Palladium-Catalyzed Addition of Arylboronic Acids to para- Quinone Methides for Preparation of Diarylacetates

Article abstract of DOI:10.1002/adsc.201601302

A palladium-catalyzed addition of arylboronic acids to para-quinone methides has been developed. The catalytic system employing 4,4′-dimethoxy-2,2′-bipyridine (DMeO-BPy) as ligand and trifluoroethanol (TFE) as solvent provides diarylacetate products in high yields. A wide range of functionalized arylboronic acids can be used and the method tolerates some variation in the scope of the para-quinone methides. (Figure presented.).

Full text of DOI:10.1002/adsc.201601302

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DOI: 10.1002/adsc.201601302
Palladium-Catalyzed Addition of Arylboronic Acids to para-
Quinone Methides for Preparation of Diarylacetates
Ruijing Zhuge,a Liang Wu,a Mao Quan,a Nicholas Butt,a Guoqiang Yang,a,*
and Wanbin Zhanga,*
a
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240,
Peopleꢀs Republic of China
Fax : (+86)-021-5474-3265; phone: (+86)-021-5474-3265; e-mail: gqyang@sjtu.edu.cn or wanbin@sjtu.edu.cn
Received: November 26, 2016; Revised: January 13, 2017; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201601302.
Abstract: A palladium-catalyzed addition of arylbor- tionalized arylboronic acids can be used and the
onic acids to para-quinone methides has been devel- method tolerates some variation in the scope of the
oped. The catalytic system employing 4,4’-dime- para-quinone methides.
thoxy-2,2’-bipyridine (DMeO-BPy) as ligand and tri-
fluoroethanol (TFE) as solvent provides diarylace- Keywords: addition; arylboron reagents; diarylace-
tate products in high yields. A wide range of func- tates; palladium; para-quinone methides
Introduction
using soft organometallic nucleophiles such as aryl-
boron reagents (e.g., Hayashi–Miyaura reactions),
Diaryl-substituted tertiary carbons are common struc- rhodium complexes perform as efficient catalysts
tural motifs present in a number of natural products, showing high activity and enantioselectivity.[6] Con-
pharmaceuticals, and bioactive compounds.[1] Among versely, the use of palladium catalysts in such reac-
them, the diarylacetate skeleton is one of the most tions is an attractive alternative due to their lower
important structural frameworks, therefore significant cost compared to rhodium catalysts. Therefore, con-
effort has been directed towards their synthesis.[2–4] siderable effort has been directed towards the devel-
The coupling of arylacetates with aryl halides or a- opment of palladium-catalyzed additions of arylboron
halide arylacetates with aryl organometallic reagents reagents to electron-deficient olefins.[7,8] The Miyaura
has been developed as an efficient methodology.[2] group has carried out a number of pioneering investi-
Reactions of a-aryl-a-diazoacetates with aryl organo- gations.[9] The Minnaard and Lu groups have reported
metallic reagents or aryl halides are also important several seminal Pd(II) catalytic systems.[10,11] The Shi,
strategies for the preparation of diarylacetates.[3] The Stoltz and Pullarkat groups have developed several
metal-catalyzed intermolecular insertion of aryl C–H highly efficient asymmetric catalytic systems for such
bonds to a-aryl-a-diazoacetates has attracted much reactions.[12–14] Although a number of palladium cata-
attention because of its atom economy and operation- lyst systems has been developed by various research
al simplicity.[4] Among these achievments, it should be groups, the substrate scope remains limited.
noted that the Zhang group has developed a gold-cat-
Recently, the Hayashi group reported an interesting
alyzed direct C–H bond functionalization of phenols Rh-catalyzed addition of arylboron reagents to aryl-
with a-aryl-a-diazoacetates, giving 2-(4-hydroxyaryl)- substituted ortho-quinone methides.[15] However, this
2-arylacetates in excellent yields and with high site se- methodology is limited to the construction of triaryl-
lectivity.[4d] Herein, we report an alternative method- methane structures. In continuation of our research
ology for the construction of diarylacetates via concerning the Pd(II)-catalyzed addition of arylbor-
a Pd(II)-catalyzed addition of arylboronic acids to ons,[16] we herein describe a Pd-catalyzed addition of
carbonyl-substituted para-quinone methides.
Transition metal-catalyzed additions of organome- thides for the preparation of 2-(4-hydroxyaryl)-2-aryl-
tallic reagents to electron-deficient olefins are useful acetates. The structural motifs of the corresponding
arylborons to carbonyl-substituted para-quinone me-
AHCTUNGTRENNUNG
reactions for the construction of C–C bonds and are products are present in numerous bioactive com-
widely applied in total syntheses.[5] For additions pounds (Scheme 1).[17]
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Table 1. Screening of the reaction conditions.[a]
Entry
Solvent
Ligand
Yield [%][b]
1
TFE
BPy
82
2
3
4
5
6
7
HFIP
MeOH
EtOH
t-AA
THF
BPy
BPy
BPy
BPy
BPy
BPy
62
69
57
trace
73
Scheme 1. Addition of arylboron to quinone methides.
