 9.9 Hz),
131.82 (d, J = 102.2 Hz), 131.80 (d, J = 2.5 Hz), 131.7 (d, J = 9.4 Hz),
131.2 (d, J = 2.7 Hz), 130.2, 128.2 (d, J = 12.1 Hz), 127.24, 127.2, 126.6
(d, J = 12.3 Hz).
13C NMR (100 MHz, CDCl3):  = 154.3, 138.7, 132.1, 131.1, 129.7,
31P NMR (162 MHz, CDCl3):  = 27.76.
128.7, 128.1, 127.0, 122.4, 115.9, 95.2, 56.2.
(1,1′-Biphenyl)-2-yldiphenylphosphane (3c)11
Gram-Scale Preparation of (S)-2q and (R)-2r
(S)-(1,1′-Binaphthalen)-2-ol [(S)-2q]
The title compound 3c was prepared from 3b (1.2 g, 3.4 mmol) as a
colorless solid in 90% yield (1.04 g, eluent: PE/EtOAc 100:1 to 20:1);
Rf = 0.32 (PE).
1H NMR (400 MHz, CDCl3):  = 7.39 (t, J = 7.4 Hz, 1 H), 7.35–7.14 (m,
17 H), 7.10–7.03 (m, 1 H).
13C NMR (100 MHz, CDCl3):  = 148.6, 148.3, 141.9 (d, J = 6.1 Hz),
137.8 (d, J = 11.9 Hz), 136.0 (d, J = 14.2 Hz), 134.2, 134.0 (d, J = 19.9
Hz), 130.2 (d, J = 4.8 Hz), 129.9 (d, J = 3.7 Hz), 128.8, 128.6, 128.5 (d, J =
6.8 Hz), 127.7 , 127.4 (d, J = 19.0 Hz).
To a 100 mL tube were added (R)-1q (2.09 g, 5.0 mmol), Pd(OAc)2
(56.1 mg, 0.25 mmol), and DPPF (278.2 mg, 0.5 mmol) in a N2-filled
glovebox. The tube was capped with a rubber plug and removed from
the glovebox. A solution of HCO2H (460.0 mg, 0.38 mL, 88% wt) and
Et3N (1.52 g, 2.1 mL) in DMF (25 mL) was added via syringe. The reac-
tion mixture was heated to 120 °C in an oil bath and stirred vigorous-
ly for 15 h. Upon completion, the mixture was slowly cooled to rt,
poured into H2O (25 mL), and extracted with EtOAc (3 × 20 mL). The
combined organic layers were washed with brine (30 mL), dried (an-
hyd Na2SO4), filtered, and concentrated under reduced pressure. The
residue was purified by silica gel column chromatography to afford
the desired product (S)-2q (1.18 g, 87%).
31P NMR (162 MHz, CDCl3):  = –13.44.
5-Phenyl-5H-benzo[b]phosphindole 5-Oxide (3d)12
The title compound 3d was prepared from 3c (101.5 mg, 0.3 mmol) as
a colorless oil in 53% yield (44.0 mg, eluent: PE/EtOAc 200:1 to 50:1);
Rf = 0.25 (PE/EtOAc 1:1).
1H NMR (400 MHz, CDCl3):  = 7.84–7.78 (m, 2 H), 7.74–7.53 (m, 6 H),
(R)-5,5′,6,6′,7,7′,8,8′-Octahydro-(1,1′-binaphthalen)-2-ol [(R)-2r]
To a 100 mL tube were added (S)-1r (2.56 g, 6.0 mmol), Pd(OAc)2 (67.4
mg, 0.3 mmol), and DPPF (332.6 mg, 0.6 mmol) in a N2-filled glove-
box. The tube was capped with a rubber plug and removed from the
glovebox. A solution of HCO2H (552.0 mg, 0.46 mL, 88% wt) and Et3N
(1.82 g, 2.5 mL) in DMF (30 mL) was added via syringe. The reaction
was heated to 80 °C in an oil bath and stirred vigorously for 24 h.
