Palladium-catalyzed allylation of sulfonyl hydrazides with alkynes to synthesize allylic arylsulfones

Article abstract of DOI:10.1039/C6OB01929C

A novel method for the construction of allyl arylsulfone derivatives was developed by palladium catalyzed allylation of sulfonyl hydrazides with alkynes. A series of structurally diverse allyl arylsulfones can be regioselectively synthesized in high yields under mild conditions.

Full text of DOI:10.1039/C6OB01929C

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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PAPER
Palladium-Catalyzed Allylation of Sulfonyl Hydrazides with
Alkynes to Synthesize Allylic Arylsulfones
Received 00th January 20xx,
Accepted 00th January 20xx
Chuan-Jun Lu,* Hong Chen, Dong-Kai Chen, Hong Wang, Zhen-Ping Yang, Jianrong Gao and
Hongwei Jin*
DOI: 10.1039/x0xx00000x
A novel method for the construction of allyl arylsulfone derivatives was developed by palladium catalyzed allylation of
sulfonyl hydrazides with alkynes. A series of structurally diverse allyl arylsulfones can be regioselectively synthesized in
high yields under mild conditions.
www.rsc.org/
with simple alkynes for the synthesis of linear allyl arylsulfones
in high yields with high regioselectivities (Scheme 1, eqn 3).10
Introduction
Allyl arylsulfone derivatives are important structural motifs due
to their wide presence in biologically active compounds, such
as anticancer agents, antibacterial agents and antiglaucoma
agents.1 Additionally, they can also serve as versatile building
blocks in a number of carbonꢀcarbon bondꢀforming reactions,2
including Julia olefination, olefin crossꢀmetathesis, and Michael
addition reaction. Therefore, considerable effort has been
directed toward the development of efficient synthetic
methodologies for the preparation of allylic sulfones.3
One of the reliable approaches for the synthesis of this class
of compounds is transitionꢀmetalꢀcatalyzed allylic alkylation
reactions.4 Several Pdꢀ, Irꢀ or Feꢀcatalyzed sulfonyl
nucleophiles with allyl alcohols, acetates, carbonates, halides,
and amines have been developed to achieve the allyl
arylsulfone derivatives (Scheme 1, eqn 1).5 However, most of
these methods mentioned above require preinstallation of a
leaving group and sometimes need a stoichiometric amount of
base.
From an economic point of view, arylpropyne is an ideal
precursor to form the πꢀallylmetal complex. In 1998,
Yamamoto reported the first allylation of methylmalononitrile
with arylpropyne in the presence of Pd(0)/carboxylic acid
combined catalyst to afford linear allylic compounds with high
regioselectivity.6 Since then, a series of Cꢀ, Nꢀ and Oꢀ
nucleophiles (Scheme 1, eqn 2) with alkynes have been
reported to synthesize linear or branched allylated carbonyl,
allylaniline, allyl ether and allyl ester compounds in the
presence of palladium7 or rhodium catalysts.8 Despite these
advantages for the allylation reactions of arylpropyne, there is
still no report of the construction of carbonꢀsulfur bonds by the
in situ formation of π palladiumꢀallyl species.9 Herein, we
report a palladium catalyzed allylation of sulfonyl hydrazides
Previous work
1)
[Pd]/L
R
Lg
+
ArSO2
R
SO2Ar
Lg = OAc, OCO2R,
OH, NH2, X
R
R
[Pd]/L, Acid
[Pd]/L, Acid
R1
Nu-H
2)
+
R1
Nu
C-, N-, O-
nuceophiles
R
This work
R1
3)
ArSO2NHNH2
R1
SO2Ar
+
R
S-nuceophile
2
1
3
Scheme 1 Different approaches for the allylic alkylation reactions catalyzed
by palladium
Results and Discussion
At the beginning of our study, we chose 1ꢀphenylꢀ1ꢀpropyne
(
1a) and TsNHNH2 (2a) as the model substrates to optimize the
reaction conditions (Table 1). The reaction proceeded smoothly
to yield the desired linear allylic sulfone 3aa in a 37% yield by
using 5 mol% Pd(dba)2 as a catalyst, 12 mol% PPh3 as a ligand
and 0.5 equiv. acetic acid as an additive in dioxane solvent at
100 °C under a N2 atmosphere for 12 hours (Table 1, entry 1).
The influence of the palladium catalyst was first examined. The
studies revealed that the palladium catalyst was crucial for this
transformation. Pd(PPh3)4 could also promote the reaction but
with a slightly lower yield (Table 1, entry 2). However, when
Pd(OAc)2 was used as a catalyst, the product 3aa was obtained
in a poor yield (entry 3), whereas by switching the palladium
catalyst to PdCl2, almost no product could be detected (entry 4).
The reaction temperature was also important for this reaction.
When the temperature was increased to 120 °C, the yield of 3aa
was substantially increased to 51% (entry 5). Subsequent ligand
screening indicated that PPh3 was still proven to be the best
a.College of Chemical Engineering, Zhejiang University of Technology, Chaowang
Road 18#, Hangzhou 310014, China; E-mail: luchuanjun@zjut.edu.cn and
jhwei828@zjut.edu.cn
†Electronic Supplementary Information (ESI) available: Copies of NMR spectra. See
DOI: 10.1039/x0xx00000x
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Table 2 Scope of sulfonyl hydrazidesa
ligand, and other electronꢀrich or bidentate ligands were not
efficient ligands (Table 1, entries 6ꢀ7). To further improve the
yield, we investigated the effects of acid additives on this
reaction. When PhCOOH and
mꢀFꢀC6H5COOH were used as
acid additives, slightly higher yields of 3aa were achieved than
with HOAc (entries 8 and 9). Gratifyingly, the yield was
remarkably improved to 70% by using
mꢀchlorobenzoic acid as
an acid additive (entry 10). CF3COOH was not an effective acid
additive and led to a poor product yield (entry 11). The
subsequent solvent examination showed that a reduced yield
was observed in toluene (entry 12). However, to our delight, the
desired product was isolated in 75% yield when the reaction
was conducted in glyme (entry 13). Furthermore, by enhancing
the amount of the mꢀchlorobenzoic acid from 0.5 equiv. to 1.0
equiv., the yield of 3aa could be further improved to 82%
(entry 14).