Results and Discussion
DCE
40
8
9
1,3-dioxane
MeCN
toluene
TFE
TFE
TFE
TFE
TFE
TFE
BPy
BPy
BPy
DMe-BPy
DMeO-BPy
DMeO2C-BPy
Phen
Neocup
DMeO-BPy
trace
trace
trace
95
98
80
93
65
94
tert-Butyl groups can be easily removed when they
are bonded to an electron-rich aromatic ring. There-
fore, a di-tert-butyl-substituted quinone methide sub-
strate 1a was used as a model substrate for our initial
studies.[18] Using phenylboronic acid as the boron re-
agent, reaction conditions were investigated employ-
ing Pd(TFA)2 as the palladium source (Table 1). Ini-
tially, different alcohol solvents were examined using
BPy as the ligand, since previous studies showed that
alcohol solvents have a strong influence on the reac-
tion (entries 1–5).[16] The desired diarylacetate product
3a was obtained in the highest yield when trifluoro-
10
11
12
13
14
15
16[c]
[a]
Reactions were carried out on a 0.20 mmol scale using
10 mol% Pd(TFA)2, 12 mol% ligand and PhB(OH)2
(0.40 mmol) in unpurified solvent (2.0 mL) at 708C for
24 h under an air atmosphere.
Yield of isolated product.
5 mol% Pd(TFA)2, 6 mol% ligand, 36 h.
TFA=trifluoroacetic acetate, TFE=trifluoroethanol,
HFIP=hexafluoroisopropyl alcohol, t-AA=tert-amyl al-
cohol, DCE=1,2-dichloroethane.
[b]
[c]
[d]
ACHTUNGTRENNUNGethanol (TFE) was used as solvent (entry 1). Lower
reaction activity was observed in HFIP, MeOH,
EtOH, and t-AA (Table 1, entries 2–5). It appears
that there is some correlation between reaction activi-
ty and the acidity and steric hindrance of the alcohol
solvents: the more acidic and less bulky solvents give
the desired product in higher yields. The addition pro-
ceeded smoothly in THF to give the desired product hindrance (entries 14 and 15). When the catalyst load-
in 73% yield (entry 6). The addition product was ob- ing was reduced to 5 mol%, a longer reaction time
tained in moderate yield when the reaction was car- (36 h) was needed to finish the reaction (entry 16).
ried out in DCE (entry 7). Dioxane, MeCN, and tolu- Thus, the optimized reaction conditions were found to
ene completely inhibited the addition reaction (en- be using DMeO-BPy as the ligand in TFE solvent.
tries 8–10). Different bidentate nitrogen ligands were
Different types of chiral ligands have also been
screened in order to improve the yield (entries 11– studied for the asymmetric addition of phenylboronic
15). Increasing the electron-donating ability of the acid to 1a (Figure 1). However, additions with differ-
para-substituents led to an increase in catalytic activi- ent chiral P,N, bisoxazoline, BINAP, and phosphor-
ty (entries 1 and 11–13). Consequently, the best ligand
ACHTUNGTRENaNGNU midite ligands gave the desired adduct as a racemic
was found to be DMeO-BPy, which promoted the ad- mixture. The pyridine-oxazoline type ligands could
dition with the best yield out of all of the tested li- only provide the product in a maximum of 10% ee.
gands (entry 12). Phenanthroline also gave the desired An enantioselective version of this reaction appears
product in good yield, but the related ligand, neocu- challenging and new ligands are likely required to
proine, showed only moderate activity due to steric induce enantioselectivity.
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(Table 3, 3r–u). Amide-substituted para-quinone me-
thides were also compatible with the reaction condi-
tions. Linear and cyclic amides gave their correspond-
ing products in high yields (3v–z). An acyl-substituted
para-quinone methide could give the corresponding
adduct in 79% yield (3aa). However, an attempt to
use the widely studied substrate, phenyl-substituted
para-quinone methide, was unsuccessful (3ab), and
only the TFE adduct was obtained in 17% yield. Ad-
dition using 4-hydroxystyrene as a substrate, which
can be considered as a para-quinone methide equiva-
lent, did not give any product.
A catalytic cycle has been proposed for this reac-
tion (Scheme 2). After sequential transmetallation
and ligand exchange, intermediate B is formed from
the catalyst. The key step is insertion of the phenyl
group into the double bond, which leads to complex
C. Complex C then tautomerizes to complex D.[18g]
Protonation of D gives the desired addition product
and regenerates the catalyst for the next cycle.
Figure 1. Results using chiral ligands.
With the optimized conditions in hand, we tested
different arylboronic acids (Table 2). Arylboronic
acids possessing both electron-donating and electron-
withdrawing groups are well tolerated (3a–p). Aryl-
boronic acids bearing electron-donating groups at the
para positions showed higher reactivity than those
bearing electron-withdrawing groups (3b, 3c vs. 3e–h).