Upon completion, the mixture was slowly cooled to rt, poured into
H2O (30 mL), and extracted with EtOAc (3 × 25 mL). The combined or-
ganic layers were washed with brine (35 mL), dried (anhyd Na2SO4),
filtered, and concentrated under reduced pressure. The residue was
purified by silica gel column chromatography to afford the desired
product (R)-2r (1.50 g, 90%).
7.53–7.44 (m, 1 H), 7.41–7.32 (m, 4 H).
13C NMR (100 MHz, CDCl3):  = 141.9 (d, J = 21.8 Hz), 133.5 (d, J = 2.2
Hz), 133.0 (d, J = 106.9 Hz), 132.3 (d, J = 3.0 Hz), 131.1 (d, J = 10.9 Hz),
131.0 (d, J = 103.4 Hz), 130.0 (d, J = 9.6 Hz), 129.6 (d, J = 11.1 Hz),
128.8 (d, J = 12.6 Hz), 121.3 (d, J = 10.1 Hz).
31P NMR (162 MHz, CDCl3):  = 33.67.
Diphenyl[2′-(triethylsilyl)-(1,1′-biphenyl)-2-yl]phosphane (3e)13
The title compound 3e was prepared from 3c (67.6 mg, 0.20 mmol) as
a colorless solid in 77% yield (69.7 mg, eluent: PE/EtOAc 300:1 to
100:1); Rf = 0.80 (PE/EtOAc 20:1).
1H NMR (400 MHz, CDCl3):  = 7.60 (d, J = 7.4 Hz, 1 H), 7.34–7.26 (m, 8
H), 7.24–7.19 (m, 4 H), 7.18–7.11 (m, 3 H), 6.96 (t, J = 7.5 Hz, 1 H), 6.53
(d, J = 7.6 Hz, 1 H), 0.88 (t, J = 7.9 Hz, 9 H), 0.66–0.42 (m, 6 H).
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

1615
R. Li et al.
Paper
Synthesis
13C NMR (100 MHz, CDCl3):  = 149.8 (d, J = 32.0 Hz), 148.2 (d, J = 7.1
Hz), 138.6 (d, J = 14.1 Hz), 137.9 (d, J = 11.8 Hz), 136.9 (d, J = 13.1 Hz),
135.6, 135.5, 134.4 (d, J = 20.4 Hz), 133.9 (d, J = 1.6 Hz), 133.8, 133.6,
131.1 (d, J = 4.2 Hz), 130.8 (d, J = 5.3 Hz), 128.7, 128.6, 128.5, 128.4 (d,
J = 6.6 Hz), 128.1 (d, J = 15.8 Hz), 127.4 (d, J = 44.7 Hz), 126.3, 7.85,
4.26.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OD-H, n-hexane/i-PrOH (70:30), flow rate = 0.8 mL/min,  = 254 nm],
tmin = 5.6 min, tmax = 6.8 min; 98% ee.
1H NMR (400 MHz, CDCl3):  = 8.00–7.95 (m, 1 H), 7.93 (d, J = 8.3 Hz, 1
H), 7.88–7.81 (m, 1 H), 7.67–7.56 (m, 2 H), 7.56–7.45 (m, 4 H), 7.37–
7.15 (m, 8 H), 7.11 (d, J = 8.6 Hz, 1 H), 7.08–7.02 (m, 2 H), 6.96–6.86
(m, 3 H).
31P NMR (162 MHz, CDCl3):  = –15.38.
13C NMR (100 MHz, CDCl3):  = 144.4, 144.3, 134.79, 134.77, 134.7,
133.6, 133.5, 133.4, 132.9, 132.8, 132.7, 132.3, 131.9, 131.8, 131.7,
131.1, 131.0, 130.9, 130.8, 130.48, 130.46, 130.3, 129.8, 129.0, 128.9,
128.1, 127.99, 127.95, 127.93, 127.88, 127.8, 127.6, 127.4, 126.90,
126.85, 125.7, 125.4, 124.8. Due to C–P coupling and the complexity
of the spectrum, doublets in the aromatic region cannot be assigned
and they are listed as singlets.