Table 1 Optimization of the reaction conditionsa
a Reaction conditions: 1a (0.36 mmol), 2 (0.30 mmol), mꢀClꢀC6H5COOH (0.3
mmol), Pd(dba)2 (5 mol %), and PPh3 (12 mol%) in glyme (2.0 mL) at 120
°C for 12 h under N2 atmosphere.
Yieldb
(%)
Entry
Catalyst
Additive
Solvent
T (oC)
Pd(dba)2
Pd(PPh3)4
Pd(OAc)2
PdCl2
HOAc
HOAc
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
toluene
glyme
100
100
100
100
120
120
120
120
120
120
120
120
120
120
37
1
2c
3
31
HOAc
12
HOAc
trace
51
4
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
Pd(dba)2
HOAc
5
6d
7e
8
Table 3 Substrate scope of akynesa
HOAc
16
HOAc
33
PhCOOH
54
3ꢀFꢀC6H5CO2H
3ꢀClꢀC6H5CO2H
CF3CO2H
3ꢀClꢀC6H5CO2H
3ꢀClꢀC6H5CO2H
3ꢀClꢀC6H5CO2H
56
9
70
10
11
12
13
14f
33
40
75
glyme
82
a Reaction conditions: 1a (0.36 mmol), 2a (0.3 mmol), additive (0.5 equiv), 5
mol% Pd catalyst, 12 mol% PPh3 in 2.0 mL solvent for 12 h. b isolated yields.
c No PPh3 was added. d 12 mol% XꢀPhos was used instead of PPh3. e 6 mol%
BINAP was used instead of PPh3. f 1.0 equiv 3ꢀClꢀC6H5CO2H was used.
Under the optimized reaction conditions, the scope of
substituted arylsulfonylhydrazides was first examined with
phenylpropyne 1a as a standard substrate. It was found that
arylsulfonylhydrazides possessing either electronꢀrich or
electronꢀdeficient groups at the
o
ꢀ,
mꢀ or
p
ꢀposition proceeded
efficiently to afford allyl arylsulfone
3
in good to excellent
yields (Table 2, 3aa-3ai). Notably, reaction with
arylsulfonylhydrazide 2e bearing an amide group can also
proceed smoothly to give the desired allylic sulfone product
3ae in 67% yield and is not affected by the NꢀH group. In
addition, 1ꢀnaphthyl and 2ꢀnaphthyl substituted sulfonyl
hydrazides were also tested in the reaction and afforded the
desired products 3ag and 3af in 78% and 80% yields,
respectively. Furthermore, alkylsulfonylhydrazide
4
can also be
a partner in the reaction to afford allyl sulfone
a relatively lower yield (eqn (1)).
5, although with
2 | Org. Biomol. Chem. 2016, 00, 1-3
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a Reaction conditions: 1 (0.36 mmol), 2 (0.30 mmol), mꢀClꢀC6H5COOH (0.3
mmol), Pd(dba)2 (5 mol %), and PPh3 (12 mol%) in glyme (2.0 mL) at 120
°C for 12ꢀ24 h under N2 atmosphere. b Pd(dba)2 (10 mol %) and PPh3 (24
mol%) were used.
Scheme 2. Plausible mechanism
We next turned to examine the scope of the alkynes for this
reaction and the results are summarized in Table 3. Various
alkynes were coupled with sulfonyl hydrazide to give the
corresponding linear allylic sulfones in moderate to good yields
with high selectivities in most cases. Several points should be
noted from these results: 1) For substituent R1, the yield was
slightly enhanced with gradually increasing the size of the
substituent from Me, to Et and finally to nPr. However, when R1
was a phenyl group, the yield was relatively lower than those
Conclusions
We have developed a new method for the construction of allyl
arylsulfone derivatives by the palladium catalyzed allylation of
sulfony hydrazides with alkynes in good yields with high
regioselectivities under mild conditions. A series of sulfonyl
hydrazides and alkynes can be utilized in this reaction.
with the alkyl groups (3oa vs. 3baꢀ
3da); 2) The R2 substituents
Experimental Section
on the benzene ring had no obvious influence on the reactivity,
regardless of their electronic properties or steric effects,
affording the desired products in 46%ꢀ75% yields; 3) Substrates
with an electronꢀdonating substituent at the metaꢀ or paraꢀ
position of the alkyne group gave better yields than those with
an electronꢀwithdrawing substituent; and 4) Several important
functional groups such as ꢀOMe (3ja), as well as the halogens ꢀ
Materials and methods
Reactions and manipulations involving organometallic or
moisture sensitive compounds were carried out under dry
nitrogen and glassware heated under oven for two hours prior to
1
use. H and 13C spectra were recorded on Bruker AVANCE III
500 MHz using CDCl3 as solvent with TMS as internal
standard. Anhydrous dioxane, glyme were freshly distilled over
Na and stored under nitrogen. Commercial reagents were used
as received without further purification unless otherwise
noticed. Melting points (m.p.) were recorded on a SGW
Melting Point Xꢀ4. HRMS were recorded on Agilent 6210 TOF
LC/MS mass spectrometer. Column chromatography was
carried out using silica gel (200ꢀ300 mesh).
F (3ka
To further demonstrate the substrate scope of this reaction,
terminal alkyne and phenylallene were also tested for
, 3la) and ꢀCl (3ma, 3na) were well tolerated.
6
7
reaction with TsNHNH2 (2a). Under the optimized reaction
conditions, the reactions proceeded well to give allylic sulfone
3aa in 65% and 70% yields, respectively (eqn (2) and (3)). This
may indicate that the terminal alkyne is transformed to an
allene via hydrometalation in the presence of a palladium
catalyst.