The reaction of a para-phenyl-substituted phenylbor-
onic acid gave its corresponding product in moderate
yield because of its poor solubility (3d). Arylboronic
Scheme 2. Proposed mechanism.
The addition products could be further manipulat-
acids bearing meta-substituents also gave the addition ed. The tert-butyl groups were deprotected via retro-
products in high yields (3i–l). However, substrates Fridel-Crafts reaction using an AlCl3-MeNO2-toluene
with substituents at the ortho position of the phenyl system, giving the deprotected product 4 in 83% yield
ring showed lower reactivities compared with those at (Scheme 3).[19] A halide substituent was introduced at
other positions. For example, an arylboronic acid the ortho-position of the phenol via a mono-bromina-
bearing the small fluoride group gave the product 3m tion.[20] The bromide can be easily transformed to
in 75% yield. Disubstituted arylboronic acids gave other functional groups. For example, a Suzuki cou-
their corresponding products in good to excellent pling was performed to give the desired coupling
yields (3n and 3o). Naphthylboronic acid showed product 6 in 52% yield.
moderate reactivity in the addition reaction (3p). To
our delight, (E)-(2-phenethenyl)boronic acid can also
afford the corresponding product in good yield (3q).
Conclusions
Substrates bearing different ester groups were also
tested. Linear and branched alkyl esters gave their In conclusion, a palladium-catalyzed addition of aryl-
corresponding products with good to excellent yields boronic acids to para-quinone methides has been de-
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Table 2. Scope of the arylboronic acids.[a,b]
[a]
Reactions were carried out on a 0.20 mmol scale using 10 mol% Pd(TFA)2, 12 mol% ligand and ArB(OH)2 (0.40 mmol)
in TFE (2.0 mL) at 708C for 24 h under an air atmosphere.
Yield of isolated product.
[b]
[c]
Results in parentheses were obtained by using 5 mol% Pd(TFA)2 and 6 mol% ligand for 36 h.
veloped for the construction of diarylacetates. A and arylboronic acids are tolerated under the reaction
range of carbonyl-substituted para-quinone methides conditions. The removal of the tert-butyl groups and
further transformations were carried out to determine
the practicality of our methodology.
Experimental Section
General Information
The NMR spectra were recorded on a Varian MERCURY
plus-400 (400 MHz, 1H; 101 MHz, 13C) spectrometer with
chemical shifts reported in ppm relative to the residual deu-
terated solvents. Mass spectrometry analysis was carried out
using an electrospray spectrometer Waters Micromass Q-
TOF Premier Mass Spectrometer at the Instrumental Analy-
sis Center of Shanghai Jiao Tong University. Melting points
were measured with an SGW X-4 micro melting point appa-
ratus. 2,2,2-Trifluoroethanol (TFE) (99.5% purity) was ob-
Scheme 3. Deprotection and further transformations.
tained from Energy Chemical Co., Ltd. The other reagents
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Table 3. Scope of the substrates.[a,b]
added and the flask was equipped with a reflux condenser.
The reaction mixture was stirred at room temperature for
30 min. The substrate (0.2 mmol) and arylboronic acid
(0.4 mmol) were then added. The temperature was increased
to 708C. After stirring for 24 h, the reaction mixture was
cooled to room temperature, and the solvent was removed
by rotary evaporation. The residue was purified by 200–300
mesh silica gel column chromatography to give the corre-
sponding products.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-phenylace-
tate (3a): Yellow solid; mp 68–708C; 1H NMR (400 MHz,
CDCl3): d=7.32 (s, 2H), 7.32–7.30 (m, 2H), 7.25 (d, J=
0.5 Hz, 1H), 7.12 (s, 2H), 5.14 (s, 1H), 4.93 (s, 1H), 3.73 (s,
3H), 1.40 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.5,
153.0, 139.2, 135.8, 129.0, 128.4, 127.0, 125.2, 56.9, 52.1, 34.3,
30.2; HR-MS (ESI): m/z=355.2266, calcd. for C23H31O3S
(M+H)+: 355.2273.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(p-tolyl)-
AHCTUNGTRENNUNG
acetate (3b): Yellow solid; mp 67–698C; 1H NMR
(400 MHz, CDCl3): d=7.21 (d, J=8.1 Hz, 2H), 7.13–7.11
(m, 4H), 5.14 (s, 1H), 4.89 (s, 1H), 3.72 (s, 3H), 2.32 (s,
3H), 1.40 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.6,
152.9, 136.6, 136.3, 135.7, 129.2, 128.3, 125.2, 56.5, 52.1, 34.3,
30.2, 21.0; HR-MS (ESI): m/z=369.2416, calcd. for
C24H33O3S (M+H)+: 369.2429.
