Gold-Catalyzed Dehydrogenative Cycloisomerization of 1,4-Enyne Esters to 3,5-Disubstituted Phenol Derivatives

Article abstract of DOI:10.1002/adsc.201701068

A method to prepare synthetically important 3,5-disubstituted phenol derivatives that relies on the sequential gold(I)-catalyzed dehydrogenative cycloisomerization of 1,4-enyne esters in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) or N-fluorobenzenesulfonimide (NFSI) is described. The synthetic versatility of the methodology was exemplified by a gram-scale reaction of one example, the ease to realize subsequent functional transformations of an adduct, and the application of the method to the synthesis of the bioactive molecule LUF5771. (Figure presented.).

Full text of DOI:10.1002/adsc.201701068

Title: Gold Catalyzed Dehydrogenative Cycloisomerization of 1,4-
Enyne Esters to 3,5-Disubstituted Phenol Derivatives
Authors: Cuili Chen, Xianxiao Chen, Xiaoxiang Zhang, Shifa Wang,
Weidong Rao, and Philip Chan
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201701068
Link to VoR: http://dx.doi.org/10.1002/adsc.201701068

10.1002/adsc.201701068
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Gold Catalyzed Dehydrogenative Cycloisomerization of 1,4-
Enyne Esters to 3,5-Disubstituted Phenol Derivatives
Cuili Chen,a Xianxiao Chen,a Xiaoxiang Zhang,a Shifa Wang,a Weidong Rao,a* and
Philip Wai Hong Chanb,c*
a
Jiangsu Key Laboratory of Biomass-based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing
Forestry University, Nanjing 210037, China. e-mail: weidong@njfu.edu.cn
School of Chemistry, Monash University, Clayton, Victoria 3800, Australia. e-mail: phil.chan@monash.edu
Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom. e-mail:
b
c
p.w.h.chan@warwick.ac.uk
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A method to prepare synthetically important 3,5-
disubstituted phenol derivatives that relies on the sequential
gold(I)-catalyzed dehydrogenative cycloisomerization of
1,4-enyne esters in the presence of 2,3-dichloro-5,6-
Keywords: 1,4-enyne esters; 3,5-disubstituted phenols;
dehydrogenative cycloisomerization; gold; homogenous
catalysis
dicyanobenzoquinone
(DDQ)
or
N-
fluorobenzenesulfonimide (NFSI) is described. The synthetic
versatility of the methodology was exemplified by a gram-
scale reaction of one example, the ease to realize subsequent
functional transformations of an adduct, and the application
of the method to the synthesis of the bioactive molecule
LUF5771.
O
Introduction
O
O
O
N
H
COOH
Phenols are important core structures and precursors
for the construction of a wide variety of bioactive
natural products, pharmaceutical compounds and
polymers.[1–5] Representative of this are members of
the family with a 3,5-disubstitution pattern that are
found in a myriad of pharmacologically interesting
compounds such as those illustrated in Figure 1.[2–5]
For this reason, the development of synthetic
approaches to construct 3,5-disubstituted phenols
with selective control of substitution patterns
efficiently is of considerable current interest. The
regiospecific preparation of 3,5-disubstituted phenols
via traditional electrophilic aromatic substitution of
phenols, however, can be synthetically challenging
due to the well-known strong o,p-directing effect of
the hydroxyl functional group. Consequently, this has
led to the establishment of a number of elegant
synthetic methodologies in recent years.[6–11] Included
in this have been synthetic approaches that have
relied on the oxidative dehydrogenation,[6] base-
O
O
COOH
Ph
Ph
S
LUF5771
LH-receptor antagonist
RO510576
LTB4 receptor antagonist
F
OH
O
NH
N
Me
Ph
O
O
COOH
CF3
BRD4(1) inhibitor
g-secretase inhibitor
Figure 1. Selected examples of bioactive 3,5-disubstituted
phenol derivatives.[2–5]
catalyzed annulation[10] of nonaromatic precursors.
The transition-metal catalyzed template assisted C–H
bond meta-functionalization of phenols has also been
recently disclosed.[11] Despite these advances, there
remains a need to realize new synthetic methods for
the efficient preparation of 3,5-disubstituted phenols
from readily accessible substrates under mild and
practical conditions.
promoted
eliminative
aromatization,[7]
[3+3]
annulation,[8] ring- closing olefin metathesis
cascade,[9] and gold(I)-
1
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10.1002/adsc.201701068
Advanced Synthesis & Catalysis
Gold-mediated cycloisomerization of 1,n-enynes
in1,2-dichloroethane at 80 °C for 12 h (entry 1).
More-
and 1,n-enyne esters has become one of the most
atom-economical and versatile synthetic strategies to
rapidly increase molecular complexity in a single
operation.[12–18] A recent notable example is the
gold(I)-catalyzed cycloisomerization of 1,4-enyne
acetates to bicyclo[3.1.0]hexenes (Scheme 1a).[15]
Following this pioneering work, we reported the
Table 1. Optimization of the reaction conditions[a]
OPNB
OPNB
OPNB
[Au] (2 mol%)
+
Ph
[O], (CH2Cl)2, 80 o
C
Ph
Me
Me
Ph
Me
2a
4a
1a
R1 R1
gold(I)-catalyzed
tandem
1,3-acyloxy
SbF6
migration/double cyclopropanation of 1-ene-4,9-
diyne and 1-ene-4,10-diyne esters to the
architecturally challenging tetracyclodecenes and
tetracycloundecenes via the bicyclic intermediate
(Scheme 1a).[16] Inspired by these studies and as part
of ongoing efforts in the field,[17] we were drawn to
the potential reactivity of 1,4-enyne esters in the
presence of an oxidant such as DDQ or NFSI
(Scheme 1b).[18] We reasoned that such
bicyclo[3.1.0]hexene adducts generated from gold(I)-
catalyzed cycloisomerization of the substrate might
be susceptible to a dehydrogenative/ring-opening
pathway due to the oxidant to provide the 3,5-
disubstituted aromatic ring system. Herein, we
describe the details of this chemistry that provides an
expedient and regioselective approach to the
synthetically important phenolic ester derivative in
good to excellent yields. The synthetic versatility of
the methodology by demonstrating the ability to carry
out a gram-scale reaction of one example and the ease
to further functionalize the adduct along with the
preparation of the LH-receptor antagonist LUF5771
in two steps is also presented.[2]
Ar
N
N Ar
P
Au NCMe
R2
O
N
Au
NTf2
R2
Cl Au
Cl
O
R2
A: R1 = t-Bu, R2 = H
B: R1 = Cy, R2 = iPr
C: Ar = 2,6-i-Pr2C6H3
D
O
Cl
NC
Cl
Cl
PhO2S
SO2Ph
N
N
F
2BF4
N
NC
F
O
NFSI
SelectFluor
DDQ
Yield [%]
Reaction
Time [h]
Entry Catalyst
[O]
2a
-
4a
82
-
1
NFSI
12
24
A
A
A
A
A
A
A
B
C
b
2
-
99
-
3
SelectFluor 120
66
99
87
99
97
85
97
80
82
4
DDQ
DDQ
DDQ
DDQ
DDQ
DDQ
4
-
5[c]
6[d]
7[d,e]
8[d]
9[d]
10[d]
11[d]
120
4
-
-
4
-
3
-
16
3
-
(a) previous works:
PPh3AuNTf2 DDQ
-
OCOMe
H
OCOR1
R3
Ar/Het
[AuI]
R1OCO
R2
R3
DDQ
24
-
D
R2
refs 15 and 16
R3
[a]All reactions were performed using 0.3 mmol of 1a, 2
mol % of gold(I) or gold(III) catalyst and 0.6 mmol of
oxidant in (CH2Cl)2 at 80 °C. [b]Reaction carried out in the
absence of an oxidant. [c]Reaction carried out at room
temperature. [d]Reaction performed with 0.36 mmol of
DDQ. [e]Reaction performed in toluene.