On the basis of the literature6 and our observations, we
propose a reaction pathway (Scheme 2). The catalytic cycle is
initiated by the coordination between Pd(0) and acid to generate
General procedure for the synthesis of alkynes 1b-1o
To a roundꢀbottomed flask, CuI (0.08 mmol, 4.0 mol%),
Pd(PPh3)2Cl2 (0.04 mmol, 2.0 mol%), PPh3 (0.4 mmol, 4.0
mol%), aryl halide (2.0 mmol) and Pr2NH (6 mL) were added.
i
After the mixture was stirred at 25 °C for 30 min under a N2
atmosphere, the alkyne (2.0 mmol) was added. The mixture was
then stirred at reflux for another 6 h. The reaction mixture was
cooled to room temperature and a saturated NH4Cl solution was
added. The mixture was extracted with ethyl acetate and the
combined organic layers were dried with MgSO4, followed by
concentration under vacuum. The residue was purified by flash
silica gel column chromatography, and petroleum ether was
used as the eluent.
the hydropalladation intermediate
hydropalladation of 1a affords vinyl palladium intermediate II
The ꢀelimination of intermediate II occurs to produce
phenylallene III and the active catalyst . Subsequently, the
allylpalladium intermediate IV is formed by the reinsertion of
hydropalladation intermediate to allene III. Finally, the
I, and the following
.
β
I
πꢀ
I
palladiumꢀallyl species IV can be attacked by an in situ formed
sulfonyl anion to afford the desired allylic sulfone 3aa and
regenerate intermediate
and H2.
I by releasing one molecule each of N2
General procedure for the synthesis of arylsulfonylhydrazides 2
and alkylsulfonylhydrazide 4
To a roundꢀbottomed flask, hydrazine hydrate (12.5 mmol, 1.25
equiv.) was added, and the flask was placed in an ice water
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bath. A solution of sulfuryl chloride (10 mmol, 1 equiv.) in (EI) m/z calculated for C17H17NO3S [M]+ 315.0929, found
tetrahydrofuran (6 mL) was then slowly added to the flask with 315.0928.
stirring. After the addition was completed, the mixture was
2-(Cinnamylsulfonyl)naphthalene (3af). 73.5 mg, 80%, white
stirred at room temperature and monitored by TLC. After the solid, m.p. 141ꢀ143 °C. 1H NMR (500 MHz, CDCl3) δ 8.49 (d, J =
reaction was completed, water was added into the flask and 1.0 Hz, 1H), 8.01ꢀ7.93 (m, 3H), 7.87 (dt, J = 8.7, 4.4 Hz, 1H), 7.72ꢀ
followed by shaking. The white solid product was later 7.66 (m, 1H), 7.66ꢀ7.60 (m, 1H), 7.30ꢀ7.26 (m, 5H), 6.42 (d, J =
separated by filtration, washed with water and dried in air 15.8 Hz, 1H), 6.16 (dt, J = 15.5, 7.6 Hz, 1H), 4.05 (dd, J = 7.6, 0.9
overnight.
Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 139.2, 135.7, 135.4, 135.3,
132.0, 130.3, 129.4, 129.2, 129.0, 128.6, 128.4, 127.9, 127.6, 126.6,
123.1, 115.1, 60.5.
Typical procedure for the palladium catalyzed allylation of sulfony
hydrazides with alkynes
1-(Cinnamylsulfonyl)naphthalene (3ag). 72 mg, 78%, white
solid, m.p. 97ꢀ99 °C. 1H NMR (500 MHz, CDCl3) δ 8.88ꢀ 8.83 (m,
1H), 8.27 (dd, J = 7.3, 1.2 Hz, 1H), 8.12 (d, J = 8.2 Hz, 1H), 7.99 (d,
J = 8.2 Hz, 1H), 7.73 (ddd, J = 8.5, 6.9, 1.3 Hz, 1H), 7.67ꢀ7.62 (m,
1H), 7.58ꢀ7.53 (m, 1H), 7.29 ꢀ7.24 (m, 3H), 7.21ꢀ7.17 (m, 2H), 6.29
(d, J = 15.8 Hz, 1H), 6.10ꢀ 6.03 (m, 1H), 4.18 (dd, J = 7.6, 0.9 Hz,
2H). 13C NMR (125 MHz, CDCl3) δ 139.0, 135.7, 135.2, 134.1,
133.5, 131.2, 129.2, 128.9, 128.6, 128.5, 128.3, 126.9, 126.5, 124.3,
124.2, 115.0, 60.0.
To a mixture of 1ꢀphenylꢀ1ꢀpropyne
ArNHNH2 2a (0.30 mmol, 1.0 equiv), Pd(dba)2 (8.6 mg, 0.015
mmol, 5 mol%), PPh3 (9.4 mg, 0.036 mmol, 12 mol%) and
1 (0.36 mmol, 1.2 equiv),
mꢀ
chlorobenzoic acid (47 mg, 0.3 mmol) in a sealed tube was
added 2 mL dry glyme under N2 atmosphere. The resulting
o
mixture was then stirred at 100 C for 12 h until the reaction
was complete (monitored by TLC). The solvent was then
removed under vacuum and the residue was purified by
chromatography on silica gel, eluting with ethyl/petroleum
1-(Cinnamylsulfonyl)-4-fluorobenzene (3ah). 68 mg, 82%,
white solid, m.p. 95ꢀ97 °C. 1H NMR (500 MHz, CDCl3) δ 7.98ꢀ
ether 1:5 (v/v) to afford the desired product
3. 3aa, 3ac, 3ad,
3af 3ag 3ba
,
,
,
3ca and 3oa are known compounds.5l
7.85 (m, 2H), 7.36ꢀ7.28 (m, 5H), 7.25ꢀ7.19 (m, 2H), 6.39 (d,
= 15.8 Hz, 1H), 6.16ꢀ6.08 (m, 1H), 3.97 (dd, = 7.7, 0.9 Hz,
2H). 13C NMR (125 MHz, CDCl3) δ 165.9 (d,
= 255.0 Hz),
139.4, 135.6, 131.4 (d, = 9.6 Hz), 129.3, 128.7 (d, = 7.5
Hz), 128.5, 127.5, 126.6, 117.1, 116.4 (d, = 22.5 Hz), 115.9,
J
1-(Cinnamylsulfonyl)-4-methylbenzene (3aa). 66.9 mg, 82%,
white solid, m.p. 124ꢀ126 °C. 1H NMR (500 MHz, CDCl3) δ 7.77 (d,
J = 8.3 Hz, 2H), 7.35ꢀ7.27 (m, 7H), 6.40 (d, J = 15.9 Hz, 1H), 6.12
(dt, J = 15.6, 7.6 Hz, 1H), 3.95 (dd, J = 7.7, 0.7 Hz, 2H), 2.45 (s,
3H). 13C NMR (125 MHz, CDCl3) δ 144.8, 139.1, 135.9, 135.6,
129.7, 128.7, 128.5, 128.4, 126.6, 115.4, 60.6, 21.6.
