Silver-promoted oxidative sulfonylation and ring-expansion of vinylcyclopropanes with sodium sulfinates leading to dihydronaphthalene derivatives

Article abstract of DOI:10.1039/d0ob01570a

Silver-promoted sulfonylation and ring-expansion of vinylcyclopropanes with sodium sulfinates is established for the construction of 1-sulfonylmethylated 3,4-dihydronaphthalenes. This sulfonylation process involves a radical pathway, including sulfonyl radical formation, radical addition, ring-opening and cyclization. The 1-sulfonylmethylated 3,4-dihydronaphthalenes can be converted into other useful products.

Full text of DOI:10.1039/d0ob01570a

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DOI: 10.1039/D0OB01570A
ARTICLE
Silver-promoted oxidative sulfonylation and ring-expansion of
vinylcyclopropanes with sodium sulfinates leading to
dihydronaphthalene derivatives
Received 00th January 20xx,
Accepted 00th January 20xx
Pu Chen,†a Quan Zhou,†a Zan Chen,a Yu-Kui Liu,a Yun Liang,b Ke-Wen Tang,*a Yu Liu*ab
DOI: 10.1039/x0xx00000x
www.rsc.org/
Silver-promoted
sulfonylation
and
ring-expansion
of Additionally, sulfonyl chlorides,9,12b sulfonohydrazides,10 sodium
vinylcyclopropanes with sodium sulfinates is established for the sulfinates11 are usually used as sulfonylation reagents in many
construction of 1-sulfonylmethylated 3,4-dihydronaphthalenes. sulfonylation reactions.
This sulfonylation process involves a radical pathway, including
HO
OH
O
R
R
Ar1
R1
Ar1
R1
SO2R
sulfonyl radical formation, radical addition, ring-opening and
cyclization. The 1-sulfonylmethylated 3,4-dihydronaphthalenes
can be converted into other useful products.
Cu(OAc)2, TBPB or air
MeOH, r.t.
Ni-TEEDA, NH4PF6, AcOH
SO2Ar
DMF, H2O, 60 oC, air
path IV
path I
O
SO2
R
R1
O
N
R1
N
H
N
N
H
O
N
O
SO2R
RSO2Na
N
Cu(OAc)2H2O, K2S2O8
CuBr, K2S2O8, CH3NO2, DCE
H2O, 40 oC, 15 h, Ar
Introduction
acetone / H2O (1 : 1)
path II
path V
O
R4
R1
N
R1
O
Dihydronaphthalene structural motifs encounter in numerous
pharmaceuticals and natural products. Dihydronaphthalene
derivatives are an important class of crucial intermediates and
skeletons in organic and pharmaceutical synthesis.1 Accordingly,
considerable effort has been devoted to the development of
efficient strategies for the construction of dihydronaphthalenes. In
recent decades, many strategies have been developed for their
synthesis.2 However, sulfur-containing dihydronaphthalenes,
especially sulfonylated dihydronaphthalenes, possess a series of
unique properties, such as enhanced bioavailability , metabolic
stability, lipophilicity and binding selectivity.3 Thus, development of
O
N
Phth
R2
SO2R
R1
O
R2
R3
PhI(O2CCF3)
2
R1 SO2
R
R3
R4
4CzIPN, Cu(OTf)2
(BuO)2P(O)OH, DMF/MeCN
3 W blue LED, r.t. 12 h
Pd(OAc)2
,
CH3CN, rt
path III
path VI
Scheme
sulfonylation reagents.
1 Selected reactions using sodium sulfinates as
Sodium sulfinates, as a sort of common and stable sulfonyl
sources, are widely used in synthesis of sulfones.11 In recent years,
many sulfonylation methods by using sodium sulfinates as sulfonyl
sources have been developed. In 2015, Taniguchi and coworkers
presented hydroxysulfonylation of alkenes with sulfinate salts (path
I, Scheme 1).11a Wu’s group developed C4-H sulfonylation of 1-
naphthylamine by employing sodium sulfinates as sulfonyl sources
(path II, Scheme 1).11b Zhu et al. described an efficient sulfonylation
and cascade cyclization of homoallenyl amides with sulfinate salts
(path III, Scheme 1).11c Kananovich and coworkers developed
oxidative sulfonylation and ring-opening of cyclopropanol
derivatives with sulfinate salts (path IV, Scheme 1).11d Pan’s group
presented sulfonylation of C(sp2)-H bonds in quinoline N‑oxides by
using sodium sulfinates as sulfonyl sources (path V, Scheme 1).11] Li
et al. reported decarbonylation and sulfonylation of aliphatic
carboxylic esters with sulfinate salts (path VI, Scheme 1).11f
Vinylcyclopropanes (VCPs), accessible three-membered
carbocyclic derivatives, are usually used for constructing
dihydronaphthalene frameworks via ring-opening and cyclization
processes.12 In 2019, our group have presented visible-light-
catalyzed sulfonylation and ring-opening/cyclization of VCPs with
sulfonyl chlorides for the construction of 1-sulfonylmethylated 3,4-
dihydronaphthalenes (Scheme 2a, eq 1).12b However, sulfonyl
efficient
methods
for
constructing
sulfonylated
dihydronaphthalenes are of ongoing interest.
Sulfones are essential synthetic intermediates in agrochemicals,
pharmaceuticals, the materials industry, flame-retardant materials,
and organic synthesis.3-4 Thus, the development of efficient and
convenient methods for the preparation of sulfones derivatives is of
remarkable interest to organic chemists.5-6 The traditional method
for the construction of sulfones is oxidation of thioethers. However,
a lot of functional groups are not compatible with the strong
oxidative conditions. Recently, many sulfonylation strategies have
been established for the synthesis of sulfones.7 The SO2 insertion is
an efficient and simple approach to the synthesis of sulfones.8
a Department of Chemistry and Chemical Engineering, Hunan Institute of Science
and Technology, Yueyang 414006, China, E-mail: lyxtmj_613@163.com
b Key Laboratory of the Assembly and Application of Organic Functional Molecules
of Hunan Province, Hunan Normal University, Changsha, Hunan 410081, China.
† These authors contributed equally to this work.
** Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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chlorides, a class of active substrates, are not stable under common Table 1 Screening of optimal reaction conditionsa
PAPER
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DOI: 10.1039/D0OB01570A
conditions. The storage and transportation of sulfonyl chlorides is
difficult. Additionally, the high price of the photocatalyst is another
disadvantage of this transformation. We also reported the
sulfonylation and ring-expansion of MCPs (methylenecyclopropanes)
with sodium sulfinates for the generation of 2-sulfonylated 3,4-
dihydronaphthalenes (Scheme 2a, eq 2).11g As a continuous work,
we develop silver-promoted oxidative sulfonylation and ring-
expansion of vinylcyclopropanes with sodium sulfinates for the
synthesis of 1-sulfonylmethylated 3,4-dihydronaphthalenes.
Ts
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
toluene, 90 oC, 24 h
SO2Na
+
1a
2a
3aa
Entry
Variation from the standard conditions
Yield (%)b
1
2
none
without AgNO3
81
31
52
40
43
55
46
38
67
73
0
a) Our previous work
3
Ag2O instead of AgNO3
AgOTf instead of AgNO3
AgI instead of AgNO3
AgIO3 instead of AgNO3
Ag2SO4 instead of AgNO3
Ag2CO3 instead of AgNO3
AgNO3 (10 mol%)
SO2R2
Ru(bpy)3Cl2, 2,6-lutidine
1,4-dioxane
4
R2SO2Cl
+
5
R1
(1)
(2)
R1
5 W blue LED light
Ar, 100 oC, 24 h
6
7
R1
8
AgNO3, K2S2O8
toluene, Ar, 80 oC, 36 h
R3SO2Na
+
9
SO2R3
SO2R2
R2
R2
R1
10
11c
12
13
14d
15
16
17
18
19
20
21d
22d
23
24
25
AgNO3 (50 mol%)
without K2S2O8
b) This work
oxone instead of K2S2O8
(NH4)2S2O8 instead of K2S2O8
PhI(OAc)2 instead of K2S2O8
CHP instead of K2S2O8
DTBP instead of K2S2O8
BQ instead of K2S2O8
THF instead of toluene
DCE instead of toluene
MeCN instead of toluene
DMSO instead of toluene
DMF instead of toluene
AcOnBu instead of toluene
at 80 oC
64
69
12
36
58
21
70
66
53
0
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
toluene, Ar, 90 oC, 24 h
R2SO2Na
+
R1
R1
Scheme 2 Sulfonylation and ring-opening/cyclization of three-
membered carbocycles
We began our research by screening reaction conditions for this
sulfonylation/ring-expansion
in
the
presence
of
(1-
0
cyclopropylvinyl)benzene 1a and sodium 4-methylbenzenesulfinate
2a (Table 1). The reaction, which was conducted by using AgNO3 as
44
62
75
80
o
at 100 oC
for 48 h
catalyst, K2S2O8 as oxidant and toluene as solvent at 90 C for 24 h,
could afford the 1-sulfonylmethylated 3,4-dihydronaphthalenes 3aa
in 81% yield (entry 1). The product 3aa could be isolated in 31%
yield when sulfonylation reaction was performed in absence of
AgNO3 (entry 2). This result indicated that AgNO3 was not
indispensable, only facilitated the reaction. Next, a series of other
silver catalysts, including Ag2O, AgOTf, AgI, AgIO3, Ag2SO4 and
Ag2CO3, were investigated. None of them afforded better results
than AgNO3 (entries 3-8). The amount of AgNO3 was tested, 20 mol%
was suitable amount (entries 9-10). The oxidant was essential for
this reaction. Performing the reaction in the absence of K2S2O8
could not give the desired product (entry 11). However, switching
the additives to other oxidants such as oxone, (NH4)2S2O8, PhI(OAc)2,
CHP, DTBP and BQ could not lead to higher reaction yields (entries
12-17). Next, other solvents, such as THF, DCE, MeCN, DMF, DMSO
and AcOnBu, were studied. All of them showed no improvement
(entries 18-23). Among the reaction temperature and time
investigation, the reaction at 90 oC for 24 h was the best choice
(entries 24-26).