( )n-1
1
2
3
for R2
-(CH )
=
2
Ar/Het
n
(b) this work:
OCOR1
[AuI]
R1OCO
R2
R3
DDQ or NFSI
(CH2Cl)2, 80 o
R2
C
R3
1
4
Scheme 1. Gold(I)-catalyzed reactivities of 1,4-enyne
esters
over, a control experiment in the absence of NFSI
was found to give the bicyclo[3.1.0]hexene adduct 2a
in 99% yield (entry 2). These promising results
encouraged us to next examine other oxidants, which
showed replacing NFSI with SelectFluor led to a
lower product yield of 66% and the need of a reaction
time of 5 days (entry 3). Changing the oxidant to
DDQ, on the other hand, was found to increase the
yield of 4a to 99% after 4 h (entry 4). Repeating these
reaction conditions at room temperature proceeded
slowly and required a reaction time of 5 days to
furnish a product yield of 87% (entry 5). Our
investigations subsequently found a product yield
99% could also be achieved under the reaction
conditions described in entry 4 and at a lower loading
of DDQ of 1.2 equiv (entry 6). Under these latter
conditions, a comparable product yield of 97% was
Results and Discussion
The 1,4-enyne esters studied in this work were
prepared from the corresponding aldehyde or
carboxylic acid starting materials in three to four
steps following literature procedures.[19] By choosing
1a as the model substrate, we commenced our studies
by examining the gold-catalyzed dehydrogenative
rearrangement of the 1,4-enyne ester in the presence
of an oxidant to establish the optimum reaction
conditions (Table 1). This initially revealed that the
anticipated phenol derivative 4a could be obtained in
82% yield on treating the substrate with 2 mol % of
gold(I) phosphine catalyst A[20a] and NFSI (2 equiv)
2
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10.1002/adsc.201701068
Advanced Synthesis & Catalysis
obtained when the reaction was conducted in toluene
instead of 1,2-dichloroethane as the solvent (entry 7).
Likewise, control reactions with the more sterically
crowded Au(I) complex B,[20b] NHC−Au(I) (NHC =
biological applications,[2,21,22] the symmetrical 1,4-
enyne ester 1x was next examined. Under the reaction
conditions of Method A at a catalyst loading of 4 mol
% and 2.4 equiv of DDQ, this gave the expected
terphenyl 4x in 53% yield. The 1,4-enyne ester 1y,
which was prepared from the bioactive natural
product betulin, was additionally shown to undergo
dehydrogenative cycloisomerization to afford 4y in
an excellent yield of 94%.
N-heterocyclic
Ph3PAuNTf2
carbene)
complex
C,[20c]
[20c]
or gold(III) complex D[20d] in place
of A as the catalyst provided 4a in 80−97% yield
(entries 8−11). On the basis of the above results,
reaction of 1a in the presence of 2 mol % of Au(I)
complex A as the catalyst and 1.2 equiv of DDQ
(Method A) or 2 equiv of NFSI (Method B) as the
oxidant in 1,2-dichloroethane at 80 °C for 4 or 12 h
were deemed to provide the optimum conditions.
OR1
OR1
Method A
R2
or Method B
R3
R2
R3
1
4
OPNB
With the optimal conditions in hand, we next
evaluated the generality of the present procedure with
a series of 1,4-enyne esters, and the results are
summarized in Scheme 2. Overall, the Au(I) complex
A-catalyzed reaction conditions were found to be
broad, providing a diverse set of 3,5-disubstituted
phenol derivatives containing a variety of substitution
patterns in 46–99% yield from the corresponding
substrates 1a–y. Under the conditions of Method A,
the introduction of an acyl (1b) instead of a p-
nitrobenzoyl (PNB) migrating group was found to
proceed well, producing the corresponding 3,5-
disubstituted phenol 4b in 74% yield. Similarly, the
reaction of substrates bearing a phenyl ether (1c),
malonate (1e) and a tertiary sulfonamide (1f) group at
the R3 position were shown to give the corresponding
3,5-disubstituted phenols 4c and 4e–f in 72–97%
yield. The dehydrogenative rearrangement of 1d with
a pendant methyl carbonate group was found to
proceed best under the conditions of Method B,
affording 4d as well as 4a as a byproduct in
respective yields of 46 and 37%. The presence of an
electron-donating (1g,l and 1m) or electron-
withdrawing (1h–k) substituent on the phenyl group
at the R2 position of the substrate was also found to
have no appreciable effect on the outcome of the
reaction. In these experiments, the corresponding
phenol products 4g–m were obtained in excellent
yields of 84–98% under the conditions of Method A.
Similarly, substrates containing a naphthyl (1n–o), or
indolyl (1p) motif at the same position were well
tolerated, furnishing the corresponding phenol
derivatives 4n–p in 62-99% yield. Under the reaction
conditions of Method B, the diphenyl substituted
substrate 1q gave the corresponding phenolic ester
adduct 4q in 68% yield. Gratifyingly, the starting
esters bearing an aliphatic substituent at both the R2
and R3 positions, as in 1r–w, were also converted to
the corresponding phenols 4r–w in 60-77% yield
using either Method A or B albeit requiring longer
reaction times. Due to the importance of terphenyls
and their derivatives in the fields of optical and
conductive materials, as well as a wide range of
OAc
OPNB
COOEt
OR
Ph
COOEt
Me
Ph
Me
Ph
A: 4b (74%, 10 h)
A: 4e (73%, 24 h)
A: 4c, R = Ph (72%, 6 h)
B: 4d, R = Ac (46%, 12 h)[a]
OPNB
OPNB
OAc
Me
Me
NTsPh
A: 4f (97%, 5 h)
Ph
R
R
A: 4g, R = Me (98%, 4 h) A: 4j, R = Br (92%, 10 h)
A: 4h, R = Br (96%, 8 h) A: 4k, R = I (87%, 28 h)
A: 4i, R = Ph (91%, 5 h)
OPNB
OPNB
OPNB
MeO
MeO
O
O
Me
Me
Me
Br
Br
A: 4l (84%, 10 h)
A: 4m (85%, 8 h)
A: 4n (99%, 12 h)
OPNB
OPNB
OPNB
Me
Me
Ph
Ph
N
Ts
A: 4o (91%, 12 h)
A: 4p (62%, 10 h)
B: 4q (68%, 12 h)
OPNB
OPNB
OPNB
Et
Me
Me
R
Me
( )n
Et
A: 4u (74%, 72h)
A: 4r, n = 1 (77%, 6 h)
B: 4s, n = 3 (60%, 96 h)
B: 4t, n = 4 (61%, 36 h)
A: 4v, R = Bn (64%, 48 h)
B: 4w, R = nBu (60%, 24 h)
AcO
Ph
AcO
OAc
Me
Me
AcO
Me
Me
Me
OAc
Me
A: 4y (94%, 12h)
Me
A: 4x (53%, 72 h)[b]
Scheme
2.