2-Hydroxy-(1,1′-biphenyl)-3-carbonitrile (3f)27
The title compound 3f was prepared from 2a (340.4 mg, 2.0 mmol) as
a colorless solid in 70% yield (274.4 mg, eluent: PE/EtOAc 50:1 to 5:1);
mp 182.2–183.9 °C; Rf = 0.50 (PE/EtOAc 5:1).
IR (neat): 3307, 2236, 1457, 1434, 1238, 1211, 763, 700, 610 cm–1
1H NMR (400 MHz, CDCl3):  = 7.56–7.51 (m, 3 H), 7.50–7.42 (m, 4 H),
7.07 (t, J = 7.7 Hz, 1 H), 5.92 (s, 1 H).
.
31P NMR (162 MHz, CDCl3):  = 27.97.
13C NMR (100 MHz, CDCl3):  = 155.1, 135.01, 134.98, 132.7, 129.8,
129.5, 129.1, 129.0, 121.3, 116.3, 100.5.
(S)-(1,1′-Binaphthalen)-2-yldiphenylphosphane [(S)-5q]15
The title compound 5q was prepared at 110 °C (oil bath) for 16 h from
(S)-4q (227.3 mg, 0.5 mmol), Et3N (1.4 mL, 10.1 mmol), HSiCl3 (0.25
mL, 2.5 mmol), and toluene (10 mL) according to the procedure for
3c;11 colorless solid; yield: 171.3 mg (78%); 98% ee (eluent: PE/EtOAc
100:1 to 30:1); Rf = 0.30 (PE); []D30.9 +97.02 (c 0.17, CHCl3); 98% ee.
HRMS (ESI+): m/z [M + Na]+ calcd for C13H9NONa: 218.0576; found:
218.0577.
6H-Dibenzo[c,e][1,2]oxaborinin-6-ol (3g)14
The title compound 3g was prepared from 2a (840.8 mg, 4.94 mmol)
as a colorless solid in 98% yield (950.1 mg).
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralpak
AD-H, n-hexane/i-PrOH (98:2), flow rate = 0.8 mL/min,  = 254 nm],
tmin = 5.8 min, tmax = 6.9 min; 98% ee.
1H NMR (400 MHz, CDCl3):  = 7.90–7.85 (m, 2 H), 7.84–7.79 (m, 2 H),
1H NMR (400 MHz, CDCl3):  = 8.21–8.01 (m, 3 H), 7.70 (t, J = 7.4 Hz, 1
H), 7.47 (t, J = 7.0 Hz, 1 H), 7.36 (d, J = 7.4 Hz, 1 H), 7.30–7.14 (m, 2 H),
4.79 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 151.3, 140.5, 133.5, 132.7, 129.1,
127.4, 123.7, 123.1, 122.8, 121.8, 119.7; the signal for the carbon,
which is attached to the boron atom was not observed.
7.43–7.32 (m, 4 H), 7.25–7.09 (m, 15 H).
13C NMR (100 MHz, CDCl3):  = 145.5, 145.2, 138.3, 138.2, 138.1,
138.0, 137.4, 137.3, 135.3, 135.2, 133.8, 133.7, 133.63, 133.60, 133.52,
133.49, 133.43, 133.36, 133.09, 133.07, 130.2, 130.1, 129.20, 129.17,
128.5, 128.40, 128.38, 128.35, 128.32, 128.27, 128.1, 128.0, 127.31,
127.29, 126.8, 126.6, 126.5, 126.1, 125.9, 125.1. Due to C–P coupling
and the complexity of the spectrum, doublets in the aromatic region
cannot be assigned and they are listed as singlets.
(S)-(1,1′-Binaphthalen)-2-yl Trifluoromethanesulfonate [(S)-3q]15
The title compound was prepared from (S)-2q (843.7 mg, 3.1 mmol),
Tf2O (0.56 mL, 3.4 mmol,), and i-Pr2NEt (0.56 mL, 3.4 mmol) accord-
ing to the procedure for 3a;9 colorless oil; yield: 1.06 g (85%) (eluent:
31P NMR (162 MHz, CDCl3):  = –14.08.
30.9
PE/EtOAc 100:1 to 30:1); Rf = 0.50 (PE/EtOAc 10:1); []D
–23.72 (c
0.50, CHCl3); >99% ee.