We started to study the substrate scope of vinylcyclopropanes 1
in the presence of sodium p-tolylsulfinate 2a, AgNO3, K2S2O8 and
toluene (Table 2). A series of VCPs 1a-q bearing different functional
group on the aryl ring could undergo the sulfonylation and ring-
opening/cyclization process smoothly (products 3aa-qa). VCPs 1b-j
bearing substituents on the para-position of the aryl ring could give
the corresponding products 3ba-ja in moderate to good yields. The
experimental results indicated that the electronic properties of the
substituents affected the reaction yields: the VCPs bearing electron-
26
a
Reaction conditions: 1a (0.2 mmol, 0.1 M), 2a (0.4 mmol, 2
equiv), AgNO3 (6.8 mg, 20 mol%), K2S2O8 (108.1 mg, 2 equiv) and
toluene (2 mL) at 90 oC (oil bath) in an argon atmosphere for 24
h. isolated yield.c Majority of 1a was recovered. Majority of
b
d
1a was decomposed.
withdrawing groups afforded lower yields than those bearing
electron-donating groups. The steric effect of the substituents also
had an important influence on the transformation. The para-
substituted substrates afforded higher yields than those ortho- and
meta-substitued ones. For VCPs 1k-m, the 6-substituted products
3ka’-ma’ could not be obtained due to quite low reaction yields
(products 3ka-ma). VCPs 1r-u bearing disubstituted aryl groups
were suitable substrates (products 3ra-ua). Moreover, halo-
substituted VCPs 1t-u could undergo ring- opening/cyclization
reaction and generate the corresponding halo-substituted 1-
sulfonylmethyl-3,4-dihydronaphthalenes in moderate yields
(products 3ta-ua). The halo-substituted position could provide a
possibility for further modification. VCP 1v bearing a 2-naphthyl
group generated the products 3va and 3va’ in the ratio of 93 : 7.
The total yield is 61%. Heteroaryl-substituted VCPs 1w-y were good
reaction candidates (products 3wa-ya). VCP 1x could furnish the
dehydrogenated product 3xa in 57% yield. This strategy was
applicable to VCP 1z bearing a methyl group at the terminal of
carbon-carbon double bond (product 3za).
Next, we continued to explore the scope of organosulfinates 2
2 | J. Name., 2012, 00, 1-3
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Table 2 The scope of vinylcyclopropanes (1)a
Table 3 The scope of sodium sulfinates (2)a
View Article Online
DOI: 10.1039/D0OB01570A
R2
SO2R2
R2
Ts
AgNO3 (20 mol%)
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
toluene, Ar, 90 oC, 24 h
K2S2O8 (2 equiv)
R2SO2Na
SO2Na
R1
+
+
R1
toluene, Ar, 90 oC, 24 h
Cl
Cl
1
2a
3
2
1h
3
Ts
Ts
Ts
Ts
R
R
OMe
O
O
S
O
S
S
O
O
R
O
R
3aa
OMe
R = H,
, 81%
3oa
R
R = OMe,
R = OBn,
R = Br,
, 77%
3pa
, 62%
3ba
R = OMe,
R = OBn,
, 87%
3ka
Cl
R = OMe,
R = OBn,
R = Me,
, 80%
3ra
, 65%
Cl
Cl
3qa
R = Me, 3hl, 66%
, 58%
3la
, 76%
3ca
, 85%
3hk
, 74%
3hb
R = OMe,
, 80%
3hm
R = Cl,
, 70%
3ma
, 70%
t
3da
R = Me,
R = Ph,
, 82%
, 77%
, 75%
3hc
R = Bu,
R = H,
R = NO2,
R = CN,
R = CF3,
R = F,
R = Cl,
R = Br,
, 75%
[b]
S
3na
R = Cl,
, 68%
3ea
3fa
3hd
, 81%
O
O
S
Ts
t
3he
, 46%
R = Bu,
Ts
Ts
S
Br
Br
3hf
, 55%
O
3ga
R = F,
R = Cl,
R = Br,
, 71%
O
3hg
, 58%
, 67%
3ha
, 76%
, 70%
3hh
3ia
MeO
3hi
3hj
, 73%
, 70%
Cl
Cl
F
3ja
R = CF3,
, 57%
Ts
Cl
OMe
3hn, 45%
3ho
, 40%
3ua
, 63%
3ta
, 58%
N
3sa
, 52%
O
S
Ts
O
S
Ts
Ts
Ts
CF3
Bn
O
O
S
N
[c]
Cl
3va
, 61%
Cl
3wa
3xa, 57%
3ya, 66%
3za, 48%
, 45%
[b]
[b]
3hq
, 0%
3hp
, 0%
a
Reaction conditions: Reaction conditions: 1 (0.2 mmol, 0.1
M), 2a (0.4 mmol, 2 equiv), AgNO3 (6.8 mg, 20 mol%), K2S2O8
(108.1 mg, 2 equiv) and toluene (2 mL) at 90 C (oil bath) in an
argon atmosphere for 24 h. The ratio of 3na (8-Cl)/3na’ (6-Cl)
is 7 : 3 as determined by H NMR analysis of the product. The
ratio of 3va [1-(tosylmethyl)-3,4-dihydrophenanthrene]/3va’ [4-
(tosylmethyl)-1,2-dihydroanthracene] is 93 : 7 as determined by
1H NMR analysis of the product.
a
Reaction conditions: 1h (0.2 mmol, 0.1 M), 2 (0.4 mmol, 2
equiv), AgNO3 (6.8 mg, 20 mol%), K2S2O8 (108.1 mg, 2 equiv)
o
o
and toluene (2 mL) at 90 C (oil bath) in an argon atmosphere
b
for 24 h. c Majority of starting material 1h was recovered.
1
c
studied.11c,13f The oxidation of product 3ha under the action of m-
CPBA could furnish 6-chloro-1-hydroxy-1-(tosylmethyl)-3,4-
dihydronaphthalen-2(1H)-one 6 in 63% yield (path I, Sheme 3e).11c
The dehydrogenated product 7 could be obtained in 56% yield
under the oxidative action of DDQ (path II, Sheme 3e).13f
in the presence of VCPs 1h, AgNO3, K2S2O8 and toluene (Table 3). A
number of sodium arylsulfinates 1b-m with either electron-
donating or electron-withdrawing substituents on the aromatic ring
all could undergo sulfonylation and ring-opening/cyclization
reactions affording the corresponding 1-sulfonylmethylated 3,4-
dihydronaphthalenes 3hb–hm in satisfactory yields. Especially,
sodium 4-nitrobenzenesulfinate 2e bearing strong electron-
withdrawing substituent was compatible with the standard
conditions (product 3he). Sodium naphthyl-1-sulfinate 2n and
sodium thienyl-2-sulfinate 2o were suitable substrates (products
3hn-ho). However, sodium alkyl sulfinates 2p and 2q could not
tolerate this reaction conditions (products 3hp-hq).