Gold(I)-catalyzed
dehydrogenative
cycloisomerization of 1,4-enyne esters 1b–y. All reaction
performed following: Method A: reaction performed with
1 (0.3 mmol), Au(I) complex A (2 mol%) and DDQ (0.36
mmol) in (CH2Cl)2 at 80 °C; or Method B: reaction
performed with 1 (0.3 mmol), Au(I) complex A (2 mol%)
and NFSI (0.6 mmol) in (CH2Cl)2 at 80 °C. Values in
parentheses denote isolated product yields and reaction
times. [a]Compound 4a was isolated in 37% yield.
[b]Reaction performed 4 mol % of Au(I) complex A and
with 2.4 equiv of DDQ.
3
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10.1002/adsc.201701068
Advanced Synthesis & Catalysis
Scheme 4. Synthesis of the LH-Receptor antagonist
To demonstrate the scalability and practicality of
LUF5771.[2,6b,8c]
the present protocol, a gram-scale reaction of 1a (4
mmol, 1.34 g) was carried out in the presence of 1
mol % gold(I) catalyst A. Under the reaction
conditions described in Scheme 3, this provided 4a in
96% yield (1.28 g). Accordingly, subjecting the
adduct to 5 mol% benzoyl peroxide (BPO) and to N-
bromosuccinimide (NBS, 1.1 equiv) in carbon
tetrachloride at 80 °C for 15 h afforded the benzylic
bromide 5 (1.05 g) in 66% yield. Subsequently, the
synthetic versatility of 5 was demonstrated by its
successfully conversion to the corresponding 3,5-
disubstituted phenols with a range of functional
groups (Scheme 3). By applying corresponding
nucleophilic substitution reaction conditions, this
included compounds with an azide (6), nitrate (7),
selenocyanate (8) and thioether (9) motif in yields of
65–97%.
To gain an insight into the reaction mechanism, a
number of control experiments were performed
(Table 2 and Scheme 5). Our initial premise reasoned
that the bicyclo[3.1.0]hexane adduct obtained from
the gold catalysis step might be susceptible to a ring-
opening/dehydrogenation process in the presence of
an oxidant. With this mind, we first examined the
reaction of 2a in the presence and absence of the
gold(I) catalyst A (2 mol %), 1.2 equiv of DDQ and
(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO, 2
equiv) under the conditions described in Table 2,
entries 1 and 4. These tests was found to result in no
reaction and, in both cases, the recovery of the
starting material in 99% yield. Initially, this led us to
consider a reaction mechanism involving the possible
formation of a radical species as well as the bicyclic
adduct as a key intermediate.[23] This was further
supported by performing the reaction again for a third
time in the absence of TEMPO and obtaining 4a in
99% yield within 4 h (entry 2). Intriguingly, the
transformation proceeded very slowly on repeating
the reaction for a fourth time in the absence of gold
catalyst A, requiring 5 days to furnish the product in
97% yield (entry 5). A similar outcome was observed
when these latter set of two control experiments with
2a was conducted with NFSI as the oxidant (entries 3
and 6). The possibility of an alternative competing
pathway involving a hydride abstraction step,
however, could not be ruled out based on findings
obtained from control reactions of 2a with BF3Et2O
or CuI in place of A as the catalyst.[24] Under the
reaction conditions detailed in entries 7 and 8, these
experiments gave the phenolic ester product in
respective yields of 98 and 82%. Consistent with this
are our findings in a control experiment treating 2a to
the conditions described in Scheme 5, which gave
compound 10 in 21% yield and
OPNB
OPNB
OPNB
A(1 mol%)
BPO (5 mol%)
Ph
DDQ (1.2 equiv)
(CH2Cl)2, 80 oC, 4 h
NBS (1.1 equiv)
CCl4, 80 oC, 15 h
Me
Ph
Me
Ph
Br
5, 1.05 g
1a, 4 mmol, 1.34 g
4a, 1.28 g
96% yield
66% yield
1) AgNO3 (1.5 equiv)
EtOAc, 70oC, 24 h
OH
OH
NaN3 (4 equiv)
2) K2CO3 (0.5 equiv)
MeOH, rt, 4 h
MeOH, rt, 24 h
N3
ONO2
Ph
Ph
OPNB
6, 91% yield
7, 65% yield
Br
Ph
5
1) KSeCN (1.5 equiv)
THF, 70oC, 24 h
p-thioresol (2 equiv)
NaOH (2 equiv)
OH
OH
2) K2CO3 (0.5 eq)
MeOH, rt, 4 h
EtOH, rt, 2 h
SeCN
8, 97% yield
Sp-tol
9, 95% yield
Ph
Ph
Scheme 3. Scale-up experiments and synthetic
transformations.
The synthetic application of the methodology was
next demonstrated by the transformation of 4q to the
O-terphenylcarbamate LUF5771, a novel inhibitor of
the human luteinizing hormone receptor.[2,6b,g,8c] As
shown in Scheme 4, methanolysis of the 3,5-
diphenyl-substituted substrate was achieved by
subjecting it to K2CO3 in methanol at room
temperature for 2 h. This was followed by treatment
Table 2. Control experiments with 2a[a]
OPNB
OPNB
catalyst (2 mol%)
of
the
resultant
crude
mixture
with
cyclopentylisocyanate to furnish LUF5771 in 95%
yield over two steps. This is comparable product
yields obtained by previously reported synthetic
methods to prepare the LH-receptor antagonist from a
cyclic or acyclic precursor.[2,6b,8c]
Ph
[O], (CH2Cl)2
80 oC
Me
Ph
Me
2a
4a
Reaction
[h]
Time
Entry Catalyst
[O]
Yield [%][b]
[d]
1[c]
2
DDQ
DDQ
NFSI
DDQ
DDQ
NFSI
24
4
-
A
A
A
-
O
1) K2CO3 (50 mol%)
OPNB
99
MeOH, rt, 2 h
O
N
H
3
4[c]
12
24
120
72
83
[d]
2)
-
Ph
Ph
NCO
Ph
Ph
5
-
97
81
Et3N, CH2Cl2, rt
4q
LUF 5771, 95% yield
6
-
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701068
Advanced Synthesis & Catalysis
NC
CN
Cl
7
8
DDQ
DDQ
6
98
82
BF3Et2O
[AuI] + 2 DDQ
O
O
[AuIII
]
CuI
24
[a]All reactions were performed using 0.2 mmol of 2a, in
the presence or absence of 2 mol % of catalyst, DDQ (0.24
mmol) or NFSI (0.4 mmol) in (CH2Cl)2 at 80 °C. [b]Isolated
product yield. [c]Reaction conducted in the presence of
TEMPO (2 equiv). [d]Compound 2a was recovered in 99%
yield.