(R)-5,5′,6,6′,7,7′,8,8′-Octahydro-(1,1′-binaphthalen)-2-yl Trifluoro-
methanesulfonate [(R)-3r]
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OD-H, hexane/i-PrOH (99:1), flow rate = 0.5 mL/min,  = 254 nm],
tmin = 15.6 min, tmax = 17.8 min; >99% ee.
1H NMR (400 MHz, CDCl3):  = 8.05–7.99 (m, 2 H), 7.97–9.92 (m, 2 H),
7.62 (t, J = 7.6 Hz, 1 H), 7.58–7.44 (m, 4 H), 7.37–7.26 (m, 3 H), 7.21 (d,
J = 7.3 Hz, 1 H).
The title compound was prepared from (R)-2r (1.71 g, 6.1 mmol), Tf2O
(1.1 mL, 6.7 mmol), and i-Pr2NEt (1.1 mL, 6.7 mmol) according to the
procedure for 3a;9 colorless oil; yield: 1.83 g (73%) (eluent: PE/EtOAc
30.9
100:1 to 30:1); Rf = 0.80 (PE/EtOAc 20:1); []D
–6.03 (c 0.62,
CHCl3); >99% ee.
13C NMR (100 MHz, CDCl3):  = 145.1, 134.0, 133.8, 132.63, 132.56,
131.0, 130.7, 130.6, 129.4, 129.3, 128.5, 128.3, 127.7, 127.18, 127.16,
126.6, 126.2, 125.8, 125.3, 119.6, 118.4 (q, J = 320.3 Hz).
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralpak
AD-H, n-hexane/i-PrOH (100:0), flow rate = 0.5 mL/min,  = 254 nm],
tmin = 7.2 min, tmax = 7.6 min; >99% ee.
IR (neat): 2934, 1420, 1249, 1208, 1184, 1142, 933, 855, 835 cm–1
.
(S)-(1,1′-Binaphthalen)-2-yldiphenylphosphine Oxide [(S)-4q]15
1H NMR (400 MHz, CDCl3):  = 7.22–7.09 (m, 4 H), 6.93 (d, J = 7.1 Hz, 1
H), 2.95–2.76 (m, 4 H), 2.52–2.36 (m, 2 H), 2.26–2.13 (m, 2 H), 1.87–
1.60 (m, 8 H).
13C NMR (100 MHz, CDCl3):  = 145.1, 138.5, 138.0, 137.9, 135.3,
134.7, 134.0, 129.7, 129.4, 127.3, 125.5, 118.5 (q, J = 320.0 Hz), 118.1,
30.0, 29.8, 28.1, 27.2, 23.3, 23.1, 22.8, 22.6.
The title compound was prepared at 100 °C (oil bath) for 8 h from (S)-
3q (374.0 mg, 0.92 mmol), Pd(OAc)2 (41.0 mg, 0.18 mmol), dppb (78.0
mg, 0.18 mmol), i-Pr2NEt (0.6 mL, 3.68 mmol), diphenylphosphine
oxide (372.0 mg, 1.84 mmol), and DMSO (4.0 mL) according to the
procedure for 3b;10 colorless solid; yield: 418.1 mg (>99%); 70% ee
(eluent: PE/EtOAc 50:1 to 4:1). The product was recrystallized several
HRMS (ESI+): m/z [M + Na]+ calcd for C21H21F3O3SNa: 433.1055; found:
433.1053.
times from CH2Cl2 and n-hexane to obtain a colorless solid; yield:
30.9
236.1 mg (63%); 98% ee; Rf = 0.35 (PE/EtOAc 1:1); []D
+16.31 (c
0.37, CHCl3); 98% ee.
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

1616
R. Li et al.
Paper
Synthesis
(R)-(5,5′,6,6′,7,7′,8,8′-Octahydro-(1,1′-binaphthalen]-2-yl)diphen-
ylphosphine Oxide [(R)-4r]
phenylethyl)silane (6b; 479 mg, 2.0 mmol) was dissolved in MeOH
(30 mL) and THF (30 mL). K2CO3 (1.7 g, 12 mmol) and KF (0.7 g, 12
mmol) were added, and the mixture was stirred for 20 min. H2O2
(30%, 2.5 mL) was added subsequently and the mixture was stirred at
rt for 20 h. The suspension was filtered through Celite with CH2Cl2.