To gain deep understanding of the cascade reaction, several
mechanistic experiments were conducted (Scheme 3).12-13 The
reaction of VCP 1aa with 2a under the standard conditions could
not give the target product 3aaa, affording the coupling product 4
in 38% yield (Scheme 3a).13g VCP 1ab bearing an aryl group and two
ester groups on the cyclopropane skeleton could not furnish the
corresponding product 3aba (Scheme 3b).12i The yields of
sulfonylation and ring-opening/cyclization reactions decreased
obviously when the radical inhibitors such as BHT, hydroquinone
and TEMPO were individually added into the reactions under the
best reaction conditions (Scheme 3c). Adding 2 equiv of 1,1-
diphenylethene into the reaction gave (2-tosylethene-1,1-
diyl)dibenzene 5 in 53% yield (Scheme 3d). These results suggested
that a radical process was involved in the transformation.13a-e Next,
the application of sulfonylation/cyclization products was
Ts
Ts
S
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
+
(a)
+ TsOH
toluene, Ar, 90 oC, 24 h
+
O2
N
O2
N
SO2Na
2a
1aa
3aaa
, 0%
4
, 38%
Ts
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
Ph
(b)
+
toluene, Ar, 90 oC, 24 h
EtO2
C
Ph
CO2Et
CO2Et
SO2Na
2a
EtO2
C
1ab
3aba
, 0%
Ts
3ab
81%
31%
14%
8%
quencher
-------
BHT
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
toluene, Ar, 90 oC, 24 h
+
(c)
hydroquinone
TEMPO
SO2Na
1a
2a
3aa
Ts
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
toluene, Ar, 90 oC, 24 h
1,1-diphenylethene
Ph
+
(d)
(e)
+
Ph
Ts
5
, 53%
SO2Na
2a
1a
3aa
, 11%
Ts
Ts
Ts
HO
DDQ (2 equiv)
PhCl (3 mL)
Ar, 80 oC, 3 h
m-CPBA (2 equiv)
O
DCM (3 mL)
Ar, rt, 10 h
Cl
Cl
Cl
path I
path II
3ha
7
, 56%
6
, 63%
Scheme 3 Control experiments.
Based on these results and previous reported literature,13-15
a
possible mechanism has been proposed for the silver-promoted
sulfonylation and ring-expansion of vinylcyclopropanes with sodium
sulfinates (Scheme 4). First, Sodium sulfinate 2a undergoes
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PAPER
oxidation by K2S2O8 to furnish the sulfonyl radical A. The addition of q = quartet, m = multiplet, and br = broad. Analytical TLC was
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intermediate A to the carbon-carbon double bond in VCP 1a gives performed on precoated silica gel platesD. OHI:ig10h.-1r0e3s9o/lDu0tiOoBn01m57a0sAs
the benzyl radical B, which delivers the alkyl radical C via cleavage spectra (HRMS) were obtained on an Agilent mass spectrometer
of carbon-carbon σ-bond. The intermediate
C goes through using ESI-TOF (electrospray ionization-time of flight).
intramolecular radical cyclization to afford intermediate D, which
General procedure for the Sulfonylation/Ring-Expasion Reaction:
•−
proceeds oxidation and deprotonation by SO4 to generate the
•−
2-
To a Schlenk tube were added VCPs 1 (0.2 mmol, 0.1 M), sodium
sulfinates 2 (0.4 mmol, 2 equiv), AgNO3 (6.8 mg, 20 mol %), K2S2O8
(108.1 mg, 2 equiv) and toluene (2 mL). Then, the reaction was
terminal product 3aa (path I). SO4 was formed from S2O8
,
accompanying with oxidizing Ag(I) into Ag(II).14-15 The oxidation and
deprotonation of the radical D can also be achieved by the
oxidation of Ag(II), recovering Ag(II) to Ag(I) (path II).11g
o
stirred at 90 C (oil bath temperature) under an argon atmosphere
for 24 h until complete consumption of the starting material was
observed by TLC and/or GC-MS analysis. Upon completion, the
reaction mixture was filtered, and the organic layer was dried over
Na2SO4. The solvent was removed, and the crude product was
purified by column chromatography (petroleum ether/ethyl acetate,
10 : 1) to provide the desired products 3. A scaled-up experiment
was carried in the presence of VCP 1a (1 g, 6.94 mmol), sodium p-
tolylsulfinate 2a (13.86 mmol, 2 equiv), AgNO3 (235.4 mg, 20 mol %),
Ts
Ts
ring-opening
radical addition
1a
B
4-MeC6H4SO2
A
C
K2S2O8
2-
SO4
S2O8
4-MeC6H4SO2Na
2a
o
K2S2O8 (3.75 g, 2 equiv) and toluene (40 mL) at 90 C under argon
atmosphere for 72 h successfully afforded the desired product 3aa
in 63% yield (1301.5 mg).
Ag(II)
Ag(I)
Ts
Ts
4-(Tosylmethyl)-1,2-dihydronaphthalene (3aa): yellow solid; mp
72.0-72.5 oC (uncorrected); 1H NMR (400 MHz, CDCl3) : 7.67 (d, J =
8.4 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.14-7.06 (m, 4H), 5.91 (t, J = 4.8
Hz, 1H ), 4.20 (s, 2H), 2.69 (t, J = 8.4 Hz, 2H), 2.38 (s, 3H), 2.25-2.20
(m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.5, 135.9, 135.3, 134.8,
132.6, 129.4, 128.7, 127.6, 127.2, 126.3, 125.8, 123.1, 59.9, 27.7,
23.3, 21.6; IR (KBr, cm-1): 3066, 1617, 1591, 1560, 1477, 1355, 1147;
HRMS (ESI-TOF) m/z: C18H19O2S (M + H)+ calcd for 299.1100, found
299.1106.
path II
path I
-H+
H
3aa
D
SO4
HSO4
Scheme 4 Proposed mechanism.
Conclusion
7-Methoxy-4-(tosylmethyl)-1,2-dihydronaphthalene (3ba): yellow
oil; H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.4 Hz, 2H), 7.22 (d, J =
In conclusion, we have developed an important and convenient
strategy for the synthesis of 1-sulfonylmethylated 3,4-
dihydronaphthalenes via silver-promoted sulfonylation and ring-
expansion of vinylcyclopropanes with sodium sulfinates. This
sulfonylation process involves a radical pathway, including sulfonyl
radical formation, radical addition, ring-opening and cyclization. The
1-sulfonylmethylated 3,4-dihydronaphthalenes can be converted
into other useful products. Further research on the application and
mechanism of sulfonylation reaction are currently underway in our
laboratory.
1
8.0 Hz, 2H), 7.06 (t, J = 8.0 Hz, 1H), 6.81 (d, J = 7.6 Hz, 1H), 6.75 (d, J
= 8.4 Hz, 1H ), 5.87 (t, J = 4.8 Hz, 1H ), 4.19 (s, 2H), 3.82 (s, 3H), 2.69
(t, J = 8.0 Hz, 2H), 2.39 (s, 3H), 2.21-2.16 (m, 2H); 13C{1H}NMR (100
MHz, CDCl3) δ: 155.9, 144.5, 135.3, 135.0, 133.7, 129.3, 128.7, 126.4,
125.7, 123.9, 116.2, 109.9, 60.3, 55.5, 22.7, 21.6, 19.4; IR (KBr, cm-1):
3069, 1609, 1584, 1541, 1475, 1343, 1125; HRMS (ESI-TOF) m/z:
C19H21O3S (M + H)+ calcd for 329.1206, found 329.1211.
7-(Benzyloxy)-4-(tosylmethyl)-1,2-dihydronaphthalene
(3ca):
yellow oil; 1H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.44-
7.38 (m, 4H), 7.36-7.32 (m, 1H), 7.23 (d, J = 8.4 Hz, 2H), 7.11 (d, J =
8.4 Hz, 1H ), 6.74-6.69 (m, 2H ), 5.72 (t, J = 4.8 Hz, 1H ), 5.03 (s, 2H),
4.17 (s, 2H), 2.66 (t, J = 7.6 Hz, 2H), 2.39 (s, 3H), 2.21-2.16 (m, 2H);
13C{1H}NMR (100 MHz, CDCl3) δ: 158.0, 144.5, 137.8, 136.9, 135.3,
132.3, 129.4, 128.7, 128.6, 128.0, 127.4, 126.0, 125.4, 124.6, 114.7,
111.6, 69.9, 60.2, 28.2, 23.2, 21.6; IR (KBr, cm-1): 3057, 1622, 1593,
1569, 1476, 1326, 1141; HRMS (ESI-TOF) m/z: C25H25O3S (M + H)+
calcd for 405.1519, found 405.1527.
Experimental
General methods
All reactions were carried out with magnetic stirring and in dried
glassware. Standard syringe techniques were applied for transfer of
dry solvents. All reagents and solvents were commercially available
and used without any further purification unless specified. Proton
(1H NMR) and carbon (13C NMR) nuclear magnetic resonance
spectra were recorded at 400 MHz and 100MHz, respectively. The
chemical shifts are given in parts per million (ppm) on the delta (δ)
7-Methyl-4-(tosylmethyl)-1,2-dihydronaphthalene (3da): yellow
1
oil; H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.23 (d, J =
8.0 Hz, 2H), 7.05 (t, J = 8.0 Hz, 1H), 6.91 (d, J = 4.0 Hz, 2H), 5.80 (t, J
= 4.8 Hz, 1H ), 4.18 (s, 2H), 2.65 (t, J = 8.0 Hz, 2H), 2.39 (s, 3H), 2.28
(s, 3H), 2.22-2.17 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.5,
137.1, 135.8, 135.3, 133.7, 130.0, 129.4, 128.7, 128.4, 126.9, 125.7,
123.2, 60.0, 27.7, 23.4, 21.6, 21.1; IR (KBr, cm-1): 3061, 1615, 1590,
1
scale. The solvent peak was used as a reference value, for H NMR:
TMS = 0.00 ppm, for 13C NMR: CDCl3 = 77.00 ppm. The following
abbreviations were used to explain multiplicities: s = singlet, d =
doublet, dd = doublet of doublet, t = triplet, td = triplet of doublet,
4 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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1562, 1481, 1336, 1145; HRMS (ESI-TOF) m/z: C19H21O2S (M + H)+ Hz, 1C), 59.8, 27.5, 23.0, 21.5; 19F NMR (282 MHz, CDCl3) : -62.6 (s,
View Article Online
-1
DOI: 10.1039/D0OB01570A
calcd for 313.1257, found 313.1268.