2
Cl
[AuIII
]
Ph
OPNB
[AuI]
EO
O
OPNB
OPNB
Me
NC
NC
Cl
2
+
refs 15
and 16
HAT
Ph
Ph
Me
Cl
2
pathway a
OH
Me
EOH
1a
2a
Ia
O
[AuI]
SET
[AuI]
NC
NC
Cl
O
OPNB
Me
as a 1.1:1 mixture of regioisomers along with the
substrate and 4a in 31 and 19% yield,
respectively.[25,26]
Cl
NC
Cl
Cl
2
2
+
O
pathway b
Ph
NC
NC
Cl
CN
OH
DDQH–
IIa
HO
O
[AuI]
OPNB
ring-open
Cl
FOH
FOH or
DDQH– DDQH2
[AuI] or
ring-
open
PNBO
OPNB
OPNB
Me
Ph
Me
OPNB
Me
4a, 19% yield
A (2 mol%)
–H+
Ph
Ph
Me
Ph
Me
OPNB
OPNB
Me
Ph
DDQ (1.2 equiv)
TMSN3 (10 equiv)
(CH2Cl)2, 80 oC, 24 h
IIa
IIIa
4a
N3
2a
Ph
Me
Ph
Scheme 6. Proposed mechanism for Au(I)-catalyzed
dehydrogenative cycloisomerization of 1,4-enyne esters in
the presence of DDQ represented by 1a.
N3
10, 21% yield, 1.1:1 mixture of regioisomers
Scheme 5. Control experiment with 2a in the presence of
TMSN3.
carboradical species Ia.[23] The gold(III) adduct EOH
also formed in this step may trigger further oxidation
of Ia via a single-electron transfer (SET) event. This
would give the allylic cation IIa and regenerate the
Au(I) catalyst along with the two equivalents of
DDQH–, which would yield DDQH2 on protonation.
Alternatively, as shown in pathway b in Scheme 6,
the bicyclic carbocation intermediate could be
generated as a result of hydride abstraction of 2a by
DDQ.[24] The oxidizing ability of the quinone may be
enhanced by the coordination of the Lewis acid to the
oxygen center of the oxidant. Protodeauration of the
ensuing gold(I) species FOH would return the Au(I)
catalyst and DDQH2. Subsequent electrophilic ring-
opening of IIa by either of these two possible routes
might furnish the carbocationic species IIIa.
Aromatization of this Wheland-type intermediate
would then deliver the 3,5-disubstituted phenolic
product 4a.
On the basis of the above observations, a tentative
mechanism for the present Au(I)-catalyzed 1,4-enyne
ester dehydrogenative cycloisomerization reaction in
the presence of DDQ is illustrated in Scheme 6. With
1a as a representative example, this initially involves
Au(I)-catalyzed
tandem
[3,3]-rearrangement/
cyclopropanation to produce the bicyclo[3.1.0]hexene
2a.[15,16] At this juncture, it is thought that the
transformation of the bicyclic adduct to the phenolic
ester product could proceed through possible
competitive pathways
speculative, pathway a might begin with oxidation of
the gold(I) catalyst by two molecules of DDQ to
provide the gold(III) species EO.[27,28] As
consequence, this could lead to two molecules of the
bicyclic adduct to undergo a hydrogen atom transfer
(HAT) process with the in situ formed Au(III)
complex to afford the
a
or b. While highly
a
Conclusion
In summary, we have developed a strategy for the
assembly of a wide variety of 3,5-disubstituted
phenol
derivatives
from
gold(I)-catalyzed
dehydrogenative cycloisomerization of 1,4-enyne
esters in the presence of DDQ or NFSI. The utility of
the present method was demonstrated by the scale-up
conversion of one example followed by its
transformation to the corresponding 3,5-disubstituted
phenols with a range of functionalities, which are
ubiquitous building blocks in a myriad of bioactive
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701068
Advanced Synthesis & Catalysis
compounds.[2–5] The synthetic application of this
approach was also exemplified by modifying one
adduct obtained to the biologically active molecule
LUF5771, a potent allosteric inhibitor of the human
luteinizing hormone receptor.[2] Further exploration
of the synthetic applications of the present reaction
are currently underway and will be reported in due
course.
(dt, 3H, J = 15.1, 4.1 Hz), 7.28-7.37 (m, 3H), 7.40 (m, 1H),
7.42-7.50 (m, 3H), 7.62 (dd, 3H, J = 5.6, 3.8 Hz), 8.34-
8.45 (m, 4H). 13C NMR (CDCl3, 150 MHz): δ 69.3, 114.9,
119.0, 119.7, 121.3, 123.8, 123.9, 127.3, 128.0, 128.9,
129.6, 131.4, 134.9, 139.7, 139.8, 143.4, 151.0, 151.2,
158.6, 163.3. IR (KBr) ν: 3461, 3112, 1742, 1518, 1259,
1078, 715 cm-1. HRMS (ESI) calcd for C26H19NO5Na
[M+Na]+: 448.1161, found: 448.1161.
5-(acetoxymethyl)-[1,1'-biphenyl]-3-yl 4-nitrobenzoate
(4d):
1
Yield: 54 mg, 46% (Method B). Pale-yellow oil. H NMR
(CDCl3, 400 MHz): δ 2.14 (s, 3H), 5.21 (s, 2H), 7.24 (s,
1H), 7.35-7.49 (m, 4H), 7.53 (s, 1H), 7.56-7.64 (m, 2H),
8.33-8.45 (m, 4H). 13C NMR (CDCl3, 100 MHz): δ 21.0,
65.6, 119.8, 120.0, 123.8, 124.9, 127.2, 128.1, 129.0, 131.4,
134.8, 138.3, 139.6, 143.5, 151.0, 163.3, 170.8. IR (neat)
ν: 3460, 3113, 1742, 1526, 1262, 1081, 716, 544 cm-1.
HRMS (ESI) calcd for C22H17NO6Na [M+Na]+: 414.0954,
found: 414.0959.
Experimental Section
Representative Experimental Procedure for Gold(I)
Complex
A
Catalyzed
Dehydrogenative
Cycloisomerization of 1,4-Enyne Esters (Method A with
DDQ as the Oxidant):
To a solution of 1,4-enyne ester 1 (0.3 mmol) and DDQ
(0.36 mmol) in 1,2-dichloroethane (6 mL) was added
gold(I) catalyst A (6 μmol) under an argon atmosphere.