J
J
J
J
J
115.0, 60.6. HRMS (EI) m/z calculated for C15H13FO2S [M]+
276.0620, found 276.0621.
1-(Cinnamylsulfonyl)-2-methylbenzene (3ab). 57 mg,
70%, white solid, m.p. 77ꢀ79 °C. 1H NMR (500 MHz, CDCl3) δ
1-(Cinnamylsulfonyl)-3-fluorobenzene (3ai). 51 mg, 62%, white
solid, m.p. 86ꢀ88 °C. 1H NMR (500 MHz, CDCl3) δ 7.69 (d, J = 7.8
Hz, 1H), 7.64ꢀ7.60 (m, 1H), 7.54 (td, J = 8.0, 5.2 Hz, 1H), 7.36ꢀ7.29
(m, 6H), 6.42 (d, J = 15.8 Hz, 1H), 6.11 (dt, J = 15.6, 7.6 Hz, 1H),
3.99 (dd, J = 7.6, 0.8 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 163.4,
161.4, 140.44 (d, J = 6.4 Hz), 139.6, 135.6, 131.0 (d, J = 7.5 Hz),
128.7 (d, J = 3.8 Hz), 126.6, 124.4 (d, J = 3.4 Hz), 121.1 (d, J = 21.0
Hz), 115.9 (d, J = 24.1 Hz), 114.6, 60.4. HRMS (EI) m/z calculated
for C15H13FO2S [M]+ 276.0620, found 276.0621.
7.96 (dd,
7H), 6.41 (d,
J
= 6.4, 2.6 Hz, 1H), 7.55ꢀ7.48 (m, 1H), 7.36ꢀ7.26 (m,
= 15.8 Hz, 1H), 6.13ꢀ6.05 (m, 1H), 4.01 (dd,
J
J =
7.7, 0.6 Hz, 2H), 2.74 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
139.0, 138.2, 136.5, 135.7, 133.7, 132.6, 130.7, 128.6, 128.4,
126.6, 126.5, 60.1, 20.6. HRMS (EI) m/z calculated for
C16H16O2S [M]+ 272.0871, found 272.0869.
(Cinnamylsulfonyl)benzene (3ac). 62.5 mg, 81%, white solid,
m.p. 111ꢀ113 °C. 1H NMR (500 MHz, CDCl3) δ 7.94ꢀ7.86 (m, 2H),
7.66 (td, J = 7.2, 3.5 Hz, 1H), 7.55 (dd, J = 10.7, 4.9 Hz, 2H), 7.33ꢀ
7.27 (m, 5H), 6.38 (d, J = 15.8 Hz, 1H), 6.16ꢀ6.07 (m, 1H), 3.97 (dd,
J = 7.6, 1.0 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 139.1, 138.3,
135.7, 133.7, 129.0, 128.6, 128.4, 128.3, 126.5, 115.0, 60.3.
1-(Cinnamylsulfonyl)-4-methoxybenzene (3ad). 55 mg, 64%,
white solid, m.p. 117ꢀ119 °C. 1H NMR (500 MHz, CDCl3) δ 7.82ꢀ
7.79 (m, 2H), 7.32ꢀ7.30 (m, 5H), 7.00ꢀ6.97 (m, 2H), 6.40 (d, J =
15.8 Hz, 1H), 6.15ꢀ6.09 (m, 1H), 3.94 (dd, J = 7.6, 0.8 Hz, 2H), 3.86
(s, 3H). 13C NMR (125 MHz, CDCl3) δ 163.7, 138.9, 135.8, 130.6,
130.0, 128.6, 128.4, 126.6, 115.5, 114.2, 60.7, 55.6.
(E)-1-Methyl-4-((4-phenylbut-3-en-2-yl)sulfonyl)benzene (3ba).
1
46 mg, 53%, white solid, m.p. 108ꢀ110 °C. H NMR (500 MHz,
CDCl3) δ 7.70 (t, J = 10.0 Hz, 2H), 7.33ꢀ7.27 (m, 7H), 6.34 (d, J =
15.8 Hz, 1H), 6.08 (dd, J = 15.8, 8.3 Hz, 1H), 3.88ꢀ3.80 (m, 1H),
2.42 (s, 3H), 1.53 (d, J = 6.9 Hz, 3H). 13C NMR (125 MHz, CDCl3)
δ 144.5, 136.2, 135.8, 133.9, 129.4, 129.1, 128.5, 128.2, 126.4,
122.1, 63.9, 21.5, 13.5.