3F); IR (KBr, cm ): 3059, 1614, 1588, 1564, 1473, 1348, 1155; HRMS
7-Phenyl-4-(tosylmethyl)-1,2-dihydronaphthalene (3ea): yellow (ESI-TOF) m/z: C19H18F3O2S (M + H)+ calcd for 367.0974, found
o
1
solid; mp 60.0-60.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 367.0982.
7.70 (d, J = 8.4 Hz, 2H), 7.57 (t, J = 7.2 Hz, 2H), 7.43 (t, J = 8.0 Hz, 8-Methoxy-4-(tosylmethyl)-1,2-dihydronaphthalene (3ka): yellow
1
2H), 7.36-7.32 (m, 3H), 7.22 (d, J = 8.4 Hz, 3H ), 5.91 (t, J = 4.8 Hz, oil; H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.22 (d, J =
1H ), 4.23 (s, 2H), 2.77 (t, J = 8.0 Hz, 2H), 2.37 (s, 3H), 2.30-2.25 (m, 8.0 Hz, 2H), 7.06 (t, J = 8.0 Hz, 1H), 6.81 (d, J = 7.6 Hz, 1H), 6.75 (d, J
2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.6, 140.6, 140.0, 136.3, = 8.4 Hz, 1H ), 5.89 (t, J = 4.8 Hz, 1H ), 4.19 (s, 2H), 3.81 (s, 3H), 2.69
135.3, 134.8, 131.8, 129.4, 128.7, 128.7, 127.3, 126.9, 126.3, 125.6, (t, J = 8.4 Hz, 2H), 2.38 (s, 3H), 2.21-2.15 (m, 2H); 13C{1H}NMR (100
125.0, 123.7, 60.0, 27.9, 23.4, 21.6; IR (KBr, cm-1): 3055, 1611, 1581, MHz, CDCl3) δ: 155.9, 144.4, 135.3, 135.0, 133.7, 129.3, 128.7, 126.3,
1550, 1470, 1318, 1136; HRMS (ESI-TOF) m/z: C24H23O2S (M + H)+ 125.7, 123.9, 116.2, 109.9, 60.3, 55.5, 22.7, 21.6, 19.4; IR (KBr, cm-1):
calcd for 375.1413, found 375.1419.
7-(tert-Butyl)-4-(tosylmethyl)-1,2-dihydronaphthalene
yellow oil; 1H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.20 8-(Benzyloxy)-4-(tosylmethyl)-1,2-dihydronaphthalene
3063, 1605, 1585, 1569, 1467, 1322, 1130; HRMS (ESI-TOF) m/z:
(3fa): C19H21O3S (M + H)+ calcd for 329.1206, found 329.1211.
(3la):
(d, J = 8.0 Hz, 2H), 7.08-7.03 (m, 3H), 5.85 (t, J = 4.8 Hz, 1H ), 4.18 (s, yellow solid; mp 61.0-61.5 oC (uncorrected); 1H NMR (400 MHz,
2H), 2.69 (t, J = 8.0 Hz, 2H), 2.37 (s, 3H), 2.25-2.20 (m, 2H), 1.28 (s, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.45-7.38 (m, 4H), 7.35 (t, J = 2.0 Hz,
9H); 13C{1H}NMR (100 MHz, CDCl3) δ: 150.3, 144.4, 135.5, 135.4, 1H), 7.21 (d, J = 8.0 Hz, 2H), 7.04 (t, J = 8.0 Hz, 1H ), 6.83-6.80 (m,
133.8, 130.0, 129.3, 128.7, 125.6, 124.7, 123.1, 122.9, 60.0, 34.4, 2H ), 5.89 (t, J = 4.8 Hz, 1H ), 5.06 (s, 2H), 4.19 (s, 2H), 2.77 (t, J = 8.0
31.2, 28.1, 23.5, 21.5; IR (KBr, cm-1): 3051, 1610, 1586, 1558, 1469, Hz, 2H), 2.37 (s, 3H), 2.22-2.17 (m, 2H); 13C{1H}NMR (100 MHz,
1322, 1153; HRMS (ESI-TOF) m/z: C22H27O2S (M + H)+ calcd for CDCl3) δ: 155.1, 144.5, 137.3, 135.3, 135.1, 133.8, 129.3, 128.7,
355.1726, found 355.1733.
128.5, 127.8, 127.2 (2C), 126.3, 125.7, 124.4, 111.5, 70.2, 60.2, 22.7,
7-Fluoro-4-(tosylmethyl)-1,2-dihydronaphthalene (3ga): yellow 21.5, 19.6; IR (KBr, cm-1): 3069, 1615, 1592, 1556, 1470, 1351, 1137;
o
1
solid; mp 94.0-94.5 C (uncorrected); H NMR (400 MHz, CDCl3) : HRMS (ESI-TOF) m/z: C25H25O3S (M + H)+ calcd for 405.1519, found
7.67 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.14-7.10 (m, 1H), 405.1527.
6.82-6.75 (m, 2H), 5.85 (t, J = 4.8 Hz, 1H ), 4.17 (s, 2H), 2.68 (t, J = 8-Methyl-4-(tosylmethyl)-1,2-dihydronaphthalene (3ma): yellow
1
8.0 Hz, 2H), 2.40 (s, 3H), 2.24-2.19 (m, 2H); 13C{1H}NMR (100 MHz, oil; H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.22 (d, J =
CDCl3) δ: 161.7 (d, J = 245.6 Hz, 1C), 144.7, 138.5 (d, J = 7.7 Hz, 1C), 8.4 Hz, 2H), 7.04-6.99 (m, 3H), 5.89 (t, J = 4.8 Hz, 1H ), 4.20 (s, 2H),
135.2, 133.9 (d, J = 2.1 Hz, 1C), 129.4, 128.9, 128.6, 125.1, 124.9 (d, 2.63 (t, J = 8.0 Hz, 2H), 2.39 (s, 3H), 2.25 (s, 3H), 2.23-2.19 (m, 2H);
J = 8.3 Hz, 1C), 114.7 (d, J = 31.5 Hz, 1C), 112.7 (d, J = 21.2 Hz, 1C), 13C{1H}NMR (100 MHz, CDCl3) δ: 144.4, 135.5, 134.8, 134.3, 134.2,
60.1, 27.9, 23.0, 21.6; 19F NMR (282 MHz, CDCl3) : -114.7 (s, 1F); IR 132.5, 129.5, 129.3, 128.7, 126.0, 125.6, 121.3, 60.3, 23.4, 23.0,
(KBr, cm-1): 3065, 1613, 1594, 1561, 1478, 1317, 1144; HRMS (ESI- 21.6, 19.8; IR (KBr, cm-1): 3063, 1621, 1594, 1561, 1462, 1346, 1152;
TOF) m/z: C18H18FO2S (M + H)+ calcd for 317.1006, found 317.1013.
HRMS (ESI-TOF) m/z: C19H21O2S (M + H)+ calcd for 313.1257, found
7-Chloro-4-(tosylmethyl)-1,2-dihydronaphthalene (3ha): yellow 313.1268.
solid; mp 105.0-105.5 oC (uncorrected); 1H NMR (400 MHz, CDCl3) : 8-Chloro-4-(tosylmethyl)-1,2-dihydronaphthalene (3na) and 6-
7.66 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 5.6 Hz, Chloro-4-(tosylmethyl)-1,2-dihydronaphthalene (3na’): yellow oil;
3H), 5.90 (t, J = 4.8 Hz, 1H), 4.16 (s, 2H), 2.67 (t, J = 4.0 Hz, 2H), 2.40 1H NMR (400 MHz, CDCl3) : 7.68-7.65 (m, 2H), 7.25-7.17 (m, 2.7H),
(s, 3H), 2.25-2.19 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.8, 7.09-6.99 (m, 2H), 6.81 (d, J = 2.0 Hz, 0.3H ), 6.10 (t, J = 4.8 Hz,
137.8, 135.2, 135.0, 132.6, 131.6, 129.5, 128.6, 127.6, 126.3, 125.2, 0.3H ), 5.94 (t, J = 4.8 Hz, 0.7H ), 4.18 (s, 1.4H), 4.14 (s, 0.6H), 2.83
124.5, 59.9, 27.6, 23.1, 21.6; IR (KBr, cm-1): 3062, 1610, 1588, 1566, (t, J = 8.0 Hz, 1.4H), 2.67 (t, J = 8.0 Hz, 0.6H), 2.38 (d, J = 9.4 Hz, 3H),
1474, 1339, 1135; HRMS (ESI-TOF) m/z: C18H18ClO2S (M + H)+ calcd 2.29-2.22 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.9, 144.7,
for 333.0711, found 333.0719.