The reaction mixture was stirred at 80 °C for 4 h. Upon
completion, the reaction mixture was cooled to room
temperature and filtered through Celite, washed with
CH2Cl2 (10 mL) and the solvent was removed under
reduced pressure. Purification by flash column
2-methyl-2-((5-((4-nitrobenzoyl)oxy)-[1,1'-biphenyl]-3-
yl)methyl)malonate (4e):
Yield: 110.7 mg, 73% (Method A). Colorless solid; mp 75-
1
76 °C. H NMR (CDCl3, 600 MHz): δ 1.25 (t, J = 7.1 Hz,
6H), 1.43 (s, 3H), 3.33 (s, 2H), 4.21 (q, 4H, J = 7.1 Hz),
7.04 (s, 1H), 7.31 (s, 1H), 7.32 (s, 1H),7.37 (t, 1H, J = 7.4
Hz), 7.44 (t, 2H, J = 7.6 Hz), 7.52-7.60 (m, 2H), 8.32-8.44
(m, 4H). 13C NMR (CDCl3, 150 MHz): δ 14.0, 20.0, 41.1,
54.9, 61.5, 118.7, 122.0, 123.8, 127.2, 127.9, 128.9, 131.3,
135.0, 142.8, 150.7, 151.0, 163.2, 171.8. IR (KBr) ν: 3413,
3116,1736, 1613, 1524, 1267, 1097, 711 cm-1. HRMS
(ESI) calcd for C28H28NO8 [M+H]+: 506.1815, found:
506.1822.
chromatography
on
silica
gel
(petroleum
ether:EtOAc:CH2Cl2 = 50:1:1 as eluent) to give the title
compound.
Representative Experimental Procedure for Gold(I)
Complex
A
Catalyzed
Dehydrogenative
Cycloisomerization of 1,4-Enyne Esters (Method B with
NFSI as the Oxidant):
5-(((4-methyl-N-phenylphenyl)sulfonamido)methyl)-
[1,1'-biphenyl]-3-yl acetate (4f):
To a solution of 1,4-enyne ester 1 (0.3 mmol) and NFSI
(0.6 mmol) in 1,2-dichloroethane (6 mL) was added
gold(I) catalyst A (6 μmol) under an argon atmosphere.
The reaction mixture was stirred at 80 °C for 12 h. Upon
completion, the reaction mixture was cooled to room
temperature and the solvent was removed under reduced
pressure. Purification by flash column chromatography on
silica gel (petroleum ether:EtOAc:CH2Cl2 = 50:1:1 as
eluent) to give title compound.
1
Yield: 137.2 mg, 97% (Method A). Pale-yellow oil. H
NMR (CDCl3, 600 MHz): δ 2.29 (s, 3H), 2.44 (s, 3H), 4.78
(s, 2H), 7.00-7.05 (m, 3H), 7.15 (t, 1H, J = 1.8 Hz), 7.22-
7.25 (m, 3H), 7.28 (d, 3H, J = 1.4 Hz), 7.32-7.34 (m, 1H),
7.40 (t, 2H, J = 7.3 Hz), 7.42-7.46 (m, 2H), 7.56 (d, 2H, J
= 8.2 Hz). 13C NMR (CDCl3, 150 MHz): δ 21.2, 21.6, 54.6,
119.6, 120.5, 124.6, 127.1, 127.8, 128.1, 128.8, 129.0,
129.1, 129.6, 135.5, 138.2, 139.0, 139.7, 142.7, 143.7,
151.1, 169.5. IR (neat) ν: 3131, 1766, 1595, 1400, 1206,
1163, 696 cm-1. HRMS (ESI) calcd for C28H25NO4SNa
[M+Na]+: 494.1402, found: 494.1402.
5-methyl-[1,1'-biphenyl]-3-yl 4-nitrobenzoate (4a):
Yield: 99 mg, 99% (Method A). Colorless solid; mp 101-
1
103 °C. H NMR (CDCl3, 400 MHz): δ 2.50 (s, 3H), 7.07
(s, 1H), 7.29 (d, 1H, J = 1.9 Hz), 7.38-7.42 (m, 2H), 7.46-
7.49 (m, 2H), 7.62-7.64 (m, 2H), 8.37-8.44 (m, 4H). 13C
NMR (CDCl3, 100 MHz): δ 21.6, 117.3, 120.8, 123.8,
126.1, 127.2, 127.8, 128.9, 131.3, 135.0, 140.1, 140.2,
142.9, 150.8, 150.9, 163.5. IR (KBr) ν: 3109, 1735, 1528,
1266, 1085, 713 cm-1. HRMS (ESI) calcd for
C20H15NO4Na [M+Na]+: 356.0899, found: 356.0894.
4',5-dimethyl-[1,1'-biphenyl]-3-yl 4-nitrobenzoate (4g):
Yield: 102 mg, 98% (Method A). Pale-yellow solid; mp
1
124-126 °C. H NMR (CDCl3, 600 MHz): δ 2.43 (s, 3H),
2.49 (s, 3H), 7.04 (s, 1H), 7.28 (d, 3H, J = 8.4 Hz,), 7.37 (s,
1H), 7.52 (d, 2H, J = 8.1 Hz), 8.37-8.43 (m, 4H). 13C NMR
(CDCl3, 150 MHz): δ 21.1, 21.5, 117.0, 120.5, 123.7,
125.9, 127.0, 129.6, 131.3, 135.1, 137.2, 137.6, 140.1,
142.8, 150.9, 150.9, 163.5. IR (KBr) ν: 3458, 3117, 1739,
1523, 1349, 1262, 1085, 711 cm-1. HRMS (ESI) calcd for
C21H17NO4Na [M+Na]+: 370.1055, found: 370.1049.
5-methyl-[1,1'-biphenyl]-3-yl acetate (4b):
1
Yield: 50.2 mg, 74% (Method A). Pale-yellow oil. H
NMR (CDCl3, 400 MHz): δ 2.33 (s, 3H), 2.43 (s, 3H), 6.91
(s, 1H), 7.12 (s, 1H), 7.29 (s, 1H), 7.35 (t, 1H, J = 7.3 Hz),
7.43 (t, 2H, J = 7.5 Hz), 7.57 (d, 2H, J = 7.6 Hz). 13C NMR
(CDCl3, 100 MHz): δ 21.2, 21.5, 117.5, 121.0, 125.6,
127.2, 127.6, 128.8, 139.9, 140.4, 142.6, 151.0, 169.6. IR
(neat) ν: 3034, 2921, 1769, 1614, 1208, 1019, 762 cm-1.
HRMS (ESI) calcd for C15H15O2 [M+H]+: 227.1072, found:
227.1077.
4'-bromo-5-methyl-[1,1'-biphenyl]-3-yl 4-nitrobenzoate
(4h):
Yield: 108.7 mg, 96% (Method A). Colorless solid; mp
1
105-107 °C. H NMR (CDCl3, 600 MHz): δ 2.47 (s, 3H),
7.06 (s, 1H), 7.22 (t, 1H, J = 1.5 Hz), 7.31 (d, 1H, J = 0.5
Hz), 7.42-7.48 (m, 2H), 7.52-7.60 (m, 2H), 8.32-8.42 (m,
4H). 13C NMR (CDCl3, 150 MHz): δ 21.5, 117.1, 121.2,
122.1, 123.8, 125.8, 128.8, 131.3, 132.0, 134.9, 139.0,
140.5, 141.6, 151.0, 163.4. IR (KBr) ν: 3450, 3166, 1736,
1527, 1265, 1091, 806, 712 cm-1. HRMS (ESI) calcd for
C20H14NO479BrNa [M+Na]+: 434.0004, found: 434.0007.