Methyl 2-[4-(tert-butyl)phenyl]-2-(3,5-di-tert-butyl-4-hy-
droxyphenyl)acetate (3c): Yellow liquid; 1H NMR
(400 MHz, CDCl3): d=7.33 (d, J=8.4 Hz, 2H), 7.24–7.23
(m, 2H), 7.16 (s, 2H), 5.14 (s, 1H), 4.89 (s, 1H), 3.71 (s,
3H), 1.41 (s, 18H), 1.29 (s, 9H); 13C NMR (101 MHz,
CDCl3): d=173.6, 153.0, 149.8, 136.3, 135.8, 129.1, 128.0,
125.4, 125.2, 56.5, 52.1, 34.40, 34.35, 31.3, 30.2; HR-MS
(ESI): m/z=411.2891, calcd. for C27H39O3S (M+H)+:
411.2899.
Methyl
2-([1,1’-biphenyl]-4-yl)-2-(3,5-di-tert-butyl-4-hy-
droxyphenyl)acetate (3d): White solid; mp 103–1058C;
1H NMR (400 MHz, CDCl3): d=7.57 (t, J=8.4 Hz, 4H),
7.47–7.36 (m, 5H), 7.18 (s, 2H), 5.17 (s, 1H), 4.98 (s, 1H),
3.76 (s, 3H), 1.43 (s, 18H); 13C NMR (101 MHz, CDCl3):
d=173.5, 153.0, 140.8, 139.9, 138.4, 135.9, 128.9, 128.7, 127.1,
127.0, 125.2, 56.6, 52.2, 34.4, 30.3; HR-MS (ESI): m/z=
431.2573, calcd. for C29H35O3S (M+H)+: 431.2586.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(4-fluoro-
phenyl)acetate (3e): Yellow solid; mp 76–798C; 1H NMR
(400 MHz, CDCl3): d=7.30–7.27 (m, 2H), 7.08 (s, 2H),
7.02–6.98 (m, 2H), 5.16 (s, 1H), 4.91 (s, 1H), 3.73 (s, 3H),
1.40 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.4, 161.9
(d, J=246.4 Hz), 153.0, 135.9, 135.0, 130.1 (d, J=8.1 Hz),
128.9, 125.0, 115.3 (d, J=21.2 Hz), 56.0, 52.2, 34.4, 30.2; HR-
MS (ESI): m/z=373.2179, calcd. for C23H30FO3S (M+H)+:
373.2173.
[a]
Reactions were carried out on a 0.20 mmol scale using
10 mol% Pd(TFA)2, 12 mol% ligand and PhB(OH)2
(0.40 mmol) in TFE (2.0 mL) at 708C for 24 h under an
air atmosphere.
Yield of isolated product.
Results in parentheses were obtained by using 5 mol%
Pd(TFA)2 and 6 mol% ligand for 36 h.
The addition of TFE to the substrate proceeded to give
the adduct in 17% yield.
[b]
[c]
[d]
Methyl 2-(4-chlorophenyl)-2-(3,5-di-tert-butyl-4-hydroxy-
phenyl)acetate (3f): Yellow liquid; 1H NMR (400 MHz,
CDCl3): d=7.30–7.25 (m, 4H), 7.08 (s, 2H), 5.17 (s, 1H),
4.89 (s, 1H), 3.73 (s, 3H), 1.40 (s, 18H); 13C NMR
(101 MHz, CDCl3): d=173.2, 153.1, 137.8, 136.0, 132.9,
129.9, 128.6, 125.0, 56.2, 52.3, 34.4, 30.2; HR-MS (ESI): m/
z=357.1734, calcd. for C23H28ClO3S (MÀH)À: 387.1727.
were purchased from Adamas-Beta Ltd., Energy Chemical
Inc. or J&K Scientific Inc. and used without further purifica-
tion unless otherwise specified.
General Procedure for Pd-Catalyzed Addition
Methyl
2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-[4-(tri-
fluoromethyl)phenyl]acetate (3g): Yellow solid; mp 95–
968C; 1H NMR (400 MHz, CDCl3): d=7.57 (d, J=8.1 Hz,
2H), 7.44 (d, J=8.1 Hz, 2H), 7.11 (s, 2H), 5.19 (s, 1H), 4.97
A
Schlenk tube (25 mL) was charged with Pd(TFA)2
(6.65 mg, 0.4 mmol, 0.1 equiv.) and 4,4’-dimethoxy-2,2’-bipyr-
idine (5.2 mg, 0.12 equiv.). Unpurified TFE (2.0 mL) was
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(s, 1H), 3.74 (s, 3H), 1.41 (s, 18H); 13C NMR (101 MHz,
CDCl3): d=172.8, 153.2, 143.3, 136.1, 129.3 (q, J=32.3 Hz),
128.9, 128.1, 126.0 (q, J=208.1 Hz), 125.4 (q, J=3.0 Hz),
125.1, 56.6, 52.4, 34.4, 30.2; HR-MS (ESI): m/z=421.1995,
calcd. for C24H28F3O3S (MÀH)À: 421.1991.