(
E
)-1-Methyl-4-((1-phenylpent-1-en-3-yl)sulfonyl)benzene
(3ca). 54 mg, 60%, light yellow solid, m.p. 66ꢀ68 °C. 1H NMR
(500 MHz, CDCl3) δ 7.72 (d, = 8.3 Hz, 2H), 7.33ꢀ7.27 (m,
7H), 6.32 (t, = 10.1 Hz, 1H), 5.92 (dd, = 15.9, 9.4 Hz, 1H),
3.60ꢀ3.53 (m, 1H), 2.43 (s, 3H), 2.29ꢀ2.25 (m, 1H), 1.80ꢀ1.76
(m, 1H), 1.00 (t,
= 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3)
J
J
J
N-(4-(Cinnamylsulfonyl)phenyl)acetamide (3ae). 63 mg,
67%, white solid, m.p. 150ꢀ152 °C. 1H NMR (500 MHz,
J
CDCl3) δ 7.84ꢀ7.78 (m, 2H), 7.69 (d,
1H), 7.32ꢀ7.27 (m, 5H), 6.41 (d, = 15.9 Hz, 1H), 6.15ꢀ6.06
(m, 1H), 3.95 (dd, = 7.6, 0.8 Hz, 2H), 2.23 (d, = 4.0 Hz,
J = 8.7 Hz, 2H), 7.60 (s,
δ 144.5, 138.1, 136.0, 134.7, 129.5, 129.2, 128.6, 128.5, 128.4,
128.3, 126.6, 121.2, 71.1, 21.6, 20.9, 11.4. HRMS (EI) m/z
calculated for C18H20O2S [M]+ 300.1184, found 300.1183.
J
J
J
3H). 13C NMR (125 MHz, CDCl3) δ 168.8, 143.2, 143.0, 140.8,
139.3, 136.3, 135.7, 135.0, 132.9, 130.4, 129.4, 128.7, 128.6,
127.0, 126.6, 120.7, 119.2, 116.7, 115.0, 60.6, 24.8. HRMS
(E)-1-Methyl-4-((1-phenylhex-1-en-3-yl)sulfonyl)benzene
1
(3da). 62 mg, 66%, light yellow oil, H NMR (500 MHz,
CDCl3) δ 7.76ꢀ7.69 (m, 2H), 7.33ꢀ7.26 (m, 7H), 6.31 (d,
15.9 Hz, 1H), 5.91 (dd, = 15.9, 9.5 Hz, 1H), 3.68ꢀ3.62 (m,
J
=
J
4 | Org. Biomol. Chem. 2016, 00, 1-3
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1H), 2.43 (s, 3H), 2.19ꢀ2.14 (m, 1H), 1.78ꢀ1.74 (m, 1H), 1.54ꢀ 69.5, 29.3, 21.6, 21.2, 20.0, 13.6. HRMS(EI) m/z calculated for
1.43 (m, 1H), 1.34ꢀ1.27 (m, 1H), 0.94 (t,
= 7.3 Hz, 3H). 13 C21H26O2S [M]+ 342.1654, found 342.1658.
NMR (125 MHz, CDCl3) δ 144.5, 137.8, 136.0, 134.7, 130.0, )-1-Methoxy-3-(3-tosylhex-1-en-1-yl)benzene (3ja). 65
129.4, 129.3, 129.2, 128.6, 128.3, 126.6, 121.5, 69.5, 29.4, mg, 63%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.71
21.6, 20.0, 13.6. HRMS (EI) m/z calculated for C19H22O2S [M]+ (d,
= 8.2 Hz, 2H), 7.29 (d, = 8.0 Hz, 2H), 7.24ꢀ7.21 (m, 2H),
314.1341, found 314.1337. 6.86ꢀ6.83 (m, 2H), 6.24 (d, = 15.8 Hz, 1H), 5.75 (dd, = 15.8,
)-1-Methyl-4-((1-(p-tolyl)pent-1-en-3-yl)sulfonyl)benzene 9.4 Hz, 1H), 3.81 (s, 3H), 3.62 (s, 1H), 2.42 (s, 3H), 2.17ꢀ2.11
J
C
(
E
J
J
J
J
(
E
1
(3ea). 54 mg, 58%, light yellow oil, H NMR (500 MHz, (m, 1H), 1.75ꢀ1.70 (m, 1H), 1.50ꢀ1.40 (m, 1H), 1.32ꢀ1.26 (m,
CDCl3) δ 7.72 (d, = 8.2 Hz, 2H), 7.31ꢀ7.27 (m, 2H), 7.19 (d, 1H), 0.93 (t,
= 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
= 8.1 Hz, 2H), 7.13 (d, = 8.0 Hz, 2H), 6.28 (d, = 15.8 Hz, 159.7, 144.4, 137.3, 134.7, 129.4, 129.2, 128.7, 127.8, 118.9,
1H), 5.86 (dd, = 15.8, 9.4 Hz, 1H), 3.57ꢀ3.51 (m, 1H), 2.43 (s, 114.0, 69.5, 55.3, 29.4, 21.6, 19.9, 13.6. HRMS (EI) m/z
3H), 2.35 (s, 3H), 2.28ꢀ2.25 (m, 1H), 1.78ꢀ1.75 (m, 1H), 0.99 calculated for C20H24O3S [M]+ 344.1446, found 344.1445.
(t, )-1-Fluoro-4-(3-tosylhex-1-en-1-yl)benzene (3ka). 63
= 7.5, 3H). 13C NMR (125 MHz, CDCl3) δ 144.4, 138.3,
138.0, 134.8, 133.2, 129.5, 129.3, 129.2, 126.5, 120.1, 71.7, mg, 62%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.71
21.6, 21.2, 21.0, 11.4. HRMS (ESI+) m/z calculated for (d, = 8.2 Hz, 2H), 7.31 (d, = 8.1 Hz, 2H), 7.27ꢀ7.24 (m, 2H),
C19H22NaO2S [M+Na]+ 337.1233, found 337.1231.