5-(phenoxymethyl)-[1,1'-biphenyl]-3-yl 4-nitrobenzoate
(4c):
Yield: 92 mg, 72% (Method A). Yellow solid; mp 80-
1
82 °C. H NMR (CDCl3, 600 MHz): δ 5.18 (s, 2H), 7.01
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701068
Advanced Synthesis & Catalysis
5-methyl-[1,1':4',1''-terphenyl]-3-yl 4-nitrobenzoate (4i): 135.0, 139.1, 139.8, 142.3, 150.4, 150.9, 163.4; IR (neat)
ν: 3114, 1741, 1526, 1397, 1263, 1082, 778, 714 cm-1.
HRMS (ESI) calcd for C24H17NO4Na [M+Na]+: 406.1055,
Yield: 111.8 mg, 91% (Method A). Yellow solid; mp 168-
1
found: 406.1055.
171 °C. H NMR (CDCl3, 400 MHz): δ 2.49 (s, 3H), 7.06
(s, 1H), 7.31 (s, 1H), 7.34-7.40 (m, 1H), 7.42 (s, 1H), 7.47
(t, J = 7.6 Hz, 2H), 7.61-7.72 (m, 6H), 8.34-8.44 (m, 4H).
13C NMR (CDCl3, 100 MHz): δ 21.6, 117.1, 120.9, 123.8,
125.9, 127.1, 127.5, 127.6, 128.9, 131.3, 135.0, 139.0,
140.3, 140.5, 140.6, 142.4, 150.9, 163.5. IR (KBr) ν: 3116,
1729, 1525, 1261, 840, 712 cm-1. HRMS (ESI) calcd for
C26H20NO4 [M+H]+: 410.1392, found: 410.1392.
3-methyl-5-(naphthalen-2-yl)phenyl
(4o):
4-nitrobenzoate
Yield: 104.7 mg, 91% (Method A). Pale-yellow solid; mp
1
154-156 °C. H NMR (CDCl3, 600 MHz): δ 2.51 (s, 3H),
7.08 (s, 1H), 7.40 (s, 1H), 7.47-7.55 (m, 3H), 7.74 (dd, 1H,
J = 8.5, 1.8 Hz), 7.85-7.95 (m, 3H), 8.06 (d, 1H, J = 1.1
Hz), 8.32-8.44 (m, 4H). 13C NMR (CDCl3, 150 MHz): δ
21.6, 117.5, 120.9, 123.8, 125.4, 126.0, 126.2, 126.3, 126.5,
127.7, 128.3, 128.6, 131.3, 132.8, 133.6, 135.0, 137.4,
140.3, 142.8, 150.9, 151.0, 163.5. IR (KBr) ν: 3125, 1741,
1523, 1256, 1080, 713 cm-1. HRMS (ESI) calcd for
C24H17NO4Na [M+Na]+: 406.1055, found: 406.1057.
2'-bromo-5-methyl-[1,1'-biphenyl]-3-yl 4-nitrobenzoate
(4j):
Yield: 113.8 mg, 92% (Method A). Colorless solid; mp
1
126-128 °C. H NMR (CDCl3, 600 MHz): δ 2.47 (s, 3H),
7.06 (s, 1H), 7.22 (t, 1H, J = 1.5 Hz), 7.31 (d, 1H, J = 0.5
Hz), 7.42-7.48 (m, 2H), 7.52-7.60 (m, 2H),8.32-8.42 (m,
4H). 13C NMR (CDCl3, 150 MHz): δ 21.5, 117.1, 121.2,
122.1, 123.8, 125.8, 128.8, 131.3, 132.0, 134.9, 139.0,
140.5, 141.6, 151.0, 163.4. IR (KBr) ν: 3449, 3166, 1736,
1527, 1336, 1265, 1092, 712 cm-1. HRMS (ESI) calcd for
C20H14NO479BrNa [M+Na]+: 434.0004, found: 434.0011.
3-methyl-5-(1-tosyl-1H-indol-3-yl)phenyl
nitrobenzoate (4p):
4-
Yield: 98 mg, 62% (Method A). Pale-yellow solid; mp
1
129-131 °C. H NMR (CDCl3, 400 MHz): δ 2.34 (s, 3H),
2.47 (s, 3H), 7.06 (s, 1H), 7.18-7.41 (m, 6H), 7.73 (s, 1H),
7.80 (t, 3H, J = 7.6 Hz), 8.06 (d, 1H, J = 8.2 Hz), 8.28-8.46
(m, 4H). 13C NMR (CDCl3, 100 MHz): δ 21.5, 21.6, 113.9,
117.9, 120.3, 121.1, 122.9, 123.4, 123.7, 123.8, 125.1,
126.7, 126.9, 129.0, 130.0, 131.3, 134.6, 134.9, 135.1,
135.5, 140.5, 145.2, 150.9, 163.5. IR (KBr) ν: 3123, 1740,
1524, 1374, 1264, 1175, 682, 577 cm-1. HRMS (ESI) calcd
for C29H22N2O6SNa [M+Na]+: 549.1096, found: 549.1087.
2'-iodo-5-methyl-[1,1'-biphenyl]-3-yl
(4k):
4-nitrobenzoate
Yield: 120 mg, 87% (Method A). Colorless solid; mp 156-
159 °C. 1H NMR (CDCl3, 600 MHz): δ 2.46 (s, 3H), 7.02-
7.07 (m, 2H), 7.10 (s, 2H), 7.33 (dd, 1H, J = 7.6, 1.5 Hz),
7.39 (t, 1H, J = 7.5 Hz), 7.95 (d, 1H, J = 7.9 Hz), 8.37 (q, J
= 8.9 Hz, 4H). 13C NMR (CDCl3, 150 MHz): δ 21.4, 98.2,
119.6, 121.2, 123.8, 128.2, 128.2, 129.1, 130.1, 131.3,
135.0, 139.6, 145.5, 145.5, 149.9, 150.9, 163.3. IR (KBr)
ν: 3421, 3130, 1743, 1522, 1256, 1077, 764, 713 cm-1.
HRMS (ESI) calcd for C20H14INO4Na [M+Na]+: 481.9865,
found: 481.9871.
[1,1':3',1''-terphenyl]-5'-yl 4-nitrobenzoate (4q):
Yield: 80.7 mg, 68% (Method B). Pale-yellow solid; mp
1
133-135 °C. H NMR (CDCl3, 400 MHz): δ 7.37-7.53 (m,
8H), 7.62-7.71 (m, 4H), 7.77 (t, 1H, J = 1.5 Hz), 8.34-8.48
(m, 4H). 13C NMR (CDCl3, 100 MHz): δ 118.9, 123.8,
124.1, 127.3, 128.0, 129.0, 131.4, 134.9, 140.0, 143.5,
151.0, 151.3, 163.4. IR (KBr) ν: 3108, 1744, 1521, 1258,
1082, 756 cm-1. HRMS (ESI) calcd for C25H17NO4Na
[M+Na]+: 418.1055, found: 418.1055.