136.2, 135.6 (2C), 135.2, 134.6, 134.2, 133.6, 133.1, 129.5 (2C),
7-Bromo-4-(tosylmethyl)-1,2-dihydronaphthalene (3ia): yellow 129.4 (2C), 128.7 (2C), 128.6 (2C), 128.3, 126.8, 125.5, 125.2, 123.1,
o
1
solid; mp 90.0-90.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 121.9, 60.1, 59.9, 27.1, 23.9, 23.2, 22.6, 21.6, 21.5; IR (KBr, cm-1):
7.66 (d, J = 8.4 Hz, 2H), 7.25-7.19 (m, 4H), 6.99 (d, J = 8.0 Hz, 1H), 3067, 1627, 1581, 1553, 1459, 1336, 1149; HRMS (ESI-TOF) m/z:
5.92 (t, J = 4.8 Hz, 1H ), 4.16 (s, 2H), 2.67 (t, J = 8.0 Hz, 2H), 2.40 (s, C18H18ClO2S (M + H)+ calcd for 333.0711, found 333.0719.
3H), 2.24-2.19 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.8, 5-Methoxy-4-(tosylmethyl)-1,2-dihydronaphthalene (3oa): yellow
o
1
138.1, 135.2, 135.2, 131.6, 130.5, 129.5, 129.3, 128.6, 125.3 124.8, solid; mp 95.0-95.5 C (uncorrected); H NMR (400 MHz, CDCl3) :
120.9, 59.9, 27.5, 23.1, 21.6; IR (KBr, cm-1): 3056, 1607, 1592, 1569, 7.51 (d, J = 8.0 Hz, 2H), 7.05 (d, J = 8.0 Hz, 2H), 7.00 (t, J = 8.0 Hz,
1481, 1333, 1141; HRMS (ESI-TOF) m/z: C18H18BrO2S (M + H)+ calcd 1H), 6.69 (d, J = 7.2 Hz, 1H), 6.46 (d, J = 8.4 Hz, 1H ), 6.04 (t, J = 4.8
for 377.0205, found 377.0214.
Hz, 1H ), 4.68 (s, 2H), 3.66 (s, 3H), 2.58 (t, J = 8.0 Hz, 2H), 2.30 (s, 3H),
4-(Tosylmethyl)-7-(trifluoromethyl)-1,2-dihydronaphthalene (3ja): 2.13-2.08 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 155.4, 143.9,
white solid; mp 119.0-119.5 oC (uncorrected); 1H NMR (400 MHz, 139.3, 136.2, 135.5, 128.7, 128.4, 127.7, 125.7, 121.3, 120.2, 109.4,
CDCl3) : 7.66 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 9.2 Hz, 2H), 7.22-7.17 62.6, 54.9, 29.0, 22.9, 21.5; IR (KBr, cm-1): 3056, 1610, 1590, 1553,
(m, 3H), 6.06 (t, J = 4.8 Hz, 1H ), 4.21 (s, 2H), 2.76 (t, J = 8.0 Hz, 2H), 1450, 1320, 1143; HRMS (ESI-TOF) m/z: C19H21O3S (M + H)+ calcd for
2.37 (s, 3H), 2.31-2.26 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 329.1206, found 329.1211.
144.9, 137.3, 136.5, 135.9, 135.1, 129.5, 128.7, 128.6, 125.3, 124.2 5-(Benzyloxy)-4-(tosylmethyl)-1,2-dihydronaphthalene
(3pa):
(q, J = 3.7 Hz, 1C), 124.0 (q, J = 270.4 Hz, 1C), 123.7, 123.2 (q, J = 3.7 yellow oil; 1H NMR (400 MHz, CDCl3) : 7.47-7.36 (m, 7H), 7.08 (d, J
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J. Name., 2013, 00, 1-3 | 5
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= 8.0 Hz, 2H), 7.02 (t, J = 8.0 Hz, 1H), 6.74 (d, J = 7.2 Hz, 1H), 6.61 (d, 1618, 1580, 1554, 1478, 1320, 1139; HRMS (ESI-TOF) m/z:
View Article Online
J = 8.0 Hz, 1H ), 5.98 (t, J = 4.8 Hz, 1H ), 4.92 (s, 2H), 4.61 (s, 2H), C18H17BrFO2S (M + H)+ calcd for 395.0111, foDuOndI: 1309.150.0319/1D80.OB01570A
2.58 (t, J = 8.0 Hz, 2H), 2.34 (s, 3H), 2.12-2.07 (m, 2H); 13C{1H}NMR 1-(Tosylmethyl)-3,4-dihydrophenanthrene
(3va)
and
4-
(100 MHz, CDCl3) δ: 154.9, 143.9, 139.5, 136.5, 136.3, 135.6, 128.8, (Tosylmethyl)-1,2-dihydroanthracene (3va’): yellow solid; mp 66.0-
o
1
128.7, 128.4, 128.2, 127.9, 127.8, 125.7, 121.7, 120.5, 110.7, 70.5, 66.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 8.02 (d, J = 8.4
62.4, 29.0, 23.0, 21.5; IR (KBr, cm-1): 3064, 1616, 1596, 1559, 1473, Hz, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.65 (d, J = 8.0 Hz, 2H), 7.58 (d, J =
1345, 1130; HRMS (ESI-TOF) m/z: C25H25O3S (M + H)+ calcd for 8.4 Hz, 1H), 7.49 (t, J = 1.2 Hz, 1H), 7.44 (t, J = 0.8 Hz, 1H), 7.33 (d, J
405.1519, found 405.1527.
= 8.4 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H ), 6.08 (t, J = 4.8 Hz, 0.1H ), 6.02
5-Bromo-4-(tosylmethyl)-1,2-dihydronaphthalene (3qa): white (t, J = 4.8 Hz, 0.9H ), 4.32 (d, J = 10.4 Hz, 2H), 3.12 (t, J = 8.4 Hz,
o
1
solid; mp 85.0-85.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 1.9H), 2.87 (t, J = 8.4 Hz, 0.1H), 2.38-2.32 (m, 2H), 2.28 (s, 2.8H),
7.55 (d, J = 8.4 Hz, 2H), 7.17 (t, J = 0.8 Hz, 1H), 7.07 (d, J = 8.0 Hz, 2.28 (s, 0.2H) ; 13C{1H}NMR (100 MHz, CDCl3) δ: 144.6, 135.1, 134.2,
2H), 7.03 (d, J = 7.6 Hz, 1H), 6.85 (t, J = 7.6 Hz, 1H ), 6.47 (t, J = 5.6 132.9, 131.6, 131.1, 129.8, 129.3, 128.7, 128.4, 126.4, 126.1, 126.1,
Hz, 1H ), 4.87 (s, 2H), 2.60 (t, J = 7.6 Hz, 2H), 2.31 (s, 3H), 2.15-2.10 125.4, 123.5, 121.7, 60.3, 23.0, 22.7, 21.4; IR (KBr, cm-1): 3068, 1622,
(m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.2, 141.7, 140.0, 135.4, 1596, 1547, 1470, 1348, 1137; HRMS (ESI-TOF) m/z: C22H21O2S (M +
132.8, 132.7, 129.1, 128.2, 127.7, 126.5, 126.3, 119.2, 60.6, 29.9, H)+ calcd for 349.1257, found 349.1265.
23.0, 21.5; IR (KBr, cm-1): 3067, 1613, 1588, 1549, 1475, 1353, 1134; 7-(Tosylmethyl)-4,5-dihydrobenzo[b]thiophene (3wa): gray solid;
o
1
HRMS (ESI-TOF) m/z: C18H18BrO2S (M + H)+ calcd for 377.0205, mp 100.0-100.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 7.70
found 377.0214.
(d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.0 Hz, 1H), 7.07 (d, J = 2.8 Hz, 1H),
5,8-Dimethoxy-4-(tosylmethyl)-1,2-dihydronaphthalene
(3ra): 6.82 (d, J = 3.2 Hz, 2H), 6.19 (t, J = 7.6 Hz, 1H ), 4.29 (s, 2H), 3.54 (t, J
yellow oil; 1H NMR (400 MHz, CDCl3) : 7.51 (d, J = 8.0 Hz, 2H), 7.07 = 5.6 Hz, 2H), 2.59-2.54 (m, 2H), 2.40 (s, 3H); 13C{1H}NMR (100 MHz,
(d, J = 8.0 Hz, 2H), 6.65 (d, J = 8.8 Hz, 1H), 6.44 (s, 1H), 6.03 (t, J = 4.8 CDCl3) δ: 144.9, 144.0, 135.8, 131.3, 129.6, 128.5, 127.3, 124.4,
Hz, 1H ), 4.69 (s, 2H), 3.77 (d, J = 0.8 Hz, 3H), 3.65 (d, J = 0.4 Hz, 3H), 124.4, 124.4, 58.1, 43.3, 32.2, 21.6; IR (KBr, cm-1): 3052, 1638, 1590,
2.58 (t, J = 8.0 Hz, 2H), 2.32 (s, 3H), 2.08-2.03 (m, 2H); 13C{1H}NMR 1566, 1480, 1315, 1123; HRMS (ESI-TOF) m/z: C16H17O2S2 (M + H)+
(100 MHz, CDCl3) δ: 150.1, 150.0, 143.9, 136.6, 135.4, 128.7, 128.5, calcd for 305.0665, found 305.0670.
