Gold-Catalyzed Oxidation Terminal Alkyne: An Approach to Synthesize Substituted Dihydronaphthalen-2(1H)-ones and Phenanthrenols

Article abstract of DOI:10.1021/acs.joc.7b01244

A facile gold-catalyzed oxidation terminal alkynes to synthesize substituted dihydronaphthalen-2(1H)-ones 3 and phenanthrenols 5 was realized. Various useful structures and drug precursors were generated in up to 99% yield under mild condition and low catalyst loading.

Full text of DOI:10.1021/acs.joc.7b01244

Note
Gold-Catalyzed Oxidation Terminal Alkyne: An Approach to Synthesize
Substituted Dihydronaphthalen-2(1H)-ones and Phenanthrenols
Hui-Bo Ling, Zi-Sheng Chen, Fang Yang, Bin Xu, Jin-Ming Gao, and Kegong Ji
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 16 Jun 2017
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Gold-Catalyzed Oxidation Terminal Alkyne: An Approach to Syn-
thesize Substituted Dihydronaphthalen-2(1H)-ones and Phenan-
threnols
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Hui-Bo Ling,‡,a Zi-Sheng Chen ‡,a, Fang Yang,a Bin Xu,b Jin-Ming Gao,a Kegong Ji*,a
a Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry and Pharmacy, Northwest A&F
University, 3 Taicheng Road, Yangling, 712100, Shaanxi, P. R. China. E-mail:jikegong@nwsuaf.edu.cn.
b Hainan Institute for Food Control, No.285, Nanhai Avenue, Xiu Ying District, Haikou 570311, PR China.
Supporting Information Placeholder
R'
R'
R'
TMetBuXPhosAuCl/NaBARf4
R''
t
R''
O
R''
TMe BuXPhosAuCl/NaBARf4
R
R
2a
N-oxide
(1.3 equiv)
2a
N-oxide
(1.3equiv)
OH
DCE, 50 °C
DCE, 50 °C
5
3
1
Up to 98% yield
Up to 99% yield
ABSTRACT: A facile gold-catalyzed oxidation terminal alkynes to synthesize substituted dihydronaphthalen-2(1H)-ones 3 and phe-
nanthrenols 5 was realized. Various useful structures and drug precursors were generated in up to 99% yield under mild condition
and low catalyst loading.
hazardous and potentially explosive α-diazo ketone precur-
Aromatic rings are “privileged structures” and important mo-
tifs in natural products and biologically active molecules. A
number of aromatic systems, such as tetrahydronaphthalene and
phenanthrene analogues, possessing interesting biological prop-
sors.6,7 Terminal alkynes as the research object is also widely
studied and the generated α-oxo gold carbene intermediates
trapped in situ by relatively electron-rich nucleophiles, such as
oxygen,8 nitrogen,9 sulfur,10 electron-rich aryl ether,11 C-C dou-
erties were reported. They are also potentially useful precursors
12
ble and triple bonds. Recently, Zhang and co-workers re-
for drug discovery programs and functional group transfor-
mations (Figure 1). 1 In this context, the development of useful
ported the gold catalyzed oxidation of propargyl aryl ethers to
methods to synthesize functionalized tetrahydronaphthalene
and phenanthrene derivatives with safe and simple conditions
continues to be actively pursued.
Scheme 1. Background and our design
A: Zhang's work: Ortho-carbon of aryl ether as nucleophiles trap the -oxo gold carbene
O
O
O
LAuNTf2 (5 mol %)
DCE, rt, 1-3 h
RO
OR
R
R
+
O
O
N
O
43-83% yield
B:Gagosz's work:Weak aryl sp2 carbon as nucleophiles in gold catalyzed oxidation of
Propynyl Arene via SN2' process
OAr
ArO
P
O
LAuNTf2(4 mol %)
L:
OMe
R
R
O
MeO
tBu
N
O
Cl
+
R''
52-76% yield
CHCl3, 20/60 °C, MsOH
R'
R'
R''
C:Our design:Weak aryl sp2 carbon as nucleophiles and flexible alkyne as substrate
O
OH
Au(I)
Ar
Ar
Ar
+
O-Z
3
5
1
[LAu]
[LAu]
O
O
No acid
and
Ar
Ar
With bulky Ligand gold complex
Figure 1. Examples of bioactive structures.
Int I
Int II
R
Recently, gold(I)-catalyzed oxidation of alkynes using pyri-
dine/quinoline N-oxides as oxidants to synthesize various use-
ful molecules were reported.2 The α-oxo gold carbene interme-
diates generated from alkynes can be trapped in situ by inter-
nal/external nucleophiles, 3, 4, 5 which circumvents the use of
RO
>
Nucleophile of C2:
Flexible:
>
C2
C2
Useful key motif
Simple N-Oxide
Weaker nucleophile
Low catalyst loading
More flexible of alkyne
No acid as additive
High yield
Mild condition
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synthesize chroman-3-ones by using internal ortho-carbon of
and 1.2 equivalents of pyridine oxides (2a–e). The reactions
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aryl ether as nucleophiles to trap the in situ generated α-oxo
gold carbenes.11 In contrast, the use of an unactivated aryl sp2
carbon to trap the highly reactive α-oxo gold carbene interme-
diates efficiently proved to be challenging because of the dou-
ble oxidation of terminal alkynes and other intractable side re-
actions. 13 Thus, reports on the successful use of aryl sp2 carbon
to trap the α-oxo gold carbene generated in situ from terminal
alkynes are limited. In 2013, Gagosz and co-workers reported
gold catalyzed oxidative cyclization of propynyl arenes into in-
dan-2-ones by using aryl sp2 carbon as nucleophiles, which sug-
gested a SN2’-type process.14 To further develop terminal al-
kynes as surrogates of hazardous α-diazo ketones in gold(I) ca-
talysis, we focused here on expanding the scope of suitable in-
ternal nucleophiles such as aryl groups. Our first target was
flexible aryl-substituted alkyne 1, as shown in Scheme 1C, our
design anticipated that a terminal α-oxo gold carbene could be
generated upon oxidation of the terminal C–C triple bond,
which was then trapped by aryl group. Gagosz and co-workers
have reported three examples of this type of C–H functionaliza-
tion using 3-butynylbenzene substrate in the presence of me-
thanesulfonic acid and bulky pyridine N-oxides with the prod-
ucts overall yield less than 45%.14 We surmised that this strat-
egy, if realized with more flexible alkynes, would offer rapid
access to synthetically versatile dihydronaphthalen-2(1H)-ones
3 and phenanthrenols 5 under mild conditions in the absence of
acid as an additive (Scheme 1).