136.0, 129.4, 129.1, 126.5, 125.6, 57.1, 52.4, 34.6, 30.6, 21.6;
HR-MS (ESI): m/z=383.2581, calcd. for C25H35O3S (M+
H)+: 383.2586.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(naphtha-
len-2-yl)acetate (3p): Red solid; mp 96–988C; 1H NMR
(400 MHz, CDCl3): d=7.85–7.70 (m, 4H), 7.49–7.43 (m,
3H), 7.18 (s, 2H), 5.16 (s, 1H), 5.10 (s, 1H), 3.75 (s, 3H),
1.40 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.5, 153.0,
136.7, 135.8, 133.3, 132.4, 128.9, 128.1, 127.9, 127.5, 127.1,
126.7, 126.0, 125.8, 125.3, 57.0, 52.2, 34.4, 30.2; HR-MS
(ESI): m/z=405.2406, calcd. for C27H32O3S (M+H)+:
405.2429.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(m-tolyl)-
1
N
7.21 (t, J=7.6 Hz, 1H), 7.14 (m, 4H), 7.06 (d, J=7.6 Hz,
1H), 5.14 (s, 1H), 4.89 (s, 1H), 3.72 (s, 3H), 2.33 (s, 3H),
1.40 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.6, 152.9,
139.1, 138.0, 135.7, 129.2, 129.0, 128.3, 127.8, 125.4, 125.2,
56.8, 52.2, 34.3, 30.2, 21.5; HR-MS (ESI): m/z=369.2415,
calcd. for C24H33O3S (M+H)+: 369.2429.
Methyl (E)-2-(3,5-di-tert-butyl-4-hydroxyphenyl)-4-phe-
nylbut-3-enoate (3q): Colorless oil; 1H NMR (400 MHz,
CDCl3): d=7.41 (d, J=7.4 Hz, 2H), 7.32 (t, J=7.4 Hz, 3H),
7.18 (s, 2H), 6.58 (dd, J=15.8, 8.2 Hz, 1H), 6.50 (d, J=
15.8 Hz, 1H), 5.21 (s, 1H), 4.40 (d, J=8.2 Hz, 1H), 3.75 (s,
3H), 1.46 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.63,
153.37, 137.09, 136.34, 132.00, 129.16, 128.74, 128.18, 127.80,
126.71, 124.73, 55.26, 52.42, 34.65, 30.50; HR-MS (ESI):
m/z=381.2436, calcd. for C25H33O3S (M+H)+: 381.2424.
Ethyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-phenylace-
tate (3r): Yellow solid; mp 72–748C; 1H NMR (400 MHz,
CDCl3): d=7.36–7.28 (m, 4H), 7.27–7.23 (m, 1H), 7.13 (s,
2H), 5.14 (s, 1H), 4.91 (s, 1H), 7.22–7.17 (m, 2H), 1.40 (s,
18H), 1.26 (t, J=7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3):
d=173.0, 152.9, 139.4, 135.7, 129.2, 128.5, 128.4, 127.0 125.2,
61.0, 57.1, 34.4, 30.3, 14.2; HR-MS (ESI): m/z=369.2420,
calcd. for C24H33O3S (M+H)+: 369.2429.
Propyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-phenylace-
tate (3s): Yellow solid; mp 62–638C; 1H NMR (400 MHz,
CDCl3): d=7.36–7.29 (m, 4H), 7.29–7.22 (m, 1H), 7.14 (s,
2H), 5.14 (s, 1H), 4.93 (s, 1H), 4.10 (t, J=6.7 Hz, 2H), 1.65
(dd, J=14.2, 6.9 Hz, 2H), 1.41 (s, 18H), 0.88 (t, J=7.4 Hz,
3H); 13C NMR (101 MHz, CDCl3): d=173.1, 152.9, 139.4,
135.7, 129.2, 128.5, 128.4, 126.9, 125.2, 66.5, 57.1, 34.3, 30.2,
21.9, 10.4; HR-MS (ESI): m/z=383.2588, calcd. for
C25H35O3S (M+H)+: 383.2586.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(3-meth-
oxyphenyl)acetate (3j): Yellow solid; mp 97–998C; H NMR
1
G
(400 MHz, CDCl3): d=7.26–7.21 (m, 1H), 7.14 (s, 2H),
6.94–6.86 (m, 2H), 6.79 (dd, J=8.2, 2.5 Hz, 1H), 5.15 (s,
1H), 4.90 (s, 1H), 3.78 (s, 3H), 3.73 (s, 3H), 1.41 (s, 18H);
13C NMR (101 MHz, CDCl3): d=173.3, 159.6, 153.0, 140.7,
135.8, 129.4, 128.8, 125.2, 120.8, 114.3, 112.4, 56.8, 55.1,
52.19, 34.3, 30.2; HR-MS (ESI): m/z=385.2365, calcd. for
C24H33O4S (M+H)+: 385.2379.