127.5, 125.7, 122.5, 110.4, 108.9, 62.4, 56.1, 55.3, 22.5, 21.5, 20.7; 8-(Tosylmethyl)isoquinoline (3xa): white solid; mp 175.0-175.5 oC
1
IR (KBr, cm-1): 3058, 1621, 1583, 1555, 1463, 1341, 1147; HRMS (uncorrected); H NMR (400 MHz, CDCl3) : 8.91-8.90 (m, 1H), 8.27
(ESI-TOF) m/z: C20H23O4S (M + H)+ calcd for 359.1312, found (d, J = 8.8 Hz, 1H), 8.10 (d, J = 8.4 Hz, 1H), 7.59-7.55 (m, 1H), 7.46 (d,
359.1318.
J = 8.4 Hz, 2H), 7.39-7.36 (m, 1H), 7.19 (t, J = 7.6 Hz, 3H ), 4.78 (s,
(3sa): 2H), 2.38 (s, 3H); 13C{1H}NMR (100 MHz, CDCl3) δ: 150.4, 148.3,
7,8-Dimethoxy-4-(tosylmethyl)-1,2-dihydronaphthalene
yellow oil; 1H NMR (400 MHz, CDCl3) : 7.67 (d, J = 8.0 Hz, 2H), 7.23 145.0, 134.5, 132.3, 131.0, 130.9, 129.6, 128.6, 128.5, 127.4, 125.1,
(d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.4 Hz, 1H), 6.66 (d, J = 8.4 Hz, 1H), 121.3, 59.3, 21.6; IR (KBr, cm-1): 3065, 1633, 1589, 1557, 1469, 1317,
5.72 (t, J = 4.8 Hz, 1H ), 4.17 (s, 2H), 3.84 (s, 3H), 3.77 (s, 3H), 2.73 (t, 1154; HRMS (ESI-TOF) m/z: C17H16NO2S (M + H)+ calcd for 298.0896,
J = 8.0 Hz, 2H), 2.39 (s, 3H), 2.17-2.14 (m, 2H); 13C{1H}NMR (100 found 298.0903.
MHz, CDCl3) δ: 152.2, 145.5, 144.4, 135.3, 132.6, 130.0, 129.3, 128.7, 8-(Tosylmethyl)-5,6-dihydroquinoline (3ya): white solid; mp 118.0-
o
1
126.5, 125.5, 119.6, 109.0, 60.4, 60.3, 55.6, 22.8, 21.6, 20.4; IR (KBr, 118.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 8.09-8.07 (m,
cm-1): 3055, 1628, 1591, 1551, 1468, 1332, 1129; HRMS (ESI-TOF) 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 2.8 Hz, 1H), 7.12 (t, J = 0.4
m/z: C20H23O4S (M + H)+ calcd for 359.1312, found 359.1318.
Hz, 2H), 6.91-6.88 (m, 1H ), 6.49 (t, J = 4.4 Hz, 1H ), 4.56 (s, 2H), 2.76
5-Bromo-7-chloro-4-(tosylmethyl)-1,2-dihydronaphthalene (3ta): (t, J = 8.0 Hz, 2H), 2.40-2.35 (m, 2H), 2.30 (d, J = 6.4 Hz, 3H);
white solid; mp 103.0-103.5 oC (uncorrected); 1H NMR (400 MHz, 13C{1H}NMR (100 MHz, CDCl3) δ: 151.1, 146.4, 144.0, 137.3, 134.4,
CDCl3) : 7.55 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 2.0 Hz, 1H), 7.11 (d, J = 130.7, 128.9 (2C), 128.6, 127.8, 121.7, 56.6, 26.8, 22.9, 21.4; IR (KBr,
8.0 Hz, 2H), 7.03 (t, J = 0.8 Hz, 1H), 6.47 (t, J = 5.2 Hz, 1H ), 4.81 (s, cm-1): 3057, 1630, 1597, 1571, 1471, 1350, 1130; HRMS (ESI-TOF)
2H), 2.59 (t, J = 8.0 Hz, 2H), 2.36 (s, 3H), 2.15-2.10 (m, 2H); m/z: C17H18NO2S (M + H)+ calcd for 300.1053, found 300.1058.
1
13C{1H}NMR (100 MHz, CDCl3) δ: 144.7, 142.9, 140.2, 135.4, 132.6, 4-(1-Tosylethyl)-1,2-dihydronaphthalene (3za): yellow oil; H NMR
132.0, 131.6, 129.2, 128.2, 126.5, 125.8, 119.2, 60.4, 29.8, 22.7, (400 MHz, CDCl3) : 7.68 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H),
21.5; IR (KBr, cm-1): 3067, 1630, 1596, 1560, 1461, 1317, 1121; 7.14-7.03 (m, 4H), 6.24 (t, J = 4.8 Hz, 1H ), 4.47-4.42 (m, 1H), 2.65 (t,
HRMS (ESI-TOF) m/z: C18H17BrClO2S (M + H)+ calcd for 410.9816, J = 8.0 Hz, 2H), 2.34 (s, 3H), 2.33-2.22 (m, 2H), 1.62 (d, J = 7.2 Hz,
found 410.9823.
3H ); 13C{1H}NMR (100 MHz, CDCl3) δ: 144.3, 136.1, 134.4, 133.6,
5-Bromo-7-fluoro-4-(tosylmethyl)-1,2-dihydronaphthalene (3ua): 131.2, 131.1, 129.3, 129.2, 127.6, 126.9, 126.3, 122.2, 59.9, 27.8,
yellow solid; mp 67.0-67.5 oC (uncorrected); 1H NMR (400 MHz, 23.1, 21.5, 15.0; IR (KBr, cm-1): 3051, 1635, 1581, 1562, 1460, 1366,
CDCl3) : 7.56 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.93 (t, J = 1117; HRMS (ESI-TOF) m/z: C19H21O2S (M + H)+ calcd for 313.1257,
8.0 Hz, 1H), 6.80-6.78 (m, 1H), 6.43 (t, J = 5.2 Hz, 1H ), 4.82 (s, 2H), found 313.1266.
2.59 (t, J = 7.2 Hz, 2H), 2.34 (s, 3H), 2.14-2.09 (m, 2H); 13C{1H}NMR 7-Chloro-4-(((4-methoxyphenyl)sulfonyl)methyl)-1,2-
(100 MHz, CDCl3) δ: 160.4 (d, J = 250.1 Hz, 1C), 144.5, 143.6 (d, J = dihydronaphthalene (3hb):
yellow solid; mp 90.0-90.5 oC
1
7.8 Hz, 1C), 139.3, 135.6, 129.3 129.2, 128.2, 125.7, 119.4 (d, J = (uncorrected); H NMR (400 MHz, CDCl3) : 7.70 (d, J = 9.2 Hz, 2H),
24.1 Hz, 1C), 119.1, 113.9 (d, J = 20.9 Hz, 1C), 60.6, 30.3, 22.7, 21.4; 7.06 (t, J = 8.8 Hz, 3H), 6.88 (d, J = 9.2 Hz, 2H), 5.91 (t, J = 4.8 Hz,
19F NMR (282 MHz, CDCl3) : -114.1 (s, 1F); IR (KBr, cm-1) : 3069, 1H), 4.16 (s, 2H), 3.85 (s, 3H), 2.68 (t, J = 8.4 Hz, 2H), 2.28-2.17 (m,
2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 163.7, 137.8, 135.0, 132.6,
6 | J. Name., 2012, 00, 1-3
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131.2, 130.8, 129.6, 127.6, 126.3, 125.4, 124.5, 114.0, 60.1, 55.7, 2.67 (t, J = 8.4 Hz, 2H), 2.25-2.20 (m, 2H); 13C{1H}NMR (100 MHz,
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27.6, 23.1; IR (KBr, cm-1): 3059, 1639, 1573, 1550, 1466, 1356, 1116; CDCl3) δ: 165.8 (d, J = 255.2 Hz, 1C), 137.7,D1O3I5: 1.30,.1103394/.D10(Od,B0J 1=5730.A2
HRMS (ESI-TOF) m/z: C18H1835ClO3S (M + H)+ calcd for 349.0660, Hz, 1C), 132.9, 131.5 (d, J = 9.6 Hz, 1C), 130.9, 127.8, 126.4, 125.1,
found 349.0664.