H2O was added and the product was extracted with CH2Cl2 (3 × 20
mL). The combined organic layers were dried (anhyd Na2SO4). The sol-
vent was evaporated under reduced pressure and purified by silica gel
column chromatography (eluent: PE/EtOAc 20:1 to 5:1) affording (S)-
The title compound was prepared at 100 °C (oil bath) for 8 h from (R)-
3r (377.6 mg, 0.92 mmol), Pd(OAc)2 (41.0 mg, 0.18 mmol), dppb (78.0
mg, 0.18 mmol), i-Pr2NEt (0.6 mL, 3.68 mmol), diphenylphosphine
oxide (372.0 mg, 1.84 mmol), and DMSO (4.0 mL) according to the
procedure for 3b;10 colorless solid; yield: 369.7 mg (87%) (eluent:
PE/EtOAc 100:1 to 30:1); mp 92.2–93.6 °C; Rf = 0.50 (PE/EtOAc 1:1);
[]D30.9 –31.81 (c 0.72, CHCl3); >99% ee.
26.3
6c (209.6 mg, 86%) as a colorless oil; Rf = 0.62 (PE/EtOAc 4:1); []D
+40.49 (c 0.68, CHCl3); 92% ee.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OD-H, n-hexane/i-PrOH (95:5), flow rate = 0.8 mL/min,  = 254 nm],
tmin = 9.8 min, tmax = 11.6 min; >99% ee.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OJ-H, n-hexane/i-PrOH (95:5), flow rate = 1.0 mL/min,  = 254 nm],
tmin = 10.3 min, tmax = 11.5 min.
1H NMR (400 MHz, CDCl3):  = 7.37–7.30 (m, 4 H), 7.29–7.21 (m, 1 H),
4.85 (q, J = 6.4 Hz, 1 H), 2.09 (s, 1 H), 1.47 (d, J = 6.5 Hz, 3 H).
IR (neat): 2930, 1436, 1198, 1116, 720, 700, 551, 537 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.62–7.48 (m, 3 H), 7.45–7.30 (m, 6 H),
7.28–7.20 (m, 2 H), 7.18–7.10 (m, 1 H), 6.81 (d, J = 7.5 Hz, 1 H), 6.72 (t,
J = 7.5 Hz, 1 H), 6.44 (d, J = 7.3 Hz, 1 H), 2.86 (t, J = 6.1 Hz, 2 H), 2.65–
2.56 (m, 1 H), 2.55–2.44 (m, 1 H), 2.24–2.08 (m, 1 H), 2.04–1.94 (m, 2
H), 1.91–1.79 (m,1 H), 1.79–1.29 (m, 8 H).
13C NMR (100 MHz, CDCl3):  = 145.9, 128.6, 127.5, 125.5, 70.5, 25.2.
(R)-1-Phenylethanol [(R)-6c]
13C NMR (100 MHz, CDCl3):  = 145.5, 145.4, 142.4, 142.3, 137.83,
137.79, 137.0, 136.89, 136.86, 135.8, 134.6, 133.8, 133.6, 132.8, 132.1,
132.03, 131.97, 131.9, 131.17, 131.16, 131.13, 131.06, 130.83, 130.81,
128.6, 128.5, 128.1, 128.0, 127.9, 127.8, 127.7, 127.5, 127.3, 124.51,
30.46, 29.8, 27.4, 27.2, 23.3, 22.9, 22.8, 22.6. Due to C–P coupling and
the complexity of the spectrum, doublets in the aromatic region can-
not be assigned and they are listed as singlets.
