Suzuki-Miyaura Coupling Reactions of Conjunctive Reagents: 2-Borylated Allylic Sulfones

Article abstract of DOI:10.1021/acs.joc.5b01253

In support of various efforts in our group, we developed methods for the convenient Suzuki-Miyaura coupling of borylated allylic sulfones with various electrophiles in both inter- and the less common intramolecular modes. The procedure facilitates the preparation of a wide variety of sulfones in a straightforward fashion, including six- through eight-membered rings.

Full text of DOI:10.1021/acs.joc.5b01253

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Suzuki-Miyaura Coupling Reactions of Conjunctive Reagents: 2-
Borylated Allylic Sulfones
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Erich F. Altenhofer and Michael Harmata*
Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65211
harmatam@missouri.edu
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ArI, 10% Pd2dba3
SO2Ph
Ar
20% AsPh3
3.0 Ag2O
Bpin
PhO2S
PhO2S
THF, rt, 2 h
ABSTRACT: In support of various efforts in our group, we developed methods for the
convenient Suzuki-Miyaura coupling of borylated allylic sulfones with various electrophiles in
both inter- and the less common intramolecular modes. The procedure facilitates the preparation
of a wide variety of sulfones in a straightforward fashion, including six- through eight-membered
rings.
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Introduction
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We recently became interested in the chemistry of the known borylated allylic sulfone 1a1 as
well as its congener 1b. For example, we reported that 1b could be readily deprotonated and
alkylated with electrophiles, the electrophilic boron atom surviving the process (e.g., 2).2 Further,
we showed that certain alkylation products could be subjected to intramolecular ring-closing
metathesis to produce cyclic boronates (e.g., 3).3 Intermolecular cross-metathesis was also
possible, though limited in scope. A procedure involving the alkylation of 1b followed by a
radical isomerization more generally gave products (e.g., 4) that were equivalent to those derived
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from cross-metathesis (Scheme 1).4
Scheme 1. Chemistry of Borylated Allylic Sulfones
O
1. (1b) LDA
2. 4-iodo-1-butene
68%
O
B
B
O
ArO2S
O
PhO2S
1a, Ar = p-Tol
1b, Ar = Ph
2
Grubbs II (5 mol %)
CH2Cl2, reflux
2 h, 92%
1. (1b) LDA
2. 3-phenyl-1-iodopropane
3. PhSO2Na, AcOH, 95 o
C
52%
O
PhO2S
O
B
B
O
ArO2S
O
Ph
4
3
In the course of these preliminary studies, we also reported a small number of reactions that
involved the inter- and intramolecular Suzuki-Miyaura (SM) coupling reactions.2-4 This paper
reports all of our studies in this area to date.
Our interest in the SM reaction was initially stimulated by a desire to pursue an asymmetric
phase-transfer-catalyzed 6π-electrocyclization reaction on substrates such as 5 (Scheme 2).5
Computational studies have suggested that with appropriate substitution on the hexatriene, such
cyclizations might take place with facility at moderate temperatures.5a
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Scheme 2. Motivation for Cross-Coupling Studies
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5
ArO2S
O
B
SM
I
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7
8
R
+
R
cross-coupling
O
ArO2S
1a/b
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Results and Discussion
Using the procedure reported in the literature,1 2-boryl allylic sulfone 1a was prepared from
commercially available 2-isopropenyl boronate ester 7. In addition, Z-iodobutadienes 8a and 8b
could be quickly prepared from the corresponding aldehydes via Z-selective Wittig olefination.6
Preliminary attempts to couple 1a and either 8a6b or 8b proceeded in moderate yields, resulting in
isolation of cyclohexadiene products 9a and 9b (Scheme 3). Diene 9a remained impure and was
not characterized, but 9b was amenable to purification and characterization. It was clear from 1H
NMR spectra that 9b was cyclic due to the presence of methylene protons, which appeared as
triplets at 2.62 ppm and 2.40 ppm and shared the same coupling constant (J = 8 Hz). Presumably,
the high temperatures necessary to promote coupling also facilitated the in situ thermal 6π
electrocyclization. This is an interesting and synthetically useful result. However, for our
purposes, we needed uncyclized trienes. This marked the beginning of our work in the
exploration of this coupling methodology.
Scheme 3. Preliminary SM Coupling Studies
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O
B
O
B
1. p-TolSO2I
Me
O
O
Ts
2. TEA
7
6
1a
7
8
9
2% PdCl2
4% RuPhos
3 equiv. NaOH
Toluene/H2O
15-17 h, 100 oC
I
Ts
+
R1
R1
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R2
R2
9a, (50%) R1 = Me; R2 = Ph
9b, (76%) R1 = Ph; R2= H
8a, R1 = Me; R2 = Ph
8b, R1 = Ph; R2= H
iPrO
OiPr
PCy2
RuPhos