124.5, 116.3 (d, J = 22.5 Hz, 1C), 60.0, 27.5, 23.1; 19F NMR (282 MHz,
CDCl3) : -103.2 (s, 1F); IR (KBr, cm-1): 3054, 1611, 1576, 1544, 1477,
4-(((4-(tert-Butyl)phenyl)sulfonyl)methyl)-7-chloro-1,2-
dihydronaphthalene (3hc): yellow solid; mp 85.0-85.5 oC 1332, 1120; HRMS (ESI-TOF) m/z: C17H15ClFO2S (M + H)+ calcd for
1
(uncorrected); H NMR (400 MHz, CDCl3) : 7.68 (d, J = 8.8 Hz, 2H), 337.0460, found 337.0467.
7.39 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 2.0 Hz, 1H), 6.95-6.92 (m, 1H), 7-Chloro-4-(((4-chlorophenyl)sulfonyl)methyl)-1,2-
6.87 (d, J = 8.4 Hz, 1H ), 6.04 (t, J = 4.8 Hz, 1H), 4.17 (s, 2H), 2.67 (t, J dihydronaphthalene (3hi): yellow solid; mp 110.0-110.5 oC
1
= 8.0 Hz, 2H), 2.27-2.22 (m, 2H), 1.29 (s, 9H); 13C{1H}NMR (100 MHz, (uncorrected); H NMR (400 MHz, CDCl3) : 7.72 (d, J = 8.8 Hz, 2H),
CDCl3) δ: 157.8, 137.8, 135.1, 132.5, 131.1, 128.5 (2C), 127.6, 126.1, 7.43 (d, J = 8.8 Hz, 2H), 7.09 (s, 3H), 5.90 (t, J = 4.8 Hz, 1H), 4.19 (s,
125.8, 125.2, 124.1, 59.9, 35.1, 31.0, 27.6, 23.1; IR (KBr, cm-1): 3066, 2H), 2.67 (t, J = 8.0 Hz, 2H), 2.26-2.20 (m, 2H); 13C{1H}NMR (100
1619, 1593, 1565, 1473, 1359, 1164; HRMS (ESI-TOF) m/z: MHz, CDCl3) δ: 140.6, 137.8, 136.5, 135.4, 133.0, 130.9, 130.1, 129.2,
C21H24ClO2S (M + H)+ calcd for 375.1180, found 375.1187.
127.8, 126.4, 125.0, 124.5, 60.0, 23.5, 23.1; IR (KBr, cm-1): 3046,
7-Chloro-4-((phenylsulfonyl)methyl)-1,2-dihydronaphthalene
1619, 1566, 1540, 1471, 1358, 1138; HRMS (ESI-TOF) m/z:
(3hd): yellow solid; mp 95.0-95.5 oC (uncorrected); 1H NMR (400 C17H15Cl2O2S (M + H)+ calcd for 353.0164, found 353.0169.
MHz, CDCl3) : 7.80 (d, J = 7.6 Hz, 2H), 7.58 (t, J = 7.6 Hz, 1H), 7.46 4-(((4-Bromophenyl)sulfonyl)methyl)-7-chloro-1,2-
(t, J = 8.0 Hz, 2H), 7.01 (s, 3H), 5.90 (t, J = 4.8 Hz, 1H ), 4.19 (s, 2H), dihydronaphthalene (3hj): white solid; mp 110.0-110.5 oC
2.66 (t, J = 8.0 Hz, 2H), 2.24-2.19 (m, 2H); 13C{1H}NMR (100 MHz, (uncorrected); 1H NMR (400 MHz, CDCl3) : 7.66-7.58 (m, 4H), 7.10-
CDCl3) δ: 138.1, 137.8, 135.2, 133.7, 132.8, 131.1, 128.9, 128.6, 7.06 (m, 3H), 5.90 (t, J = 4.8 Hz, 1H ), 4.19 (s, 2H), 2.67 (t, J = 8.0 Hz,
127.7, 126.3, 125.1, 124.5, 60.0, 27.5, 23.1; IR (KBr, cm-1): 3057, 2H), 2.26-2.20 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 137.8,
1612, 1596, 1569, 1450, 1360, 1131; HRMS (ESI-TOF) m/z: 137.0, 135.4, 133.0, 132.2, 130.8, 130.2, 129.2, 127.8, 126.4, 125.0,
C17H16ClO2S (M + H)+ calcd for 319.0554, found 319.0560.
124.5, 60.0, 27.5, 23.1; IR (KBr, cm-1): 3041, 1633, 1570, 1531, 1452,
7-Chloro-4-(((4-nitrophenyl)sulfonyl)methyl)-1,2-
1361, 1148; HRMS (ESI-TOF) m/z: C17H15BrClO2S (M + H)+ calcd for
dihydronaphthalene (3he): yellow solid; mp 150.0-150.5 oC 396.9659, found 396.9663.
1
(uncorrected); H NMR (400 MHz, CDCl3) : 8.31 (d, J = 8.8 Hz, 2H), 7-Chloro-4-((m-tolylsulfonyl)methyl)-1,2-dihydronaphthalene
8.00 (d, J = 9.2 Hz, 2H), 7.10 (t, J = 0.8 Hz, 3H), 5.91 (t, J = 4.8 Hz, (3hk): yellow oil; 1H NMR (400 MHz, CDCl3) : 7.60 (t, J = 7.2 Hz 2H),
1H ), 4.27 (s, 2H), 2.67 (t, J = 8.0 Hz, 2H), 2.26-2.22 (m, 2H); 7.38-7.32 (m, 2H), 7.06 (d, J = 8.8 Hz, 3H), 5.92 (t, J = 4.8 Hz, 1H),
13C{1H}NMR (100 MHz, CDCl3) δ: 150.8, 143.7, 137.8, 135.9, 133.3, 4.17 (s, 2H), 2.67 (t, J = 7.6 Hz, 2H), 2.35 (s, 3H), 2.25-2.20 (m, 2H);
130.5, 130.2, 128.0, 126.5, 124.7, 124.4, 124.0, 60.0, 27.5, 23.1; IR 13C{1H}NMR (100 MHz, CDCl3) δ: 139.1, 138.0, 137.8, 135.1, 134.4,
(KBr, cm-1): 3068, 1619, 1586, 1553, 1474, 1366, 1159; HRMS (ESI- 132.7, 131.1, 129.0, 128.8, 127.6, 126.2, 125.7, 125.2, 124.4, 59.9,
TOF) m/z: C17H15ClNO4S (M + H)+ calcd for 364.0405, found 27.5, 23.1, 21.1; IR (KBr, cm-1): 3054, 1636, 1577, 1529, 1448, 1314,
364.0411.
1141; HRMS (ESI-TOF) m/z: C18H18ClO2S (M + H)+ calcd for 333.0711,
4-(((6-Chloro-3,4-dihydronaphthalen-1-
found 333.0719.
yl)methyl)sulfonyl)benzonitrile (3hf): yellow solid; mp 105.0-105.5 7-Chloro-4-((o-tolylsulfonyl)methyl)-1,2-dihydronaphthalene (3hl):
1
oC (uncorrected); H NMR (400 MHz, CDCl3) : 7.92 (d, J = 8.4 Hz, yellow oil; 1H NMR (400 MHz, CDCl3) : 7.85-7.83 (m, 1H), 7.48-7.44
2H), 7.76 (d, J = 8.4 Hz, 2H), 7.11-7.01 (m, 3H), 5.90 (t, J = 4.8 Hz, (m, 1H), 7.26 (t, J = 4.8 Hz, 2H), 7.16 (d, J = 8.0 Hz, 1H), 7.10-7.07 (m,
1H), 4.24 (s, 2H), 2.66 (t, J = 8.0 Hz, 2H), 2.27-2.21 (m, 2H); 2H), 5.87 (t, J = 4.8 Hz, 1H), 4.21 (s, 2H), 2.68 (s, 3H), 2.63 (t, J = 8.0
13C{1H}NMR (100 MHz, CDCl3) δ: 142.2, 137.7, 135.8, 133.3, 132.6, Hz, 2H), 2.22-2.17 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 138.4,
130.6, 129.4, 127.9, 126.5, 124.7, 124.4, 117.5, 117.0, 59.9, 27.5, 137.8, 136.3, 135.0, 133.7, 132.8, 132.5, 131.2, 130.9, 127.6, 126.4,
23.1; IR (KBr, cm-1): 3056, 1610, 1580, 1566, 1457, 1357, 1161; 126.3, 125.0, 124.5, 59.1, 27.5, 23.1, 20.8; IR (KBr, cm-1): 3063, 1646,
HRMS (ESI-TOF) m/z: C18H15ClNO2S (M + H)+ calcd for 344.0507, 1566, 1519, 1440, 1356, 1129; HRMS (ESI-TOF) m/z: C18H18ClO2S (M
found 344.0516.
+ H)+ calcd for 333.0711, found 333.0719.