3-(6-bromobenzo[d][1,3]dioxol-5-yl)-5-methylphenyl 4-
nitrobenzoate (4l):
Yield: 115 mg, 84% (Method A). Colorless solid; mp 150-
152 °C. 1H NMR (CDCl3, 400 MHz): δ 2.44 (s, 3H), 6.02
(s, 2H), 6.83 (s, 1H), 7.06 (d, 2H, J = 0.7 Hz), 7.07-7.13
(m, 2H), 8.31-8.42 (m, 4H). 13C NMR (CDCl3, 100 MHz):
δ 21.4, 102.0, 110.8, 113.0, 113.0, 119.8, 121.1, 123.7,
128.4, 131.3, 134.7, 135.0, 139.6, 142.4, 147.4, 147.9,
150.0, 150.9, 163.3. IR (KBr) ν: 3109, 1743, 1519, 1260,
1233, 1081, 869, 716 cm-1. HRMS (ESI) calcd for
C21H15NO679Br [M+H]+: 456.0083, found: 456.0088.
3-cyclopropyl-5-methylphenyl 4-nitrobenzoate (4r):
Yield: 68.7 mg, 77% (Method A). Colorless solid; mp 77-
1
79 °C. H NMR (CDCl3, 600 MHz): δ 0.64-0.77 (m, 2H),
0.96-1.00 (m, 2H), 1.87-1.92 (m, 1H), 2.35 (s, 3H), 6.71 (s,
1H), 6.83 (d, 2H, J = 11.4 Hz), 8.28-8.41 (m, 4H). 13C
NMR (CDCl3, 100 MHz): δ 9.4, 15.3, 21.4, 115.6, 119.0,
123.7, 124.8, 131.2, 135.2, 139.6, 146.1, 150.6, 150.9,
163.5. IR (KBr) ν: 3110, 1737, 1519, 1268, 1089, 715 cm-1.
HRMS (ESI) calcd for C17H15NO4Na [M+Na]+: 320.0899,
found: 320.0891.
2'-bromo-4',5'-dimethoxy-5-methyl-[1,1'-biphenyl]-3-yl
4-nitrobenzoate (4m):
Yield: 120 mg, 85% (Method A). Colorless solid; mp 183-
1
185 °C. H NMR (CDCl3, 400 MHz): δ 2.46 (s, 3H), 3.88
3-cyclopentyl-5-methylphenyl 4-nitrobenzoate (4s):
(s, 3H), 3.91 (s, 3H), 6.85 (s, 1H), 7.06 (s, 1H), 7.09 (s,
1H), 7.11 (s, 1H), 7.15 (d, 1H, J = 0.6 Hz), 8.33-8.41 (m,
4H). 13C NMR (CDCl3, 100 MHz): δ 21.5, 56.2, 56.3,
112.4, 113.8, 115.8, 119.8, 121.0, 123.7, 128.4, 131.3,
133.6, 135.0, 139.6, 142.5, 148.3, 149.0, 150.0, 150.9,
163.4. IR (KBr) ν: 3413, 3109, 1741, 1524, 1248, 1139,
714 cm-1. HRMS (ESI) calcd for C22H19NO679Br [M+H]+:
472.0396, found: 472.0393.
Yield: 58.6 mg, 60% (Method B). Colorless solid; mp 103-
105 °C. 1H NMR (CDCl3, 400 MHz): δ 1.89-1.54 (m, 6H),
2.02-2.13 (m, 2H), 2.37 (s, 3H), 2.92-3.06 (m, 1H), 6.86 (s,
1H), 6.89 (s, 1H), 7.00 (s, 1H), 8.31-8.42 (m, 4H).13C
NMR (CDCl3, 100 MHz): δ 21.4, 25.5, 34.5, 45.7, 116.9,
119.2, 123.7, 126.2, 131.3, 135.2, 139.5, 148.5, 150.5,
150.9, 163.5. IR (KBr) ν: 2924, 1745, 1521, 1263, 1087,
871, 711 cm-1. HRMS (ESI) calcd for C19H19NO4Na
[M+Na]+: 348.1212, found: 348.1215.
3-methyl-5-(naphthalen-1-yl)phenyl
(4n):
4-nitrobenzoate
3-cyclohexyl-5-methylphenyl 4-nitrobenzoate (4t):
1
Yield: 113.9 mg, 99% (Method A). Pale-yellow oil. H
NMR (CDCl3, 600 MHz): δ 2.50 (s, 3H), 7.14 (s, 1H), 7.19
(s, 1H), 7.28 (s, 1H), 7.43-7.55 (m, 4H), 7.88 (d, 1H, J =
8.2 Hz), 7.91 (d, 1H, J = 7.7 Hz), 7.96 (d, 1H, J = 8.3 Hz),
8.32-8.37 (m, 2H), 8.37-8.42 (m, 2H). 13C NMR (CDCl3,
150 MHz): δ 21.5, 120.2, 120.9, 123.7, 125.3, 125.8, 125.9,
126.3, 127.0, 128.1, 128.4, 129.0, 131.3, 131.4, 133.8,
Yield: 62.1 mg, 61% (Method B). Colorless solid; mp 97-
99 °C. 1H NMR (CDCl3, 600 MHz): δ 1.18-1.32 (m, 2H),
1.32-1.46 (m, 4H), 1.70-1.78 (m, 1H), 1.80-1.94 (m, 4H),
2.38 (s, 3H), 2.48-2.53 (m, 1H), 6.87 (d, 2H, J = 2.0 Hz),
6.97 (s, 1H), 8.29-8.42 (m, 4H). 13C NMR (CDCl3, 100
MHz): δ 21.4, 26.1, 26.8, 34.4, 44.4, 76.7, 77.0, 77.4,
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701068
Advanced Synthesis & Catalysis
116.7, 119.3, 123.7, 125.9, 131.2, 135.3, 139.5, 149.9,
150.5, 150.9, 163.5. IR (KBr) ν: 3118, 2925, 1741, 1516,
1258, 1088, 712 cm-1. HRMS (ESI) calcd for C20H22NO4
[M+H]+: 340.1549, found: 340.1552.
Acknowledgements
This work was supported by National Natural Science
Foundation of China Grants (21502093 and 21302096), Natural
Science Foundation of Jiangsu Province Grants (BK20150871
and BK20171449), the Project Fund from the Priority Academic
Program Development of Jiangsu Higher Education Institutions
(PAPD) and Top-Notch Academic Programs Project of Jiangsu
Higher Education Institutions (TAPP) (to W.R.), and a Discovery
Project Grant (DP160101682) from the Australian Research
Council (to P.W.H.C.).
3-methyl-5-(pentan-3-yl)phenyl 4-nitrobenzoate (4u):
Yield: 72.7 mg, 74% (Method A). Pale-yellow solid; mp
1
74-76 °C. H NMR (CDCl3, 600 MHz): δ 0.81 (t, 6H, J =
7.4 Hz), 1.52-1.60 (m, 2H), 1.66-1.73 (m, 2H), 2.30-2.35
(m, 1H), 2.38 (s, 3H), 6.80 (s, 1H), 6.88 (s, 1H), 6.90 (s,
1H), 8.33-8.41 (m, 4H). 13C NMR (CDCl3, 150 MHz): δ
12.2, 21.5, 29.2, 49.6, 117.5, 119.3, 123.7, 126.9, 131.2,
135.3, 139.4, 147.8, 150.5, 150.8, 163.4. IR (KBr) ν: 3115,
1733, 1529, 1348, 1267, 712 cm-1. HRMS (ESI) calcd for
C19H22NO4 [M+H]+: 328.1549, found: 328.1541.