were carried out at 50℃in 1, 2-dichloroethane (DCE) and mon-
itored by 1H NMR spectroscopy for 5 hours. To our delight, it
was observed that 1a was converted to the corresponding 3a in
83 % yield with 2, 6-dichloropyridine 1-oxide 2a as the oxidant
(entry 1). Other N-oxides, such as 2b–2d, were inefficient even
after longer times (entries 2–4). Notably, Zhang and co-workers
recently reported that Hantzsch esters N-oxide 2e is the best ox-
idant for promoting the cyclizations of propargyl aryl ethers to
chroman-3-ones selectively, however, no superior result was
observed in our case (entry 5). Different counter anions gener-
ated from silver salts, like AgNTf2 and AgOTf, were both inef-
ficient (entries 6-7). The effect of the solvents, like toluene and
THF, were also considered, but no better results were observed
(entries 8-9). Other cationic gold complexes derived from typi-
cal ligands such as Ph3P, Mor-dalPhos, IPr and Phosphite were
largely ineffective, thus resulting in 3-butyn-1-ylbenzene, 1a,
with little desired product (entries 10 - 14). In these reactions,
only trace amounts of the 1, 2-dihydronaphthalene 4a was
formed through a gold-catalyzed 6-endo-dig cyclization in the
absence of the oxidant 2a.
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Table 2. Gold-catalyzed oxidation terminal alkynes to
synthesize substituted dihydronaphthalen-2(1H)-ones a, b
The commercially available 3-butyn-1-ylbenzene, 1a, was
chosen as a model substrate to determine the catalytic condi-
tions leading to the corresponding 3, 4-dihydronaphthalen-
2(1H)-one 3a. The reaction optimization results are shown in
Table 1. Initially, the substrate 1a was treated with
t
Me4 BuXPhosAuCl (2 mol %)/NaBARF4 (3 mol %)
Table 1. Screening conditions. a
t
With Me4 BuXPhosAuCl (2 mol %)/NaBARF4 (3 mol %) as
the catalyst system and pyridine 1-oxide 2a as the oxidant, the
scope of the transformation was first examined with various 3-
butyn-1-ylbenzenes, as shown in Table 2. For the para-elec-
tron-donating substitution on the benzene ring, like, methoxy,
benzoxy and allyloxy, reacted smoothly to give corresponding
products in good to excellent yields (3b–d). More methoxy sub-
stitutions on the benzene ring, like1e-f, were also tested, and the
desired products overall yields were mostly less than 25%,
along with 6-endo-dig cyclization products 4e-f. In these cases,
in the absence of the oxidant 2a, a gold-catalyzed 6-endo-dig
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cyclization was facile, which suggested that electron rich sub-
Scheme 2. The application of 3, 4-dihydronaphthalen-
4
5
6
7
8
9
stitution on the benzene ring played the requisite role of accel-
erating this side reaction. For this, 1.5 equiv of MsOH was
added and the proton was coordinated with the methoxy substi-
tutions, which reduced the electron on the benzene ring. Fortu-
nately, substrate 1e was smoothly converted to the desired prod-
uct 3e in 62% yields. To our delight, 2.0 equiv of MsOH was
used in transforming 1f, an excellent yield of 3f (98% yield)
was obtained. With an electron-withdrawing group, like 1g, the
reaction worked well and an accepted yield of corresponding
product 3g was obtained. The functional group tolerance of this
chemistry is good as substrates with aliphatic R2 group, methyl
group (1h) and aliphatic ring group (1i) reacted well. Substrates
1-(but-3-yn-1-yl)naphthalene 1j-k were readily tolerated and
the desired product 3j-k were obtained in an excellent yield.
While considering synthetically useful transformations and
expand the scope of this reaction, we examined the direct con-
version of o-ethynyl-1, 1'-biaryls 1aa–1ag in the presence of
Me4tBuXPhosAuCl (2 mol %)/NaBARF4 (3 mol %)/2a system.
Much to our delight, this strategy worked well with different R
group substituents, thus affording various functionalized phe-
nanthrenols 5aa-5ad in good to excellent yield as shown in Ta-
ble 3. For the substrate 1ae, by installing a methyl group on
mata position, the regioselectivity in the case was 2:1. Other o-
ethynyl-1, 1'-biaryl such as 1af with an electron-withdrawing R’
group worked well to give the corresponding phenanthrenol 5af
in good yields. The substrate 1ag with a benzo[b]thiophene R
group can also afford the desired product 2ag in 92% yield. In
these reactions, no gold-catalyzed 6-endo-dig cyclization prod-
ucts were observed which is shown an excellent selectivity.15
2(1H)-one 3a and phenanthrenol 5a
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and electron-donating substitutions were tolerated. Based on
our developed method, various useful aromatic structures and
drug precursors were synthesized under mild condition.
■ EXPERIMENTAL SECTION
General Information. Ethyl acetate (ACS grade), hexanes
(ACS grade), diethyl ether (ACS grade) and anhydrous 1, 2-di-
chloroethane (anhydride, 99.8%) were purchased from Fisher
Scientific and used without further purification. Methylene
chloride and tetrahydrofuran were purified using MBraun Sol-
vent Purifier. Commercially available reagents were used with-
out further purification. Reactions were monitored by thin layer
chromatography (TLC) using Sorbent Technologies’ pre-
coated silica gel plates. Flash column chromateography was
performed over Sorbent Technologies silica gel (230-400 mesh).