7-Chloro-4-(((4-(trifluoromethyl)phenyl)sulfonyl)methyl)-1,2-
7-Chloro-4-(((2-chlorophenyl)sulfonyl)methyl)-1,2-
1
dihydronaphthalene (3hg): yellow oil; H NMR (400 MHz, CDCl3) : dihydronaphthalene (3hm): yellow solid; mp 70.0-70.5 oC
1
7.93 (d, J = 7.2 Hz, 2H), 7.71 (d, J = 8.4 Hz, 2H), 7.08-7.00 (m, 3H), (uncorrected); H NMR (400 MHz, CDCl3) : 7.93 (d, J = 8.0 Hz, 1H),
5.94 (t, J = 4.8 Hz, 1H ), 4.23 (s, 2H), 2.67 (t, J = 8.0 Hz, 2H), 2.28-2.21 7.53 (m, 2H), 7.36 (s, 1H), 7.29 (d, J = 8.4 Hz, 1H), 7.14 (m, 1H), 7.06
(m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 141.6, 137.7, 135.7, 133.1, (d, J = 1.6 Hz, 1H), 6.05 (t, J = 4.8 Hz, 1H), 4.49 (s, 2H), 2.59 (t, J = 8.0
130.7, 129.3 (2C), 127.8, 126.3, 125.9 (t, J = 3.7 Hz, 1C), 125.7 (q, J = Hz, 2H), 2.22-2.17 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ: 137.8,
267.4 Hz, 1C), 124.8, 124.3, 59.9, 27.5, 23.1; 19F NMR (282 MHz, 135.9, 135.5, 134.7, 132.9, 132.8, 132.3, 131.7, 131.1, 127.6 (2C),
CDCl3) : -63.2 (s, 3F); IR (KBr, cm-1): 3069, 1634, 1591, 1555, 1438, 127.2, 126.4, 124.7, 57.4, 27.5, 23.1; IR (KBr, cm-1): 3046, 1630,
1363, 1165; HRMS (ESI-TOF) m/z: C18H15ClF3O2S (M + H)+ calcd for 1565, 1519, 1429, 1352, 1142; HRMS (ESI-TOF) m/z: C17H15Cl2O2S (M
387.0428, found 387.0433.
+ H)+ calcd for 353.0164, found 353.0169.
7-Chloro-4-(((4-fluorophenyl)sulfonyl)methyl)-1,2-
1-(((6-Chloro-3,4-dihydronaphthalen-1-
dihydronaphthalene (3hh): yellow solid; mp 120.0-120.5 oC yl)methyl)sulfonyl)naphthalene (3hn): yellow solid; mp 92.0-92.5
(uncorrected); 1H NMR (400 MHz, CDCl3) : 7.82-7.79 (m, 2H), 7.16- oC (uncorrected); H NMR (400 MHz, CDCl3) : 8.35 (d, J = 1.2 Hz,
1
7.14 (m, 2H), 7.12-7.08 (m, 3H), 5.89 (t, J = 4.8 Hz, 1H), 4.20 (s, 2H), 1H), 7.90 (t, J =7.2 Hz, 3H), 7.79-7.76 (m, 1H), 7.67-7.61 (m, 2H),
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7.10 (d, J = 8.4 Hz, 1H), 7.01-6.96 (m, 2H), 5.87 (t, J = 4.8 Hz, 1H), For Postgraduate (CX20201133), Natural Science Foundation of
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4.26 (s, 2H), 2.63 (t, J = 8.0 Hz, 2H), 2.18-2.13 (m, 2H); 13C{1H}NMR Hunan Province (No. 2018JJ3208 and 2019JJ50204) and National
DOI: 10.1039/D0OB01570A
(100 MHz, CDCl3) δ: 137.6, 135.2, 135.2, 135.0, 132.7, 131.9, 131.1, Natural Science Foundation of China (No. 2191061) for financial
130.6, 129.3, 129.2, 129.1, 127.9, 127.7, 127.6, 126.3, 125.2, 124.5, support.
123.2, 60.1, 27.5, 23.0; IR (KBr, cm-1): 3067, 1639, 1581, 1533, 1434,
1330, 1140; HRMS (ESI-TOF) m/z: C21H18ClO2S (M + H)+ calcd for Notes and references
369.0711, found 369.0719.
2-(((6-Chloro-3,4-dihydronaphthalen-1-
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yl)methyl)sulfonyl)thiophene (3ho): yellow solid; mp 82.0-82.5 oC
(uncorrected); 1H NMR (400 MHz, CDCl3) : 7.64-7.63 (m, 1H), 7.57-
7.56 (m, 1H), 7.09-7.04 (m, 4H), 6.02 (t, J = 4.8 Hz, 1H), 4.29 (s, 2H),
2.71 (t, J = 8.0 Hz, 2H), 2.30-2.25 (m, 2H); 13C{1H}NMR (100 MHz,
CDCl3) δ: 138.9, 137.7, 135.4, 134.8, 134.4, 132.8, 131.0, 127.7,
127.7, 126.3, 125.2, 124.1, 60.9, 27.6, 23.1; IR (KBr, cm-1): 3058,
1625, 1574, 1531, 1445, 1323, 1127; HRMS (ESI-TOF) m/z:
C15H14ClO2S2 (M + H)+ calcd for 325.0118, found 325.0126.
(2-Tosylethene-1,1-diyl)dibenzene (5): white solid; mp 91.0-91.5 oC
1
(uncorrected); H NMR (400 MHz, CDCl3) : 7.47 (d, J = 8.0 Hz, 2H),
7.38-7.35 (m, 2H), 7.32-7.28 (m, 4H), 7.22 (t, J = 7.2 Hz, 2H), 7.15 (d,
J = 8.0 Hz, 2H), 7.10 (t, J = 6.8 Hz, 2H), 7.0 (s, 1H), 2.38 (s, 3H);
13C{1H}NMR (100 MHz, CDCl3) δ: 154.7, 143.7, 139.2, 138.5, 135.5,
130.2, 129.7, 129.3, 128.9, 128.8, 128.5, 128.2, 127.8, 127.7, 21.5;
IR (KBr, cm-1): 3067, 1615, 1568, 1527, 1453, 1348, 1151; HRMS
(ESI-TOF) m/z: C21H19O2S (M + H)+ calcd for 335.1100, found
335.1107.
6-Chloro-1-hydroxy-1-(tosylmethyl)-3,4-dihydronaphthalen-2(1H)-
1
one (6): yellow oil; H NMR (400 MHz, CDCl3) : 7.87 (d, J = 8.4 Hz,
1H), 7.77 (d, J = 8.0 Hz, 2H), 7.35-7.27 (m, 4H), 4.09 (s, 1H), 3.48 (s,
2H), 3.15-3.12 (m, 2H), 2.74-2.67 (m, 1H), 2.45 (s, 3H), 2.30-2.26 (m,
1H); 13C{1H}NMR (100 MHz, CDCl3) δ: 195.8, 145.0, 144.4, 140.9,
137.5, 130.0, 129.8, 128.9, 128.3, 128.1, 127.8, 74.1, 60.0, 33.8,
25.8, 21.6; IR (KBr, cm-1) IR (KBr, cm-1): 3321, 3060, 1564, 1522,
1455, 1311, 1182, 1126; HRMS (ESI-TOF) m/z: C18H18ClO4S (M + H)+
calcd for 365.0609, found 365.0614.
6-Chloro-1-(tosylmethyl)naphthalene (7): gray solid; mp 120.0-
o
1
120.5 C (uncorrected); H NMR (400 MHz, CDCl3) : 7.80 (t, J = 5.2
Hz, 2H), 7.73 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.38-7.34
(m, 2H), 7.16 (d, J = 8.0 Hz, 3H), 4.76 (s, 2H), 4.24 (s, 3H);
13C{1H}NMR (100 MHz, CDCl3) δ: 144.9, 134.8, 134.4, 131.8, 130.7,
130.4, 129.5, 128.7, 128.6, 127.3, 127.1, 126.2, 125.6, 124.9, 59.8,
21.5; IR (KBr, cm-1): 3061, 1633, 1554, 1517, 1423, 1362, 1187;
HRMS (ESI-TOF) m/z: C18H16ClO2S (M + H)+ calcd for 331.0554, found
331.0559.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
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We thank the Scientific Research Fund of Hunan Provincial
Education Department (No. 18B350), the Science and Technology
Planning Project of Hunan Province (No. 2018TP1017), Innovation
research group project of Natural Science Foundation of Hunan
Province (No. 2020JJ1004), Hunan Provincial Innovation Foundation
8 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Organic & Biomolecular Chemistry
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DOI: 10.1039/D0OB01570A
Table of Contents
Silver-promoted oxidative sulfonylation and ring-expansion of vinylcyclopropanes with sodium sulfinates leading
to dihydronaphthalene derivatives
Pu Chen,†a Quan Zhou,†a Zan Chen,a Yu-Kui Liu,a Yun Liang,b Ke-Wen Tang,*a Yu Liu*ab
R2
SO2R3
R2
AgNO3 (20 mol%)
K2S2O8 (2 equiv)
toluene, Ar, 90 oC, 24 h
R3SO2Na
R1
+
R1
Sulfonylation and ring-expansion strategy
Mild reaction conditions
General: 40 examples, up to 87% yield
A simple and efficient Silver-promoted sulfonylation and ring-expansion of vinylcyclopropanes with sodium sulfinates is
established for the construction of 1-sulfonylmethylated 3,4-dihydronaphthalenes.