Methyl 2-(3-chlorophenyl)-2-(3,5-di-tert-butyl-4-hydroxy-
phenyl)acetate (3k): Yellow solid; mp 94–968C; 1H NMR
(400 MHz, CDCl3): d=7.32 (s, 1H), 7.24–7.22 (m, 3H), 7.10
(s, 2H), 5.19 (s, 1H), 4.89 (s, 1H), 3.74 (d, J=1.8 Hz, 3H),
1.41 (s, 18H); 13C NMR (101 MHz, CDCl3): d=172.9, 153.2,
141.2, 136.0, 134.2, 129.6, 128.7, 128.3, 127.3, 126.6, 125.1,
56.5, 52.3, 34.4, 30.2; HR-MS (ESI): m/z=389.1862, calcd.
for C23H30ClO3S (M+H)+: 389.1883.
Methyl 2-(3-bromophenyl)-2-(3,5-di-tert-butyl-4-hydroxy-
phenyl)acetate (3l): Yellow solid; mp 95–978C; 1H NMR
(400 MHz, CDCl3): d=7.48 (t, J=1.7 Hz, 1H), 7.38 (ddd,
J=7.9, 1.8, 1.1 Hz, 1H), 7.28 (s, 1H), 7.19 (t, J=7.8 Hz,
1H), 7.10 (s, 2H), 5.19 (s, 1H), 4.88 (s, 1H), 3.74 (s, 3H),
1.41 (s, 18H); 13C NMR (101 MHz, CDCl3): d=173.2, 153.4,
141.7, 136.2, 131.9, 130.5, 130.2, 128.5, 127.4, 125.4, 122.7,
56.7, 52.6, 34.6, 30.5; HR-MS (ESI): m/z=433.1360, calcd.
for C23H30BrO3S (M+H)+: 433.1378.
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(3-fluoro-
phenyl)acetate (3m): Colorless oil; 1H NMR (400 MHz,
CDCl3): d=7.26–7.21 (m, 2H), 7.13 (s, 2H), 7.09–7.03 (m,
2H), 5.21 (s, 1H), 5.20 (s, 1H), 3.75 (s, 3H), 1.43 (s, 18H);
13C NMR (101 MHz, CDCl3): d=172.9, 160.4 (d, J=
247.4 Hz), 153.0 (d, J=23.2 Hz), 136.0, 129.9 (d, J=3.0 Hz),
128.7 (d, J=8.0 Hz), 128.5, 127.2, 125.4, 124.0 (d, J=3.0 Hz),
115.2 (d, J=22.2 Hz), 52.4, 49.6, 34.4, 30.2; HR-MS (ESI):
m/z=373.5587, calcd. for C23H30FO3S (M+H)+: 373.5584.
Methyl 2-(benzo[d][1,3]dioxol-5-yl)-2-(3,5-di-tert-butyl-4-
hydroxyphenyl)acetate (3n): Yellow solid; mp 88–908C;
1H NMR (400 MHz, CDCl3): d=7.11 (s, 2H), 6.83 (d, J=
1.1 Hz, 1H), 6.76–6.72 (m, 2H), 5.93 (s, 2H), 5.15 (s, 1H),
4.84 (s, 1H), 3.72 (s, 3H), 1.41 (s, 18H); 13C NMR
(101 MHz, CDCl3): d=173.5, 153.0, 147.7, 146.6, 135.9,
133.2, 129.1, 125.0, 121.7, 109.1, 108.1, 101.0, 56.4, 52.2, 34.4,
30.2; HR-MS (ESI): m/z=399.2123, calcd. for C24H31O5S
(M+H)+: 399.2093.
Isopropyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-phenyl-
1
N
7.34–7.29 (m, 4H), 7.25–7.21 (m, 1H), 7.11 (s, 2H), 5.13 (s,
1H), 5.06 (dt, J=12.5, 6.3 Hz, 1H), 4.88 (s, 1H), 1.40 (s,
18H), 1.23 (dd, J=6.3, 1.9 Hz, 6H); 13C NMR (101 MHz,
CDCl3): d=172.5, 152.8, 139.5, 135.6, 129.3, 128.5, 128.3,
126.8, 125.2, 68.3, 57.2, 34.4, 30.3, 21.7; HR-MS (ESI): m/z=
383.2584, calcd. for C25H35O3S (M+H)+: 383.2586.
Butyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-phenylace-
tate (3u): Yellow liquid; 1H NMR (400 MHz, CDCl3): d=
7.35–7.24 (m, 5H), 7.12 (s, 2H), 5.13 (s, 1H), 4.91 (s, 1H),
4.13 (t, J=6.7 Hz, 2H), 1.40 (s, 18H), 1.33–1.25 (m, 4H),
0.88 (t, J=7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3): d=
173.1, 152.9, 139.4, 135.7, 129.2, 128.5, 128.4, 126.9, 125.3,
64.8, 57.2, 34.3, 30.6, 30.2, 19.1, 13.6; HR-MS (ESI): m/z=
397.2733, calcd. for C26H37O3S (M+H)+: 397.2742.