1H NMR and 13C NMR spectra were recorded on Bruker 500
MHz spectrometers using residue solvent peaks as internal
standards. Mass spectra were recorded with Micromass QTOF2
Quadrupole/Time-of-Flight Tandem mass spectrometer using
electron spray ionization or Waters GCT Premier time-of-flight
mass spectrometer with a field ionization (FI) ion source.
Chemical shifts are reported in ppm with the internal chloro-
form signal at 7.26 and 77.0 ppm as a standard.
General procedure A: Methods for the synthesis 3-butyn-1-
ylbenzene derivatives 1a-k. Step 1: A well-stirred solution of
the Aluminum (405 mg, 15 mmol, 1.5 equiv) and Hg2Cl2 (30
mg, 0.06 mmol, 6 mol%) in THF (10 mL) heated to 60~70℃.
The 3-bromoprop-1-yne (1.78 g, 15 mmol, 1.5 equiv) diluted
by THF(10 mL) was added dropwise via syringe and the reac-
tion was stirred at room temperature for 30 minutes under nitro-
gen atmosphere. The resulting mixture was then added drop-
wise to the solution of Arylaldehyde (10 mmol, 1.0 equiv) in
THF (10 mL) at -78℃. The reaction was stirred under N2 until
substrate disappeared as judged by TLC, and then quenched
with sat aq. NH4Cl. The solution was washed with brine solu-
tion and extracted with ethyl acetate (3×10 mL). The combined
organic layers were dried over anhydrous Na2SO4, filtered, and
concentrated under reduced pressure. The crude product was
purified by chromatography on silica gel using petroleum
ether/EtOAc (20:1) as the eluent to afford 3-butyn-1-ylbenzene
derivatives in 96% yield.
Table 3. Gold-catalyzed oxidation terminal alkynes to
synthesize substituted phenanthrenols a, b
For the products 3a and 5a, the motifs can be easily trans-
ferred to useful structure and drug molecular, as shown in
scheme 2.16
In summary, we have described an efficient approach to syn-
thesize substituted dihydronaphthalen-2(1H)-ones 3 and phe-
nanthrenols 5 via gold-catalyzed oxidation terminal alkyne in
low catalyst loading. The reaction proceeded smoothly to pro-
vide the corresponding products dihydronaphthalen-2(1H)-
ones 3 in good to excellent yield. Phenanthrenols 5 were ob-
tained smoothly in good yield and both electron-withdrawing
Step 2: To a solution of 3-butyn-1-ylbenzene derivatives (9
mmol, 1.0 equiv) in DCM (27 mL) at 0℃ under N2 atmosphere
was added Et3SiH (18 mmol, 2.09 g, 2.0 equiv), the reaction
was stirred at this temperature for 30 min and then TFA or
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BF3•Et2O (36 mmol, 4.10g, 4.0 equiv) was added dropwise via
20.8, 6.8, 6.4. HRMS (ESI) m/z calcd for C17H17O+ (M+H)+:
4
5
6
7
8
9
syringe. The mixture was slowly warmed to room temperature
and stirred until substrate disappeared, and quenched with sat
aq. NaHCO3. The solution was washed with brine solution and
extracted with DCM (3×10 mL). The combined organic layers
were dried over anhydrous Na2SO4, filtered, and concentrated
under reduced pressure. The crude product purified by chro-
motagraphy on silica gel using petroleum ether/EtOAc (15:1)
as the eluent to afford product 1a-k in 85% yield.
General procedure B: Methods for the synthesis 2-ethynyl-
1,1'-biphenyl derivatives 1aa-1ag. Step 1: To a solution of
Pd(OAc)2 (0.3 mml, 67.2 mg, 0.03 equiv) and Na2CO3 (20
mmol, 1.68 g, 2.0 equiv) in 20 mL DMF/H2O (2:1) was added
phenylboronic acid (10.5 mmol, 1.28 g, 1.05 equiv), and the re-
sulting mixture was stirred for 15 min. To this solution was
added 2-bromobenzaldehyde (10 mmol, 1.85g, 1.0 equiv) at
0℃, which was stirred for 3 h at room temperature. Quenched
by Ammoium chloride solution, the solution was washed with
brine solution and extracted with diethyl ether (3×15mL). The
combined organic layers were dried over anhydrous Na2SO4,
filtered, and concentrated under reduced pressure. The crude
product was purified by chromatography on silica gel using pe-
troleum ether/EtOAc (40:1) as the eluent affording [1,1'-bi-
phenyl]-2-carbaldehyde in 87% yield.
Step 2: To a solution of [1,1'-biphenyl]-2-carbaldehyde (8.7
mmol, 1.58 g, 1.0 equiv) and in CBr4 (13.1 mmol, 4.3 g, 1.5
equiv) in anhydrous DCM (20 mL) cooled to 0℃ (ice-water
bath) was added PPh3 (26.1 mmol, 6.8 g, 3.0 equiv) as a solid
in small portions. The light-yellow reaction mixture was then
stirred at ambient temperature for 3-5 h. Solvent was removed
in vacuo, and the residure was dissolved in petroleum
ether/EtOAc (60:1). Triphenylphosphine oxide was filtered off
by suction. The filtrate was concentrated under reduced pres-
sure, and the crude gem-dibromide was purified by chromatog-
raphy on silica gel using petroleum ether/EtOAc (40:1) as the
eluent affording the product of gem-dibromide in 95% yield. A
well-stirred solution of the gem-dibromide (8.3 mmol, 1.0 equiv)
in anhydrous THF (20 mL) was cooled to -40℃ under an argon
atmosphere, n-BuLi (2.5 M in hexane, 6.84 mL, 2.05 equiv) was
then added dropwise via syringe. The stirring was continued at
-40℃ until the reaction was complete as monitored by TLC.