7.03ꢀ6.99 (m, 2H), 6.28 (d, = 15.9 Hz, 1H), 5.87ꢀ5.78 (m,
)-1-Methyl-3-(3-tosylpent-1-en-1-yl)benzene (3fa). 60.5 1H), 3.66ꢀ3.60 (m, 1H), 2.44 (s, 3H), 2.16ꢀ2.11 (m, 1H), 1.79ꢀ
mg, 64%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.72 1.71 (m, 1H), 1.51ꢀ1.43 (m, 1H), 1.35ꢀ1.29 (m, 1H), 0.93 (t,
(d, = 8.2 Hz, 2H), 7.30 (d, = 8.0 Hz, 2H), 7.21 (t, = 246.3
= 7.6 Hz, 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 162.7 (d,
1H), 7.10 (dd, = 16.4, 9.0 Hz, 3H), 6.29 (d, = 15.9 Hz, 1H), Hz), 144.4, 136.6, 134.6, 132.6, 131.3, 129.4 (d, = 23.6 Hz),
5.91 (dd, = 15.8, 9.4 Hz, 1H), 3.58ꢀ3.51 (m, 1H), 2.43 (s, 3H), 128.2 (d, = 8.1 Hz), 121.2 (d, = 2.2 Hz), 115.6 (d, = 21.5
2.35 (s, 3H), 2.28ꢀ2.24 (m, 1H), 1.80ꢀ1.76 (m, 1H), 1.00 (t, Hz), 69.4, 29.4, 21.6, 20.0, 13.6. HRMS (EI) m/z calculated for
7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 144.5, 138.24, C19H21FO2S [M]+ 332.1246, found 332.1249.
138.18, 135.9, 134.8, 129.5, 129.2, 129.1, 128.5, 127.2, 123.8, )-1-Fluoro-3-(3-tosylhex-1-en-1-yl)benzene (3la). 64 mg,
120.9, 71.2, 21.6, 21.3, 21.0, 11.4. HRMS (ESI+) m/z 64%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.71 (d,
calculated for C19H22NaO2S [M+Na]+ 337.1233, found = 8.3 Hz, 2H), 7.34ꢀ7.27 (m, 3H), 7.05 (d,
= 7.8 Hz, 1H),
337.1238. 6.99ꢀ6.95 (m, 2H), 6.28 (d, = 15.9 Hz, 1H), 5.92 (dd, = 15.8,
)-1-Methyl-3-(3-tosylhex-1-en-1-yl)benzene (3ga). 74 9.5 Hz, 1H), 3.68ꢀ3.61 (m, 1H), 2.44 (s, 3H), 2.19ꢀ2.12 (m,
mg, 75%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.72 1H), 1.76ꢀ1.74 (m, 1H), 1.51ꢀ1.43 (m, 1H), 1.33ꢀ1.27 (m, 1H),
(d, = 8.2 Hz, 2H), 7.30 (d, = 8.0 Hz, 2H), 7.21 (t, = 7.6 Hz, 0.94 (t,
= 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 163.0
1H), 7.09 (dd, = 17.9, 8.1 Hz, 3H), 6.26 (d, = 15.9 Hz, 1H), (d, = 244.4 Hz), 144.7, 138.2 (d, = 7.6 Hz), 136.7 (d, = 2.5
5.90 (dd, = 15.8, 9.5 Hz, 1H), 3.68ꢀ3.61 (m, 1H), 2.43 (d, Hz), 134.6, 130.0 (d, = 21.8 Hz), 129.5, 129.2 (d,
4.6 Hz, 3H), 2.35 (s, 3H), 2.16 (d, = 3.3 Hz, 1H), 1.80ꢀ1.72 Hz), 122.7, 122.1, 115.2 (d, = 21.3 Hz), 113.0 (d,
(m, 1H), 1.53ꢀ1.44 (m, 1H), 1.36ꢀ1.29 (m, 1H), 0.94 (t,
Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 144.5, 138.2, 137.9, C19H21FO2S [M]+ 332.1246, found 332.1243.
135.9, 134.7, 129.4, 129.2, 129.1, 128.5, 127.2, 123.8, 121.2, )-1-Chloro-4-(3-tosylhex-1-en-1-yl)benzene (3ma). 70.5
69.5, 30.9, 29.3, 21.6, 21.3, 20.0, 13.6. HRMS (EI) m/z mg, 67%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.70
J
J
J
J
J
J
J
(E
J
J
J
(
E
J
=
J
J
J
J
J
J
J
J
J
J
J
J
=
(
E
J
J
J
J
(
E
J
J
J
J
J
J
J
J
J
J
J
=
J
J
J
= 10.8
= 21.8
J
J
J
= 7.3 Hz), 69.3, 29.4, 21.6, 20.0, 13.6. HRMS (EI) m/z calculated for
(
E
calculated for C20H24O2S [M]+ 328.1497, found 328.1498.
)-1-Methyl-4-((1-(p-tolyl)hex-1-en-3-yl)sulfonyl)benze-
(d,
(d,
J
J
= 8.3 Hz, 2H), 7.32ꢀ7.27 (m, 4H), 7.22ꢀ7.19 (m, 2H), 6.26
= 15.9 Hz, 1H), 5.89 (dd, = 15.9, 9.5 Hz, 1H), 3.67ꢀ3.61
(
E
J
ne (3ha). 74 mg, 75%, light yellow oil, 1H NMR (500 MHz, (m, 1H), 2.43 (s, 3H), 2.17ꢀ2.10 (m, 1H), 1.79ꢀ1.70 (m, 1H),
CDCl3) δ 7.75ꢀ7.68 (m, 2H), 7.29 (d,
= 6.2 Hz, 2H), 7.13 (d, = 8.0 Hz, 2H), 6.26 (d,
1H), 5.85 (dd,
J
= 8.0 Hz, 2H), 7.18 (t,
J
1.50ꢀ1.43 (m, 1H), 1.34ꢀ1.26 (m, 1H), 0.93 (t, J = 7.5 Hz, 3H).