References
[1] a) The Chemistry of Phenols, Z. Rappoport. Ed.; John
Wiley & Sons: New York, 2003; b) Modern Arene
Chemistry; D. Astruc. Ed., Wiley-VCH: Weinheim,
2002; c) J. H. P. Tyman. Synthetic and Natural
Phenols; Elsevier: New York, 1996.
3-methyl-5-(3-phenylpropyl)phenyl
(4v):
4-nitrobenzoate
Yield: 72.1 mg, 64% (Method A). Pale-yellow solid; mp
1
53-55 °C. H NMR (CDCl3, 400 MHz): δ 1.92-2.08 (m,
2H), 2.69 (q, 4H, J =14.6 Hz), 6.90 (d, 2H, J = 5.2 Hz),
6.98 (s, 1H), 7.16-7.38 (m, 5H), 8.31-8.46 (m, 4H). 13C
NMR (CDCl3, 100 MHz): δ 21.4, 32.7, 35.2, 35.5, 118.3,
119.4, 123.7, 125.9, 127.5, 128.4, 128.5, 131.3, 135.2,
139.7, 142.1, 144.1, 150.6, 150.9, 163.5. IR (KBr) ν: 2932,
1731, 1522, 1264, 1087, 869, 714 cm-1. HRMS (ESI) calcd
for C23H21NO4Na [M+Na]+: 398.1368, found: 398.1372.
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3-hexyl-5-methylphenyl 4-nitrobenzoate (4w):
Yield: 61.5 mg, 60% (Method B). Pale-yellow oil. 1H
NMR (CDCl3, 400 MHz): δ 0.89 (t, 3H, J = 6.7 Hz), 1.25-
1.41 (m, 6H), 1.56-1.68 (m, 2H), 2.37 (s, 3H), 2.56-2.66
(m, 2H), 6.86 (d, 2H, J = 4.1 Hz), 6.95 (s, 1H), 8.32-8.40
(m, 4H). 13C NMR (CDCl3, 100 MHz): δ 14.1, 21.4, 22.6,
29.0, 31.2, 31.7, 35.8, 118.2, 119.1, 123.7, 127.4, 131.2,
135.2, 139.5, 144.8, 150.5, 150.8, 163.5. IR (neat) ν: 3121,
2926, 1744, 1529, 1259, 1140, 712 cm-1. HRMS (ESI)
calcd for C20H23NO4Na [M+Na]+: 364.1525, found:
364.1525.
5,5''-dimethyl-[1,1':4',1''-terphenyl]-3,3''-diyl diacetate
(4x):
[4] F. Wilson, A. Reid, V. Reader, R. J. Harrison, M.
Sunose, R. Hernandez-Perni, J. Mayor, C. Boussard, K.
Smelt, J. Taylor, A. Le Formal, A. Cansfield, S.
Burckhardt, Eur. Pat. Appl. EP1849762A1, 2007.
Yield: 59.5 mg, 53% (Method A). Pale-yellow solid; mp
1
174-176 °C. H NMR (CDCl3, 600 MHz): δ 2.33 (s, 6H),
2.44 (s, 6H), 6.92 (s, 2H), 7.16 (s, 2H), 7.32 (s, 2H), 7.63
(s, 4H). 13C NMR (CDCl3, 150 MHz): δ 21.2, 21.5, 117.3,
121.2, 125.4, 127.5, 139.5, 140.0, 142.0, 151.1, 169.7. IR
(KBr) ν: 3128, 1752, 1587, 1399, 1216, 1144, 841 cm-1.
HRMS (ESI) calcd for C24H22O4Na [M+Na]+: 397.1416,
found: 397.1408.
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((1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-9-
acetoxy-1-(5-acetoxy-[1,1'-biphenyl]-3-yl)-
5a,5b,8,8,11a-pentamethylicosahydro-3aH-
cyclopenta[a]chrysen-3a-yl)methyl acetate (4y):
Yield: 196.5 mg, 94% (Method A). Pale-yellow solid; mp
[6] Recent examples: a) Y.-F. Liang, X. Li, X. Wang, M.
Zou, C. Tang, Y. Liang, S. Song, N. Jiao, J. Am. Chem.
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1
161-163 °C. H NMR (CDCl3, 400 MHz): δ 0.52-0.67 (m,
1H), 0.67-0.92 (m, 10H), 0.93 (s, 3H), 0.99-1.29 (m, 9H),
1.29-1.46 (m, 6H), 1.47-1.83 (m, 6H), 1.86-1.95 (m, 3H),
2.03 (s, 3H), 2.10 (s, 3H), 2.32 (s, 4H), 2.87-2.94 (m, 1H),
3.95 (d, 1H, J = 11.0 Hz), 4.32 (d, 1H, J = 10.9 Hz), 4.42 (t,
1H, J = 7.6 Hz), 6.90 (s, 1H), 7.11 (t, 1H, J = 1.8 Hz), 7.27
(s, 1H), 7.33-7.37 (m, 1H), 7.43 (t, 2H, J = 7.5 Hz), 7.51-
7.61 (m, 2H). 13C NMR (CDCl3, 100 MHz): δ 14.7, 16.0,
16.1, 18.2, 20.8, 21.1, 21.3, 21.3, 23.7, 27.0, 27.1, 28.0,
29.8, 34.1, 34.2, 34.8, 37.0, 37.5, 37.8, 38.3, 40.8, 42.6,
46.5, 46.7, 49.9, 54.2, 55.3, 62.8, 80.9, 117.6, 127.2, 127.6,
128.8, 140.5, 142.5, 150.9, 151.1, 169.4, 171.0, 171.6. IR
(KBr) ν: 2948, 1769, 1735, 1455, 1366, 1243, 1029, 763,
701 cm-1. HRMS (ESI) calcd for C45H61O6 [M+H]+:
697.4468, found: 697.4464.
8
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10.1002/adsc.201701068
Advanced Synthesis & Catalysis
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W. Rao, J. W. Boyle, P. W. H. Chan, Chem. Eur. J.
2016, 22, 6532; b) D. Susanti, L.-J. Liu, W. Rao, S. Lin,
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[18] To our knowledge, the only other known example in
gold
catalysis
is
the
dehydrogenative
cycloisomerization of cyclopropane-tethered 1,5-
enynes: G.-Q. Chen, W. Fang, Y. Wei, X.-Y. Tang, M.
Shi, Chem. Commun. 2016, 52, 10799.
[19] Refer to the Supporting Information for details.
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9
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10.1002/adsc.201701068
Advanced Synthesis & Catalysis
A. S. K. Hashmi, M. Rudolph, J. P. Weyrauch, M.
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10
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Advanced Synthesis & Catalysis
FULL PAPER
Gold Catalyzed Dehydrogenative
Cycloisomerization of 1,4-Enyne Esters to 3,5-
Disubstituted Phenol Derivatives
Adv. Synth. Catal. Year, Volume, Page – Page
Cuili Chen,a Xianxiao Chen,a Xiaoxiang Zhang,a
Shifa Wang,a Weidong Rao,a* and Philip Wai
Hong Chanb,c*
11
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