After completion of the reaction, the resultant light-yellow/or-
ange mixture was diluted with distilled water, and the stirring
was continued for 0.5 h to allow the mixture to slowly reach
room temperature. The layers were separated, and the aqueous
layer was extracted with Et2O. The combined organic layers
were washed with brine, dried over anhydrous Na2SO4, filtered,
and concentrated under reduced pressure. The crude product
was purified by chromatography on silica gel using petroleum
ether/EtOAc (40:1) as the eluent to afford the products 1aa-1ag
in 96% yield.
237.1274, found 237.1274. GCMS (m/z): 236.12
1-(allyloxy)-4-(but-3-yn-1-yl)benzene (1d) was prepared in
82% yield (1.53 g) through the General Procedure A.1H NMR
(500 MHz, CDCl3) δ 7.19 – 7.09 (m, 2H), 6.97 – 6.80 (m, 2H),
6.08 (ddt, J = 17.2, 10.5, 5.3 Hz, 1H), 5.43 (ddd, J = 17.3, 3.2,
1.6 Hz, 1H), 5.35 – 5.23 (m, 1H), 4.53 (dt, J = 5.3, 1.5 Hz, 2H),
2.81 (t, J = 7.5 Hz, 2H), 2.53 – 2.40 (m, 2H), 2.00 (t, J = 2.6 Hz,
1H).13C NMR (126 MHz, CDCl3) δ 157.2, 133.4, 132.8, 129.3,
117.5, 114.7, 83.9, 68.8, 68.8, 34.0, 20.8. HRMS (M+H)+ calcd
for C13H15O+: 187.1117, found 187.1117.
4-(but-3-yn-1-yl)-1,2-dimethoxybenzene (1e) is known com-
pound19. 1H NMR (500 MHz, CDCl3) δ 6.93 – 6.64 (m, 3H),
3.88 (s, 3H), 3.86 (s, 3H), 2.80 (t, J = 7.5 Hz, 2H), 2.47 (td, J =
7.5, 2.6 Hz, 2H), 1.98 (t, J = 2.6 Hz, 1H).
10
11
12
13
14
15
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19
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5-(but-3-yn-1-yl)-1,2,3-trimethoxybenzene (1f) is known
compound20. 1H NMR (500 MHz, CDCl3) δ 6.46 (s, 2H), 3.85
(s, 5H), 3.83 (s, 3H), 2.79 (t, J = 7.5 Hz, 2H), 2.48 (td, J = 7.5,
2.6 Hz, 2H), 2.09 – 1.77 (m, 1H).
4-(but-3-yn-1-yl)phenyl acetate (1g). was prepared in 73%
yield (1.37 g) through the General Procedure A. 1H NMR (500
1
MHz, CDCl3) H NMR (500 MHz, CDCl3) δ 7.23 (d, J = 8.5
Hz, 2H), 7.02 (d, J = 8.5 Hz, 2H), 2.84 (t, J = 7.5 Hz, 2H), 2.48
(td, J = 7.5, 2.6 Hz, 2H), 2.29 (s, 3H), 1.99 (t, J = 2.6 Hz, 1H).
13C NMR (126 MHz, CDCl3) δ 169.5, 149.1, 137.9, 129.3,
121.4, 83.5, 69.0, 34.2, 21.1, 20.4. HRMS (ESI) m/z calcd for
+
C12H13O2 (M+H)+: 189.0910, found 189.0907. GCMS (m/z):
188.08.
1-methoxy-4-(pent-4-yn-2-yl)benzene (1h) was prepared in
82% (1.43 g) yield through the General Procedure A by using
1
BF3•OEt2 instead of the TFA. H NMR (500 MHz, CDCl3) δ
7.23 – 7.13 (m, 2H), 6.93 – 6.82 (m, 2H), 3.81 (s, 3H), 3.09 –
2.84 (m, 1H), 2.57 – 2.28 (m, 2H), 1.99 (t, J = 2.6 Hz, 1H), 1.47
– 1.31 (m, 3H). 13C NMR (126 MHz, CDCl3) δ 158.1, 137.7,
127.7, 113.8, 83.2, 69.4, 55.2, 38.0, 27.8, 20.9. HRMS (ESI)
m/z calcd for C12H15O+ (M+H)+: 175.1117, found 175.1118.
GCMS (m/z): 174.10
6-methoxy-1-(prop-2-yn-1-yl)-1,2,3,4-tetrahydronaphtha-
lene (1i) was prepared in 82% yield (1.64 g) through the Gen-
eral Procedure A by using BF3•OEt2 instead of the TFA. H
1
NMR (500 MHz, CDCl3) δ 7.15 (d, J = 8.5 Hz, 1H), 6.70 (ddd,
J = 14.4, 8.4, 2.6 Hz, 1H), 6.61 (d, J = 2.5 Hz, 1H), 3.78 (s, 3H),
3.04 – 2.90 (m, 1H), 2.87 – 2.65 (m, 2H), 2.62 – 2.50 (m, 1H),
2.50 – 2.35 (m, 1H), 2.01 (t, J = 2.6 Hz, 1H), 1.96 – 1.90 (m,
2H), 1.86 – 1.71 (m, 2H). HRMS (ESI) calcd for C14H17O+
(M+H)+: 201.1274, found 201.1274.
1-(but-3-yn-1-yl)naphthalene (1j) is known compound21,22
.