J
J
= 15.8 Hz, 13C NMR (125 MHz, CDCl3) δ 144.6, 136.6, 134.6, 134.4,
J
= 15.8, 9.5 Hz, 1H), 3.67ꢀ3.60 (m, 1H), 2.43 (s, 134.1, 129.5, 129.2, 128.8, 127.7, 122.2, 69.4, 29.4, 21.6, 20.0,
3H), 2.35 (s, 3H), 2.20ꢀ2.13 (m, 1H), 1.80ꢀ1.71 (m, 1H), 1.53ꢀ 13.6. HRMS (EI) m/z calculated for C19H21ClO2S [M]+
1.44 (m, 1H), 1.35ꢀ1.28 (m, 1H), 0.96ꢀ0.92 (m, 3H). 13C NMR 348.0951, found 348.0958.
(125 MHz, CDCl3) δ 144.4, 138.3, 137.7, 134.7, 133.2, 129.4,
129.3, 128.8, 126.5, 120.4, 69.5, 29.4, 21.6, 21.2, 20.0, 13.6. mg, 56%, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.71
HRMS (EI) m/z calculated for C20H24O2S [M]+ 328.1497, (d,
= 8.2 Hz, 2H), 7.31 (d, = 8.1 Hz, 2H), 7.25 (d, = 5.2
found 328.1500. Hz, 3H), 7.17ꢀ7.13 (m, 1H), 6.25 (d, = 15.9 Hz, 1H), 5.93 (dd,
)-1,3-Dimethyl-5-(3-tosylhex-1-en-1-yl)benzene (3ia). 71 = 15.9, 9.5 Hz, 1H), 3.68ꢀ3.61 (m, 1H), 2.44 (s, 3H), 2.18ꢀ
mg, 70 %, light yellow oil, 1H NMR (500 MHz, CDCl3) δ 7.72 2.11 (m, 1H), 1.80ꢀ1.70 (m, 1H), 1.51ꢀ1.43 (m, 1H), 1.33ꢀ1.26
(d, = 8.2 Hz, 2H), 7.30 (d, = 8.1 Hz, 2H), 6.92 (d, = 7.5 (m, 1H), 0.93 (t,
= 7.3 Hz, 3H). 13C NMR (125 MHz, CDCl3)
Hz, 3H), 6.22 (d, = 15.9 Hz, 1H), 5.90 (dd, = 15.8, 9.5 Hz, δ 144.7, 137.7, 136.4, 134.62, 134.56, 129.9, 129.5, 129.2,
(E)-1-Chloro-3-(3-tosylhex-1-en-1-yl)benzene (3na). 58
J
J
J
J
(
E
J
J
J
J
J
J
J
1H), 3.66ꢀ3.60 (m, 1H), 2.44 (s, 3H), 2.31 (s, 6H), 2.20ꢀ2.13 128.3, 126.5, 124.7, 123.2, 69.3, 29.4, 21.6, 20.0, 13.6. HRMS
(m, 1H), 1.80ꢀ1.72 (m, 1H), 1.49ꢀ1.46 (m, 1H), 1.33ꢀ1.27 (m, (EI) m/z calculated for C19H21ClO2S [M]+ 348.0951, found
1H), 0.93 (t,
J
= 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 348.0950.
144.41, 138.1, 135.9, 134.8, 130.0, 129.4, 129.2, 124.5, 121.0,
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(E)-(3-Tosylprop-1-ene-1,3-diyl)dibenzene (3oa). 48 mg, 46%,
white solid, m.p. 150ꢀ152 °C. 1H NMR (500 MHz, CDCl3) δ 7.57 (d,
J = 8.2 Hz, 2H), 7.39ꢀ7.32 (m, 9H), 7.31ꢀ7.27 (m, 1H), 7.22 (d, J =
8.1 Hz, 2H), 6.66ꢀ6.54 (m, 2H), 4.87 (d, J = 8.4 Hz, 1H), 2.40 (s,
3H). 13C NMR (125 MHz, CDCl3) δ 144.5, 137.9, 135.9, 134.4,
132.5, 129.7, 129.2, 128.8, 128.6, 128.5, 128.4, 126.7, 120.2, 75.3,
21.5.
Organic & Biomolecular Chemistry
Ostercamp, Pure Appl. Chem. 2000, 72, 1671; (c) K. Plesniak,
A. Zarecki and J. Wicha, Top. Curr. Chem. 2007, 275, 163; (d)
A. El-Awa, M. N. NoShi, X. M. du Jourdin and P. L. Fuchs,
Chem. Rev. 2009, 109, 2315; (e) A. R. Alba, X. Companyó and
R. Rios, Chem. Soc. Rev. 2010, 39, 2018.
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3
Oxford, U.K., 1991; Vol.
6, pp 133; (c) H.-J. Gais, In
(E)-1-Methyl-4-(3-(phenylsulfonyl)hex-1-en-1-yl)benzene
Asymmetric Synthesis with Chemical and Biological Methods;
D. Enders and K.-E. Jäger, Eds.; Wiley-VCH: Weinheim,
Germany, 2007; p 215.
For reviews on transition metal-catalyzed allylic substitution,
see: B. M. Trost and M. L. Crawley, Chem. Rev., 2003, 103,
2921.
(a) B. M. Trost and N. R. Schmuff, J. Am. Chem. Soc., 1985,
107, 396; (b) K. Hiroi and K. Makino, Chem. Lett., 1986, 617;
(c) B. M. Trost, M. G. Organ and G. A. O’Doherty, J. Am.