2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-N,N-diethyl-2-phe-
nylacetamide (3v): Brown solid; mp 89–918C; 1H NMR
(400 MHz, CDCl3): d=7.23–7.16 (m, 4H), 7.14–7.09 (m,
1H), 6.97 (s, 2H), 5.03 (s, 1H), 4.97 (s, 1H), 3.40 (dt, J=
13.8, 6.9 Hz, 1H), 3.27–3.17 (m, 3H), 1.30 (s, 18H), 1.04 (q,
J=7.0 Hz, 6H); 13C NMR (101 MHz, CDCl3): d=171.3,
152.6, 140.5, 135.6, 130.2, 129.0, 128.2, 126.5, 125.5, 54.3,
Methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(3,5-dime-
1
thylphenyl)acetate (3o): Colorless oil; H NMR (400 MHz,
CDCl3): d=7.14 (s, 2H), 6.95 (s, 2H), 6.89 (s, 1H), 5.14 (s,
1H), 4.84 (s, 1H), 3.72 (s, 3H), 2.29 (s, 6H), 1.41 (s, 18H);
13C NMR (101 MHz, CDCl3): d=173.9, 153.2, 139.2, 138.2,
Adv. Synth. Catal. 0000, 000, 0 – 0
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42.1, 40.5, 34.3, 30.2, 14.5, 12.8; HR-MS (ESI): m/z=
396.2933, calcd. for C26H38NO2S (M+H)+: 396.2956.
To a stirred solution of 100 mg of the substrate in HBr
(45%, 1.5 mL) and AcOH (1 mL), was added DMSO
(0.5 mL) dropwise. The reaction progress was monitored by
TLC. After completion of the reaction, the system was ex-
tracted with ethyl acetate (3ꢂ10 mL). The organic layers
were combined, washed with brine (10 mL), dried with an-
hydrous Na2SO4 and filtered. The filtrate was concentrated
under reduced pressure. The residue was purified by 200–
300 mesh silica gel column chromatography (n-hexane/ethyl
acetate=10:1) to give the brominated product 5 as a slightly
yellow oil; yield: 79 mg (60%).
N,N-Dibutyl-2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-phe-
nylacetamide (3w): Brown liquid; 1H NMR (400 MHz,
CDCl3): d=7.33–7.19 (m, 5H), 7.04 (s, 2H), 5.10 (s, 1H),
5.06 (s, 1H), 3.48–3.41 (m, 1H), 3.25–3.18 (m, 3H), 1.39 (s,
18H), 1.31–1.25 (m, 6H), 0.91 (td, J=7.3, 3.2 Hz, 8H);
13C NMR (101 MHz, CDCl3): d=172.0, 152.9, 140.8, 135.9,
130.5, 129.3, 128.4, 126.8, 125.8, 54.9, 48.1, 46.4, 34.6, 31.7,
30.5, 30.0, 20.5, 20.4, 14.2, 14.10; HR-MS (ESI): m/z=
452.3521, calcd. for C30H46NO2S (M+H)+: 452.3528.
2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-2-phenyl-1-(pyrroli-
din-1-yl)ethan-1-one (3x): Brown solid; mp 118–1198C;
1H NMR (400 MHz, CDCl3): d=7.34–7.27 (m, 4H), 7.23–
7.19 (m, 1H), 7.10 (s, 2H), 5.09 (s, 1H), 4.96 (s, 1H), 3.48
(d, J=30.5 Hz, 4H), 1.86 (d, J=13.0 Hz, 4H), 1.39 (s, 18H);
13C NMR (101 MHz, CDCl3): d=170.63, 152.60, 140.11,
135.42, 129.98, 128.81, 128.30, 126.57, 125.62, 56.23, 46.64,
46.08, 34.25, 30.25, 26.13, 24.23; HR-MS (ESI): m/z=
394.2744, calcd. for C26H36NO2S (M+H)+: 394.2746.
2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-2-phenyl-1-(piperi-
din-1-yl)ethan-1-one (3y): Brown solid; mp 114–1168C;
1H NMR (400 MHz, CDCl3): d=7.52–7.07 (m, 7H), 7.02 (s,
1H), 7.00 (s, 1H), 5.11 (t, J=13.3 Hz, 2H), 3.76–3.62 (m,
2H), 3.53–3.43 (m, 2H), 3.41–3.21 (m, 2H), 1.54–1.51 (m,
2H), 1.39 (s, 18H). 13C NMR (101 MHz, CDCl3): d=170.7,
152.8, 140.7, 135.8, 130.4, 129.2, 128.5, 126.8, 126.0, 55.0,
47.4, 43.6, 34.6, 30.6, 26.1, 25.8, 24.8; HR-MS (ESI): m/z=
408.2897, calcd. for C27H38NO2S (M+H)+: 408.2902.
2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-1-morpholino-2-
phenylethan-1-one (3z): Brown solid; mp 128–1308C;
1H NMR (400 MHz, CDCl3): d=7.34–7.25 (m, 5H), 7.03 (s,
2H), 5.16 (s, 1H), 5.08 (s, 1H), 3.78–3.65 (m, 4H), 3.47–3.35
(m, 4H), 1.42 (s, 18H); 13C NMR (101 MHz, CDCl3): d=
170.9, 152.7, 139.9, 135.8, 129.6, 128.9, 128.4, 126.8, 125.6,
66.8, 66.3, 54.7, 46.5, 42.6, 30.3, 30.2, 29.45, 29.40; HR-MS
(ESI): m/z=401.2691, calcd. for C26H36NO3S (M+H)+:
410.2695.