1H NMR (500 MHz, CDCl3) δ 8.03 (d, J = 8.3 Hz, 1H), 7.87 (d,
J = 7.8 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H), 7.56 – 7.45 (m, 2H),
7.45 – 7.34 (m, 2H), 3.34 (t, J = 7.7 Hz, 2H), 2.64 (td, J = 7.8,
2.6 Hz, 2H), 2.03 (t, J = 2.6 Hz, 1H).
1-(but-3-yn-1-yl)-4-methoxynaphthalene (1k) was prepared
in 82% (1.73 g) yield through the General Procedure A. 1H
NMR (500 MHz, CDCl3) δ 8.35 (dd, J = 8.3, 0.9 Hz, 1H), 7.96
(d, J = 8.2 Hz, 1H), 7.52 (dddd, J = 24.4, 8.1, 6.8, 1.3 Hz, 2H),
7.28 (d, J = 7.8 Hz, 1H), 6.74 (d, J = 7.8 Hz, 1H), 3.97 (s, 3H),
3.27 (t, J = 7.7 Hz, 2H), 2.66 – 2.57 (m, 2H), 2.06 (t, J = 2.6 Hz,
1H). HRMS (M+H)+ calcd for C15H15O+: 211.1117, found
211.1120.
3-butyn-1-ylbenzene (1a)17 is commercially available product.
1-(but-3-yn-1-yl)-4-methoxybenzene (1b) is known com-
pound 18.1H NMR (500 MHz, CDCl3) δ 7.15 (d, J = 8.6 Hz, 2H),
6.83 (t, J = 9.1 Hz, 2H), 3.79 (s, 3H), 2.79 (t, J = 7.5 Hz, 2H),
2.55 – 2.40 (m, 2H), 2.10 – 1.84 (m, 1H).
1-(benzyloxy)-4-(but-3-yn-1-yl)benzene (1c) was prepared in
78% yield (1.84 g) through the General Procedure A.1H NMR
(500 MHz, CDCl3) δ 7.48 – 7.44 (m, 2H), 7.44 – 7.38 (m, 2H),
7.37 – 7.33 (m, 1H), 7.19 – 7.14 (m, 2H), 7.01 – 6.89 (m, 2H),
5.07 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.53 – 2.43 (m, 2H), 2.01
(t, J = 2.6 Hz, 1H).13C NMR (126 MHz, CDCl3) δ 157.4, 137.1,
132.8, 129.4, 128.5, 127.9, 127.4, 114.8, 83.9, 70.0, 68.8, 34.0,
2-ethynyl-4'-methoxy-1,1'-biphenyl (1ab) is known com-
1
pound23. H NMR (500 MHz, CDCl3) δ 7.60 (dd, J = 7.7, 0.9
Hz, 1H), 7.56 – 7.49 (m, 2H), 7.42 – 7.33 (m, 2H), 7.29 – 7.26
(m, 1H), 7.00 – 6.93 (m, 2H), 3.86 (s, 3H), 3.05 (s, 1H).
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4'-chloro-2-ethynyl-1,1'-biphenyl (1ac) is known compound
3.00 (t, J = 6.7 Hz, 2H), 2.56 – 2.51 (m, 2H). 13C NMR (126
MHz, CDCl3) δ 210.6, 157.6, 134.5, 133.3, 129.0, 128.6, 117.7,
114.5, 113.2, 69.0, 45.2, 38.6, 27.5. HRMS (M+H)+ calcd for
24. 1H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 2.2 Hz, 1H), 7.57
– 7.52 (m, 2H), 7.46 – 7.41 (m, 2H), 7.40 – 7.36 (m, 2H), 7.33
– 7.28 (m, 1H), 3.07 (s, 1H). 13C NMR (126 MHz, CDCl3) δ
142.9, 139.2, 133.4, 132.8, 130.8, 129.2, 129.1, 128.1, 127.9,
122.1, 81.8, 81.2.
+
C13H15O2 : 203.1067, found 203.1069.
6,7-dimethoxy-3,4-dihydronaphthalen-2(1H)-one (3e) is
known compound28 and was prepared in 62% yield (12.8 mg)
1
2-ethynyl-4'-fluoro-1,1'-biphenyl (1ad) is known compound
23. 1H NMR (500 MHz, CDCl3) δ 7.73 – 7.66 (m, 1H), 7.66 –
7.58 (m, 2H), 7.48 – 7.32 (m, 3H), 7.23 – 7.12 (m, 2H), 3.11 (d,
J = 2.4 Hz, 1H).
2-ethynyl-3'-methyl-1,1'-biphenyl (1ae) was prepared in 82%
yield (1.58 g) through the General Procedure B. 1H NMR (500
MHz, CDCl3) δ 7.63 (d, J = 7.5 Hz, 1H), 7.39 (ddd, J = 11.1,
9.3, 5.3 Hz, 4H), 7.31 (ddd, J = 10.7, 8.8, 4.7 Hz, 2H), 7.20 (d,
J = 7.5 Hz, 1H), 3.05 (s, 1H), 2.43 (s, 3H).13C NMR (126 MHz,
CDCl3) δ 144.6, 140.2, 137.6, 133.9, 130.0, 129.6, 129.0, 128.3,
127.9, 126.9, 126.4, 120.5, 83.2, 80.1, 21.5. HRMS (M+H)+
calcd for C15H13+: 193.1012, found 193.1010.
according to the general procedure C. H NMR (500 MHz,
CDCl3) δ 6.74 (s, 1H), 6.62 (s, 1H), 3.88 (s, 3H), 3.86 (s, 3H),
3.52 (s, 2H), 3.00 (t, J = 6.7 Hz, 2H), 2.56 (t, J = 6.7 Hz, 2H).
6,7, 8-trimethoxy-3,4-dihydronaphthalen-2(1H)-one (3f) is
known compound 20 and was prepared in 98% yield (23.1 mg)
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13
14
15
16
17
18
19
20
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22
23
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according to the general procedure C. H NMR (500 MHz,
CDCl3) δ 6.55 (s, 1H), 3.89 – 3.81 (m, 9H), 3.50 (s, 2H), 3.00
(t, J = 6.7 Hz, 2H), 2.61 – 2.49 (m, 2H).