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(e) S. Kamijo, M. Al-Masum and Y. Yamamoto, Tetrahedron
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Jagusch, N. Spalthoff, F. Gerhards, M. Frank and G. Raabe,
1
(3hc). 63.3 mg, 68%, light yellow oil, H NMR (500 MHz,
CDCl3) δ 7.88ꢀ7.81 (m, 2H), 7.64ꢀ7.59 (m, 1H), 7.50 (dd,
10.7, 4.8 Hz, 2H), 7.14 (dd, = 21.1, 8.1 Hz, 4H), 6.22 (d,
15.8 Hz, 1H), 5.85 (dd,
1H), 2.35 (s, 3H), 2.22ꢀ2.15 (m, 1H), 1.83ꢀ1.73 (m, 1H), 1.54ꢀ
1.45 (m, 1H), 1.35ꢀ1.28 (m, 1H), 0.94 (t,
= 7.5 Hz, 3H). 13
J
=
4
5
J
J
=
J
= 15.8, 9.5 Hz, 1H), 3.69ꢀ3.61 (m,
J
C
NMR (125 MHz, CDCl3) δ 138.4, 137.9, 137.6, 133.5, 133.1,
129.3, 129.2, 128.8, 126.5, 120.2, 69.5, 29.2, 21.2, 20.0, 13.6.
HRMS (EI) m/z calculated for C19H22O2S [M]+ 314.1341,
found 314.1348.
(E)-1-Fluoro-4-((1-(p-tolyl)hex-1-en-3-yl)sulfonyl)benzene
1
(3hh). 64 mg, 64%, light yellow oil, H NMR (500 MHz,
CDCl3) δ 7.88ꢀ7.80 (m, 2H), 7.20ꢀ7.15 (m, 4H), 7.13 (d, = 8.1
Hz, 2H), 6.23 (d, = 15.9 Hz, 1H), 5.85 (dd, = 15.9, 9.5 Hz,
1H), 3.67ꢀ3.60 (m, 1H), 2.35 (s, 3H), 2.22ꢀ2.15 (m, 1H), 1.82ꢀ
1.73 (m, 1H), 1.52ꢀ1.48 (m, 1H), 1.36ꢀ1.28 (m, 1H), 0.95 (t,
7.3 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 165.8 (d,
= 254.6
Hz), 138.6, 138.1, 133.7, 132.9, 132.1 (d, = 9.6 Hz), 129.4,
126.5, 120.1, 116.1 (d, = 22.3 Hz), 69.7, 29.2, 21.2, 20.0,
Chem.–Eur. J., 2003,
Y.-M. Liang, Tetrahedron Lett., 2005, 46, 3469; (i) F. X. Felpin,
Y. Landais, J. Org. Chem., 2005, 70 6441; (j) S.
9, 4202; (h) M.-C. Liao, X.-H. Duan and
J
J
J
,
Chandrasekhar, V. Jagadeshwar, B. Saritha and C.
Narsihmulu, J. Org. Chem., 2005, 70, 6506; (k) M. Ueda and J.
F. Hartwig, Org. Lett., 2010, 12, 92; (l) X.-S. Wu, Y. Chen, M.-
J
=
J
B. Li, M.-G. Zhou and S.-K. Tian, J. Am. Chem. Soc., 2012, 134
,
J
14694; (m) T.-T. Wang, F.-X. Wang, F.-L. Yang and S.-K. Tian,
Chem. Commun., 2014, 50, 3802; (n) M. Jegelka and B.
Plietker, Org. Lett., 2009, 11, 3462; (o) L. M. Stanley, C. Bai,
J
13.6. HRMS (EI) m/z calculated for C19H21FO2S [M]+
332.1246, found 332.1245.
M. Ueda and J. F. Hartwig, J. Am. Chem. Soc., 2010, 132
8918; (p) M. Jegelka and B. Plietker, Chem.–Eur. J., 2011, 17
10417;
,
,
(
E
)-(3-(Ethylsulfonyl)prop-1-en-1-yl)benzene (5). 20 mg,
32%, white solid, m.p. 95ꢀ97 °C. 1H NMR (500 MHz, CDCl3) δ
7.44ꢀ7.39 (m, 2H), 7.38ꢀ7.27 (m, 3H), 6.71 (d, = 15.9 Hz, 1H),
6.31ꢀ6.21 (m, 1H), 3.87 (d, = 7.5 Hz, 2H), 3.02 (q, = 7.5 Hz,
2H), 1.40 (t,
= 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
6
7
I. Kadota, A. Shibuya, Y. S. Gyoung and Y. Yamamoto, J. Am.
Chem. Soc., 1998, 120, 10262.
J
J
J
(a) I. Kadota, A. Shibuya, L. M. Lutete and Y. Yamamoto, J.
Org. Chem., 1999, 64, 4570; (b) N. T. Patil, H. Wu, I. Kadota
and Y. Yamamoto, J. Org. Chem., 2004, 69, 8745; (c) N. T.
Patil and Y. Yamamoto, J. Org. Chem., 2004, 69, 6478; (d) L.
M. Lutete, I. Kadota and Y. Yamamoto, J. Am. Chem. Soc.,
2004, 126, 1622; (e) N. T. Patil, F. N. Khan and Y. Yamamoto,
Tetrahedron Lett., 2004, 45, 8497; (f) G. B. Bajracharya, Z.
Huo and Y. Yamamoto, J. Org. Chem., 2005, 70, 4883; (g) N.
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Yamamoto, J. Org. Chem., 2006, 71, 4270; (h) N. Patil, Z. Huo,
J
138.6, 135.4, 128.7, 128.6, 126.6, 115.4, 56.4, 45.7, 6.4. HRMS
(ESI+) m/z calculated for C11H14NaO2S [M+Na]+ 233.0607,
found 233.0597.
Acknowledgements
G. B. Bajracharya and Y. Yamamoto, J. Org. Chem., 2006, 71
,
Financial support from the National Natural Science
Foundation of China (21402175) is acknowledged.
3612; (i) N. T. Patil, H. Wu and Y. Yamamoto, J. Org. Chem.,
2007, 72, 6577; (j) M. Narsireddy and Y. Yamamoto, J. Org.
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,
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Notes and references
1
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6 | Org. Biomol. Chem. 2016, 00, 1-3
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DOI: 10.1039/C6OB01929C
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Breit group has developed an elegant rhodium catalyzed
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