1-(3,5-Di-tert-butyl-4-hydroxyphenyl)-1-phenylpropan-2-
one (3aa): Colorless oil; 1H NMR (400 MHz, CDCl3): d=
7.37–7.31 (m, 2H), 7.28–7.25 (m, 2H), 7.24 (dd, J=2.9,
1.1 Hz, 1H), 7.03 (s, 2H), 5.18 (s, 1H), 5.04 (s, 1H), 2.25 (s,
3H), 1.42 (s, 18H). 13C NMR (101 MHz, CDCl3): d=207.23,
152.93, 138.91, 135.91, 128.90, 128.61, 128.51, 126.97, 125.59,
65.01, 34.33, 30.23, 29.96. HR-MS (ESI): m/z=373.2154,
calcd. for C23H28F3O2S (MÀH)À: 393.4708.
To a solution of substrate (45 mg, 0.14 mmol) in THF/
H2O (2 mL, 9:1) were added Pd(PPh3)4 (16 mg,
0.014 mmol), phenylboronic acid (34 mg, 0.28 mmol), and
Na2CO3 (22 mg, 0.21 mmol). The resulting mixture was
stirred at 808C for 4 h under N2. Water (10 mL) was added
and the system was extracted with CH2Cl2 (3ꢂ10 mL). The
combined organic layers were dried with anhydrous Na2SO4
and filtered. The filtrate was concentrated under reduced
pressure. The residue was purified by 200–300 mesh silica
gel column chromatography (n-hexane/ethyl acetate=10:1)
to give the coupling product 6 as a colorless oil; yield:
23 mg (52%).
Methyl
2-(4-hydroxyphenyl)-2-phenylacetate
(4):[4d]
1H NMR (400 MHz, CDCl3): d=7.36–7.25 (m, 5H), 7.17 (d,
J=8.4 Hz, 2H), 6.77 (d, J=8.6 Hz, 2H), 5.09 (s, 1H), 4.97
(s, 1H), 3.74 (s, 3H); HR-MS (ESI): m/z=241.0859, calcd.
for C15H13O3S (MÀH)À: 241.0865.
Methyl
2-(3-bromo-4-hydroxyphenyl)-2-phenylacetate
(5):[4d] 1H NMR (400 MHz, CDCl3): d=7.42 (d, J=2.1 Hz,
1H), 7.36–7.26 (m, 5H), 7.16 (dd, J=8.4, 2.1 Hz, 1H), 6.96
(d, J=8.4 Hz, 1H), 5.51 (s, 1H), 4.93 (s, 1H), 3.74 (s, 3H);
HR-MS (ESI): m/z=318.9976, calcd. for C15H12BrO3S
(MÀH)À: 318.9970.
Methyl 2-(6-hydroxy-[1,1’-biphenyl]-3-yl)-2-phenylacetate
1
(6): H NMR (400 MHz, CDCl3): d=7.50–7.40 (m, 5H), 7.33
(d, J=4.5 Hz, 4H), 7.23–7.17 (m, 3H), 6.94 (dd, J=7.5,
1.3 Hz, 1H), 5.25 (s, 1H), 5.00 (s, 1H), 3.75 (s, 3H);
13C NMR (101 MHz, CDCl3): d=173.2, 151.7, 138.8, 136.8,
131.0, 130.4, 129.3, 129.1, 128.6, 128.4, 128.1, 128.0, 127.7,
127.2, 116.0, 56.2, 52.3; HR-MS (ESI): m/z=317.1177, calcd.
for C21H17O3S (MÀH)À: 317.1178.
Acknowledgements
This work was partly supported by the National Nature Sci-
ence Foundation of China (Nos. 21302124 and 21232004),
Shanghai Chenguang Project (No.14CG11), and Science and
Technology Commission of Shanghai Municipality (Nos.
14XD1402300 and 15Z111220016). We thank the Instrumen-
tal Analysis Center of SJTU.
Transformations of 3a
Dry MeNO2 (16 mL, 0.3 mmol) and AlCl3 (40 mg, 0.3 mmol)
were added to flame-dried glass flask under an atmosphere
of nitrogen. The mixture was stirred for 30 min and then the
substrate (70 mg, 0.2 mmol) and toluene (4 mL) were added.
After stirring for 30 min at room temperature, the system
was quenched with water and extracted with ethyl acetate References
(3ꢂ20 mL). The organic layers were combined, washed with
brine (10 mL), dried with anhydrous Na2SO4 and filtered.
The filtrate was concentrated under reduced pressure. The
residue was purified by 200–300 mesh silica gel column
chromatography (n-hexane/ethyl acetate=5:1) to give the
compound 4 as a colorless oil; yield: 40 mg (83%).
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