7-oxo-5,6,7,8-tetrahydronaphthalen-2-yl acetate (3g) was
prepared in 53% yield (10.8 mg) according to the general pro-
cedure C. 1H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 8.1 Hz,
1H), 6.93 (dd, J = 8.2, 2.4 Hz, 1H), 6.87 (d, J = 2.1 Hz, 1H),
3.57 (s, 2H), 3.05 (t, J = 6.7 Hz, 2H), 2.59 – 2.53 (m, 2H), 2.29
(s, 3H). 13C NMR (126 MHz, CDCl3) δ 209.7, 169.6, 149.4,
134.7, 134.3, 128.6, 121.3, 120.0, 44.9, 38.1, 27.8, 21.1. HRMS
2-ethynyl-5-fluoro-1,1'-biphenyl (1af) is known compound23.
1H NMR (500 MHz, CDCl3) δ 7.63 – 7.55 (m, 3H), 7.49 – 7.37
(m, 3H), 7.13 – 7.08 (m, 1H), 7.02 (td, J = 8.3, 2.7 Hz, 1H), 3.01
(s, 1H).
2-(2-ethynylphenyl)benzo[b]thiophene (1ag) is known com-
pound23. 1H NMR (500 MHz, CDCl3) δ 7.89 – 7.84 (m, 2H),
7.84 – 7.80 (m, 1H), 7.66 (dd, J = 7.7, 1.2 Hz, 1H), 7.62 (dd, J
= 7.9, 0.8 Hz, 1H), 7.42 (td, J = 7.7, 1.4 Hz, 1H), 7.40 – 7.34
(m, 2H), 7.34 – 7.29 (m, 1H), 3.30 (s, 1H).
General procedure C: Gold catalyzed oxidation functional-
ization of terminal alkyne to dihydronaphthalen-2(1H)-ones 3
and phenanthrenols 5. To a dram vial containing 2 mL of DCE
was added sequentially the alkyne 1 (0.1 mmol), 2, 6-dichloro-
pyridine 1-oxide 2a (20 mg, 0.12 mmol, 1.2 equiv),
TMetBuXPhosAuCl (1.4 mg, 0.002 mmol), and NaBArF4 (2.6
mg, 0.003 mmol). The resulting mixture was stirred at 50 ºC,
and the progress of the reaction was monitored by TLC. Upon
completion, the reaction mixture was concentrated under vac-
uum. The residue was purified by chromatography on silica gel
(eluent: hexanes/ethyl acetate) to afford the desired dihy-
dronaphthalen-2(1H)-ones 3 and phenanthrenols 5.
+
(ESI) m/z calcd for C12H13O3 (M+H)+: 205.0859, found
205.0859. GCMS (m/z): 204.08.
7-methoxy-4-methyl-3,4-dihydronaphthalen-2(1H)-one (3h)
was prepared in 70% yield (13.3 mg) according to the general
procedure C. 1H NMR (500 MHz, CDCl3) δ 7.19 (d, J = 8.4 Hz,
1H), 6.80 (dd, J = 8.4, 2.6 Hz, 1H), 6.66 (d, J = 2.6 Hz, 1H),
3.79 (s, 3H), 3.57 (dt, J = 13.9, 12.4 Hz, 2H), 3.28 – 3.15 (m,
1H), 2.74 – 2.64 (m, 1H), 2.31 (dd, J = 16.4, 7.5 Hz, 1H), 1.31
(d, J = 7.0 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 210.2, 158.5,
134.1, 133.4, 127.0, 113.6, 112.5, 55.4, 46.7, 44.8, 32.8, 20.4.
+
HRMS (M+H)+ calcd for C12H15O2 :191.1067, found 191.1071.
8-methoxy-3a,4,5,6-tetrahydro-1H-phenalen-2(3H)-one (3i)
was prepared in 86% yield (18.6 mg) according to the general
procedure C.1H NMR (500 MHz, CDCl3) δ 7.31 – 7.25 (m, 3H),
7.18 (dd, J = 7.8, 4.1 Hz, 1H), 3.64 (s, 2H), 3.12 (t, J = 6.7 Hz,
2H), 2.66 – 2.56 (m, 2H). 13C NMR (126 MHz, CDCl3) δ 210.4,
158.2, 137.8, 134.6, 128.4, 112.4, 111.5, 55.3, 46.0, 46.0, 33.2,
+
30.6, 29.9, 22.5. HRMS (M+H)+ calcd for C14H17O2 :217.1223,
3,4-dihydronaphthalen-2(1H)-one (3a) is known compound
found 217.1223.
25
and was prepared in 83% yield (12.1 mg) according to the
3,4-dihydrophenanthren-2(1H)-one (3j) is known com-
pound29 and was prepared in 94% yield (18.4 mg) according to
the general procedure C. 1H NMR (500 MHz, CDCl3) δ 8.05
(dd, J = 8.7, 5.2 Hz, 1H), 7.87 (t, J = 9.1 Hz, 1H), 7.73 (dd, J =
9.8, 5.2 Hz, 1H), 7.59 – 7.53 (m, 1H), 7.53 – 7.47 (m, 1H), 7.22
(d, J = 8.4 Hz, 1H), 3.75 (s, 2H), 3.51 (t, J = 6.8 Hz, 2H), 2.78
– 2.65 (m, 2H).
general procedure C. 1H NMR (500 MHz, CDCl3) δ 7.31 – 7.25
(m, 3H), 7.18 (dd, J = 7.8, 4.1 Hz, 1H), 3.64 (s, 2H), 3.12 (t, J
= 6.7 Hz, 2H), 2.66 – 2.56 (m, 2H).
7-methoxy-3,4-dihydronaphthalen-2(1H)-one (3b) is known
compound26 and was prepared in 98% (17.3 mg) yield accord-
ing to the general procedure C. 1H NMR (500 MHz, CDCl3) δ
7.31 – 7.25 (m, 3H), 7.18 (dd, J = 7.8, 4.1 Hz, 1H), 3.64 (s, 2H),
3.12 (t, J = 6.7 Hz, 2H), 2.66 – 2.56 (m, 2H). 13C NMR (126
MHz, CDCl3) δ 210.6, 158.6, 134.5, 128.8, 128.6, 113.6, 112.4,
55.4, 45.2, 38.6, 27.5.