To a mixture of [PdCl(-C3H5)]2 (7.5 mg, 0.0205 mmol, 0.5 mol% Pd)
and ligand (R)-5r (18.3 mg, 0.041 mmol, 1.0 mol%) was added styrene
(6a; 427 mg, 4.1 mmol). The solution was cooled to 0 °C, and HSiCl3
(0.5 mL, 4.9 mmol) was added dropwise. The solution was stirred at
0 °C for 48 h. Distillation of the reaction mixture gave trichloro-
(1-phenylethyl)silane (6b; 764.0 mg, 78% yield). The title compound
(R)-6c was prepared from 6b as a colorless oil in 91% yield (221.9 mg,
eluent: PE/EtOAc 20:1 to 5:1) according to the above procedure for
(S)-6c; Rf = 0.62 (PE/EtOAc 4:1); []D30.9 –32.43 (c 0.58, CHCl3); 62% ee.
31P NMR (162 MHz, CDCl3):  = 27.37.
HRMS (ESI+): m/z [M + H]+ calcd for C32H32OP: 463.2186; found:
463.2191.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OJ-H, n-hexane/i-PrOH (95:5), flow rate = 1.0 mL/min,  = 254 nm],
tmin = 10.3 min, tmax = 11.5 min.
(R)-(5,5′,6,6′,7,7′,8,8′-Octahydro-[1,1′-binaphthalen]-2-yl)diphen-
ylphosphane [(R)-5r]
The title compound was prepared at 110 °C (oil bath) for 16 h from
(R)-4r (351.6 mg, 0.76 mmol), Et3N (2.1 mL, 15.3 mmol), HSiCl3 (0.4
mL, 3.7 mmol), and toluene according to the procedure for 3c;11 white
solid; yield: 309.5 mg (91%) (eluent: PE/EtOAc 100:1 to 30:1); mp
101.6–102.6 °C; Rf = 0.30 (PE); []D30.9 –90.53 (c 0.17, CHCl3); >99% ee.
(S,E)-[3-(Benzyloxy)prop-1-ene-1,3-diyl]dibenzene [(S)-7b]16b
To a 10 mL tube were added [PdCl(-C3H5)]2 (0.00375 mmol, 1.4 mg),
ligand (R)-5r (0.0075 mmol), and CH2Cl2 (0.3 mL), and the mixture
was stirred at rt in a N2-filled glovebox. After 30 min, 7a (0.15 mmol,
37.8 mg), Cs2CO3 (0.45 mmol, 146.6 mg), BnOH (0.30 mmol, 32.4 mg),
and CH2Cl2 (0.45 mL) were added. The tube was capped with a rubber
plug and removed from the glovebox. After stirring vigorously at rt for
4 h, the mixture was poured into H2O (5 mL), and extracted with
CH2Cl2 (3 × 5 mL). The combined organic layers were dried (anhyd
Na2SO4), filtered, and concentrated under reduced pressure. The resi-
due was purified by silica gel column chromatography with PE/EtOAc
IR (neat): 2928, 2857, 1452, 1434, 779, 741, 697, 503 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.26 (s, 6 H), 7.21–7.12 (m, 4 H), 7.02
(t, J = 8.8 Hz, 2 H), 6.96–6.84 (m, 2 H), 6.50 (d, J = 7.3 Hz, 1 H), 2.80 (s,
4 H), 2.35–2.19 (m, 2 H), 2.18–2.07 (m, 2 H), 1.77–1.53 (m, 8 H).
13C NMR (100 MHz, CDCl3):  = 147.8, 147.5, 140.14, 140.07, 138.63,
138.59, 138.5, 138.3, 138.1, 137.2, 135.5, 135.4, 134.90, 134.89, 134.0,
133.9, 133.8, 133.7, 133.4, 133.3, 131.0, 128.5, 128.34, 128.28, 128.24,
128.18, 128.17, 128.1, 127.5, 127.4, 124.9, 30.3, 30.1, 28.0, 27.94,
27.87, 27.8, 23.5, 23.3, 23.2, 22.9. Due to C–P coupling and the com-
plexity of the spectrum, doublets in the aromatic region cannot be as-
signed and they are listed as singlets.
25.1
(100:2) to afford the desired product (S)-7b (35.9 mg, 80%); []D
+12.50 (c 0.50, CHCl3); 80% ee.
Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OD-H, n-hexane/i-PrOH (98:2), flow rate = 0.7 mL/min,  = 254 nm],
tmax = 6.6 min, tmin = 6.9 min.
31P NMR (162 MHz, CDCl3):  = –14.61.