9-methoxy-3,4-dihydrophenanthren-2(1H)-one
(3k)
is
konwn compound30 and was prepared in 96% yield (21.7 mg)
1
according to the general procedure C. H NMR (500 MHz,
CDCl3) δ 8.34 (d, J = 8.3 Hz, 1H), 8.01 (d, J = 8.5 Hz, 1H), 7.62
(ddd, J = 8.3, 6.9, 1.3 Hz, 1H), 7.54 (dd, J = 11.2, 4.0 Hz, 1H),
6.57 (s, 1H), 4.04 (d, J = 5.1 Hz, 3H), 3.77 (s, 2H), 3.47 (t, J =
6.8 Hz, 2H), 2.82 – 2.71 (m, 2H). 13C NMR (126 MHz, CDCl3)
δ 210.6, 154.6, 132.2, 130.8, 127.1, 124.9, 124.8, 123.2, 122.8,
122.6, 104.5, 55.6, 45.1, 38.7, 24.0.
7-(benzyloxy)-3,4-dihydronaphthalen-2(1H)-one (3c) is
known compound 27 and was prepared in 90% yield (22.7 mg)
1
according to the general procedure C. H NMR (500 MHz,
CDCl3) δ 7.47 – 7.28 (m, 5H), 7.14 (t, J = 6.2 Hz, 1H), 6.84 (dd,
J = 8.3, 2.6 Hz, 1H), 6.76 (d, J = 2.5 Hz, 1H), 5.05 (s, 2H), 3.55
(s, 2H), 3.01 (t, J = 6.7 Hz, 2H), 2.57 – 2.51 (m, 2H).
7-(allyloxy)-3,4-dihydronaphthalen-2(1H)-one (3d) was pre-
pared in 79% yield (16.0 mg) according to the general proce-
dure C. 1H NMR (500 MHz, CDCl3) δ 7.13 (d, J = 8.3 Hz, 1H),
6.77 (dd, J = 8.3, 2.6 Hz, 1H), 6.69 (d, J = 2.5 Hz, 1H), 6.04
(ddt, J = 17.2, 10.5, 5.3 Hz, 1H), 5.40 (dq, J = 17.3, 1.6 Hz, 1H),
5.33 – 5.24 (m, 1H), 4.52 (dt, J = 5.3, 1.5 Hz, 2H), 3.54 (s, 2H),
phenanthren-9-ol (5aa) is known compound31 and was pre-
pared in 95% yield (18.4 mg) according to the general proce-
dure C.1H NMR (500 MHz, CDCl3) δ 7.31 – 7.25 (m, 3H), 7.18
(dd, J = 7.8, 4.1 Hz, 1H), 3.64 (s, 2H), 3.12 (t, J = 6.7 Hz, 2H),
2.66 – 2.56 (m, 2H).
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2-methoxyphenanthren-9-ol (5ab) is known compound32 was
To a dram vial containing 2 mL of DCE was added sequen-
4
5
6
7
8
9
prepared in 99% yield (22.2 mg) according to the general pro-
cedure C.1H NMR (500 MHz, CDCl3) δ 8.56 (t, J = 8.4 Hz, 1H),
8.48 (d, J = 9.0 Hz, 1H), 8.27 (dd, J = 8.1, 1.0 Hz, 1H), 7.71 –
7.61 (m, 1H), 7.57 (ddd, J = 8.1, 7.0, 1.1 Hz, 1H), 7.16 – 7.10
(m, 1H), 7.10 – 7.05 (m, 1H), 6.95 (s, 1H), 5.81 – 5.33 (m, 1H),
3.92 (d, J = 18.1 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 158.7,
150.2, 134.2, 131.7, 127.3, 125.4, 124.5, 124.2, 122.3, 122.2,
121.1, 114.5, 107.3, 106.0, 55.4.
tially the alkyne 1 (0.1 mmol), TMetBuXPhosAuCl (1.4 mg,
0.002 mmol), and NaBArF (2.6 mg, 0.003 mmol). The resulting
4
mixture was stirred at appropriate temperature, and the progress
of the reaction was monitored by TLC. Upon completion, the
reaction mixture was concentrated under vacuum. The residue
was purified by chromatography on silica gel (eluent:hex-
anes/ethyl acetate) to afford the desired 1,2-dihydronaphthalene
4e and 4f.
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2-chlorophenanthren-9-ol (5ac) is known compound33 and
was prepared in 94% yield (21.4 mg) according to the general
procedure C. 1H NMR (500 MHz, CDCl3) δ 8.61 (d, J = 8.9 Hz,
1H), 8.56 (d, J = 8.0 Hz, 1H), 8.35 (d, J = 2.3 Hz, 1H), 7.76 –
7.71 (m, 1H), 7.70 – 7.64 (m, 1H), 7.62 – 7.52 (m, 2H), 7.31 (s,
1H), 7.07 (s, 1H), 5.60 (s, 1H). 13C NMR (126 MHz, CDCl3) δ
148.6, 132.6, 132.6, 129.9, 127.7, 127.2, 126.9, 126.7, 126.3,
124.7, 124.4, 122.5, 122.1, 107.2.
2-fluorophenanthren-9-ol (5ad) was prepared in 74% yield
(15.7 mg) according to the general procedure C. 1H NMR (500
MHz, CDCl3) δ 8.62 – 8.52 (m, 2H), 8.31 (dd, J = 8.1, 1.0 Hz,
1H), 7.70 (ddd, J = 8.3, 5.5, 1.4 Hz, 1H), 7.64 (ddd, J = 8.1, 7.1,
1.1 Hz, 1H), 7.33 (dd, J = 9.7, 2.7 Hz, 1H), 7.23 (ddd, J = 9.0,
8.5, 2.7 Hz, 1H), 6.95 (s, 1H), 5.52 (s, 1H).13C NMR (126 MHz,
CDCl3) δ 162.7, 160.8, 150.6, 134.2 (d, JF-C = 9.2 Hz), 131.4,
127.6, 126.2, 125.0, 124.8 (d, JF-C = 9.1 Hz), 123.3 (d, JF-C = 1.8
Hz), 122.5, 113.0 (d, JF-C = 23.7 Hz), 110.8 (d, JF-C = 21.2 Hz),
105.5 (d, JF-C = 3.6 Hz). HRMS (ESI) m/z calcd for C14H10FO+
(M+H)+ 213.0710, found 213.0706.
4-methylphenanthren-9-ol (5ae) 1-methylphenanthren-9-ol
(5ae’) is known compound34 and was prepared in 71% yield
(14.8 mg) according to the general procedure C. 5ae:5ae’=1:2,
In this 1HNMR, 5ae is 1, 5ae’is 2. 1H NMR (500 MHz, CDCl3)
δ 8.70 (d, J = 8.3 Hz, 1H), 8.67 (d, J = 8.2 Hz, 2H), 8.35 – 8.26
(m, 3H), 7.74 – 7.57 (m, 8H), 7.40 (dd, J = 6.5, 3.6 Hz, 2H),
7.37 (dt, J = 7.4, 3.7 Hz, 2H), 7.21 (s, 1H), 6.99 (s, 2H), 5.71 –
4.77 (m, 4H), 2.66 (s, 3H), 2.59 (s, 6H). 13C NMR (126 MHz,
CDCl3) δ 149.4, 148.8, 135.8, 133.8, 132.8, 131.9, 131.5, 131.2,
130.8, 130.4, 129.4, 128.6, 128.0, 127.2, 127.0, 126.8, 126.6,
126.6, 126.2, 125.7, 125.1, 124.5, 123.8, 123.0, 122.7, 122.4,
122.3, 122.2, 120.7, 106.0, 102.7, 21.9, 20.0.
6-fluorophenanthren-9-ol (5af) was prepared in 75% yield
(15.9 mg) according to the general procedure C. 1H NMR (500
MHz, CDCl3) δ 8.45 (d, J = 8.2 Hz, 1H), 8.32 (dd, J = 9.0, 6.0
Hz, 1H), 8.26 (dd, J = 11.1, 2.5 Hz, 1H), 7.72 – 7.67 (m, 1H),
7.55 (tt, J = 5.5, 2.7 Hz, 1H), 7.49 (ddd, J = 13.5, 7.5, 4.0 Hz,
1H), 7.38 (ddd, J = 8.9, 8.1, 2.5 Hz, 1H), 6.96 (s, 1H), 5.37 (d,
J = 72.8 Hz, 1H). 13C NMR (126 MHz, CDCl3) δ 163.2, 161.2,
149.4, 133.3, 127.6, 126.8, 126.2 (d, JF-C = 4.0 Hz), 125.0 (d,
JF-C = 9.0 Hz), 124.3, 122.8, 122.3 (d, JF-C = 1.5 Hz), 115.3 (d,
JF-C = 23.8 Hz), 107.9 (d, JF-C = 22.5 Hz), 105.3 (d, J JF-C = 2.1
Hz). HRMS (ESI) m/z calcd for C14H10FO+ (M+H)+ 213.0710,
found 213.0710.
6, 7-dimethoxy-1, 2-dihydronaphthalene (4e) is known com-
pound28 and was prepared in 75% yield (14.3 mg) according to
the general procedure D at 60℃. 1H NMR (500 MHz, CDCl3)
δ 6.66 (s, 1H), 6.60 (s, 1H), 6.38 (d, J = 9.6 Hz, 1H), 5.99 – 5.87
(m, 1H), 3.88 (s, 3H), 3.86 (s, 3H), 2.73 (t, J = 8.3 Hz, 2H), 2.29
(tdd, J = 8.1, 4.4, 1.8 Hz, 2H).
5, 6, 7-trimethoxy-1, 2-dihydronaphthalene (4f) is known
compound35 and was prepared in 69% yield (15.2 mg) accord-
1
ing to the general procedure D at 40℃. H NMR (500 MHz,
CDCl3) δ 6.74 (dt, J = 9.8, 1.7 Hz, 1H), 6.52 (s, 1H), 5.99 (dt, J
= 9.7, 4.4 Hz, 1H), 3.95 – 3.84 (m, 10H), 2.75 (dd, J = 12.4, 4.6
Hz, 2H), 2.31 (tdd, J = 8.0, 4.4, 1.8 Hz, 2H).
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/XXXX
Detailed experimental procedures, 1H, 13C and HRMS (PDF)
AUTHOR INFORMATION
Corresponding Author
* E-mail: jikegong@nwsuaf.edu.cn.
Orcid
Kegong Ji: 0000-0001-5707-894X
Author Contributions
‡These authors contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful for the financial support from National Natural Sci-
ence Foundation of China (NSF-21502150, 21402154), the Chi-
nese Universities Scientific Fund (No 2452016093) and Youth
Training Programme of Northwest A&F University (Z111021404)
benzo[b]naphtho[2,1-d]thiophen-5-ol (5ag) was prepared in
92% yield (23.0 mg) according to the general procedure C. 1H
NMR (500 MHz, CDCl3) δ 8.51 (d, J = 8.0 Hz, 1H), 8.35 (d, J
= 8.3 Hz, 1H), 7.94 – 7.70 (m, 3H), 7.31 – 7.25 (m, 3H), 7.05 –
6.81 (m, 2H), 5.67(s,1H). 13C NMR (126 MHz, CDCl3) δ 149.2,
139.6, 136.2, 131.4, 130.5, 130.1, 128.5, 126.6, 126.0, 124.8,
124.6, 124.4, 123.6, 123.2, 122.8, 107.9. HRMS (M+H)+ calcd
for C16H11OS+: 251.0525, found 251.0533.
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terminal alkynes anti-Markovnikov's rule to 1,2-dihydronaph-
thalene 4e and 4f.
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