HRMS (ESI+): m/z [M + H]+ calcd for C32H32P: 447.2236; found:
1H NMR (400 MHz, CDCl3):  = 7.43 (d, J = 7.6 Hz, 2 H), 7.35 (dd, J =
16.2, 8.0 Hz, 8 H), 7.29 (t, J = 7.4 Hz, 4 H), 7.21 (t, J = 7.2 Hz, 1 H), 6.62
(d, J = 15.9 Hz, 1 H), 6.42–6.20 (m, 1 H), 5.01 (d, J = 7.0 Hz, 1 H), 4.62–
4.50 (m, 2 H).
447.2237.
13C NMR (100 MHz, CDCl3):  = 141.2, 138.5, 136.7, 131.7, 130.4,
128.67, 128.65, 128.5, 127.9, 127.7, 127.1, 126.7, 81.7, 70.2.
(S)-1-Phenylethanol [(S)-6c]6,16a
To a mixture of [PdCl(-C3H5)]2 (1.5 mg, 0.0041 mmol, 0.1 mol% Pd)
and ligand (S)-5q (3.6 mg, 0.0082 mmol, 0.2 mol%) was added styrene
(6a; 427 mg, 4.1 mmol). The reaction mixture was cooled to 0 °C for
30 min, and HSiCl3 (0.5 mL, 4.9 mmol) was added dropwise. The mix-
ture was stirred at 0 °C for 12 h. Distillation of the mixture gave tri-
chloro(1-phenylethyl)silane (6b; 876.9 mg, 89% yield). Trichloro(1-
(1R,2S)-2-Phenyl-1,2-dihydronaphthalen-1-ol [(1R,2S)-8b]16c,d
To a 10 mL tube were added the palladium catalyst [0.006 mmol, 3.6
mg; prepared from (S)-5q and Pd(OAc)2 according to the reported
procedure]16c 1,2,3,4-tetrahydro-1,4-epoxynaphthalene (8a; 0.20
© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618

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R. Li et al.
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mmol, 28.8 mg), PhB(OH)2 (0.24 mmol, 29.3 mg), and Cs2CO3 (0.20
mmol, 65.0 mg) in a N2-filled glovebox. The tube was capped with a
rubber plug and removed from the glovebox. Then CHCl3 (3.0 mL) and
H2O (20 L) were added, and the reaction mixture was cooled to 0 °C
and stirred vigorously for 16 h. The mixture was poured into H2O (10
mL), and extracted with EtOAc (3 × 10 mL). The combined organic lay-
ers were dried (anhyd Na2SO4), filtered, and concentrated under re-
duced pressure. The residue was purified by silica gel column chro-
matography with PE/EtOAc (20:1) to afford the desired product
(1R,2S)-8b (40.5 mg, 91%); []D28.2 –128.55 (c 0.40, CHCl3); 79% ee.
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Enantiomeric excess was determined by chiral HPLC [Daicel Chiralcel
OD-H, n-hexane/i-PrOH (90:10), flow rate = 1.0 mL/min,  = 254 nm],
tmax = 8.1 min, tmin = 13.0 min.
1H NMR (400 MHz, CDCl3):  = 7.34–7.18 (m, 8 H), 7.15 (d, J = 7.2 Hz, 1
H), 6.68 (d, J = 9.6 Hz, 1 H), 6.10 (dd, J = 9.6, 3.9 Hz, 1 H), 4.88 (s, 1 H),
3.83 (s, 1 H).
13C NMR (100 MHz, CDCl3):  = 137.8, 136.2, 132.7, 129.8, 129.4,
128.7, 128.4, 128.3, 128.1, 127.5, 126.8, 126.5, 71.4, 47.4.
Funding Information
This project was supportedby National Natural Science Foundation of
China (Grant Nos. 21702056, 21971059, and 21702055), Hunan Pro-
vincial Natural Science Foundation of China (Grant No. 2020JJ5040),
National Program for Thousand Young Talents of China, and Funda-
mental Research Funds for the Central Universities.
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/a-1337-5153.
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© 2020. Thieme. All rights reserved. Synthesis 2021, 53, 1605–1618