We thus set out to find mild conditions for the SM reaction of 1a/b and various congeners.
Efforts to achieve coupling without cyclization were focused on tuning the reactivity of boronate
coupling partner and choosing the appropriate catalyst system for this reaction. Although the
reactivity of the free boronic acids has proven to be effective for SM cross-coupling, the pinacol
ester derivatives are typically preferred for their increased stability towards moisture/air, making
them easier to handle.7
The search for optimal cross-coupling conditions began with a survey of various organoboron
derivatives of 1b. To further explore potential options for the optimal organoboron derivative,
the MIDA,8 DABO,9 and potassium trifluoroborate10 derivatives of 1b, 12, 13, and 10,
respectively, were prepared (Scheme 4). In the event, ester 1b was converted to the potassium
trifluoroborate 10 by treatment with potassium bifluoride in methanol (Scheme 4).11 The
potassium trifluoroborate could be hydrolyzed to the parent acid 11 in nearly quantitative yield in
under four hours by stirring with silica in the presence of water.12 Esters 12-13 were prepared
from 11 under normal esterification procedures using a Dean-Stark apparatus.
Scheme 4. Preliminary SM Coupling Studies
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B(pin)
BF3K
KHF2
SiO2/H2O
PhO2S
PhO2S
10
MeOH/H2O
4 h, 90%
1b
4 h,98%
6
7
8
9
MeN
O
MIDA
B
O
O
toluene/DMSO
reflux, 16 h
66%
PhO2S
12
O
B(OH)2
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PhO2S
O
DEA, Et2O
rt, 2 h, 70%
NH
11
B
PhO2S
13
O
With each derivative in hand, their relative reactivities were examined through a simple cross-
coupling reaction with p-iodoacetophenone (Table 1). Under the relatively mild conditions
originally developed by Molander and co-workers,10 the trifluoroborate derivative provided the
cross-coupled product in the highest yield (Table 1, entry 1). Although each derivative would
most likely require individual optimization with respect to each of the reaction variables, this
study provided a benchmark that gave a rough approximation of the relative reactivities of the
boron derivatives. The mass balance for several coupling reactions was low and while it would
have been nice to identify side-products, they tended to be very polar and difficult to isolate from
silica colums (reverse phase was not helpful here).
Table 1. Suzuki-Miyaura Couplings of 1b and 10-13 with p-Iodoacetophenone
I
5% PdCl2(dppf)
Ac
3 equiv Cs2CO3
X
+
PhO2S
toluene/H2O (3:1)
PhO2S
80 °C , 8 h
14a
Ac
1b, 10-13
entry
#, -X
yield (%)
1
2
10, -BF3K
59
53
11, -B(OH)2
O
B
3
4
5
21
34
32
O
1b,
MeN
O
O
O
B
O
12,
13,
O
NH
B
O
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We anticipated that the boronate esters 1b, 12 and 13 would afford a lower yield than the
boronic acid 11 because they need to hydrolyze to engage in transmetalation.13 We made no
special effort to optimize the yields of their SM reactions. For our purposes, given the popularity
of potassium organotrifluoroborates, their facile synthesis, and the results of Table 1, this
derivative seemed the best choice for further exploration.10,14
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We therefore examined the reaction of 10 with a small number of para-substituted
nitrobenzenes in order to determine the best “leaving group” in the coupling process. The results
are summarized in Scheme 5. They show that for this class of substrates, bromide, iodide and
triflate all function with essentially the same efficiency, with the triflate group performing only
slightly better than the two halogens.
Scheme 5. Leaving Group Effects on SM Coupling of 10
X
5% PdCl2(dppf)
3 equiv Cs2CO3
toluene/H2O (3:1)
80 °C , 8 h
K
BF3
+
PhO2S
10
NO2
NO2
PhO2S
14b
X = I, 53%
X = Br, 50%
X = OTf, 56%
With the results in hand we decided to explore the reaction of 10 with a variety of aryl iodides
in order to determine the scope of the reaction. The results are summarized in Table 2. Cross-
coupling was effective with aryl substituents in the ortho, meta or para position, though the yield
of coupling product obtained from 2–bromoiodobenzene was rather low (Table 2, entry 9). This
particular reaction afforded a complex reaction mixture from which only a small amount of
product could be isolated. We were unable to isolate anything else of sufficient purity to
characterize by proton NMR. Yields were otherwise fair to good across the range of substrates
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examined. Interestingly, the adduct 14h was obtained in reasonable yields; the aliphatic iodide
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did not interfere with the coupling reaction.
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Table 2. Coupling Reactions of 10
ArI, 5% PdCl2(dppf)
K
Ar
3 equiv Cs2CO3
toluene/H2O (3:1)
80 °C , 8 h
BF3
PhO2S
PhO2S
14
10
entry
1
product
yield (%)
Ac
59
53
56
74
72
PhO2S
14a
NO2
2
3
4
5
PhO2S
14b
PhO2S
14c
F
PhO2S
14d
CF3
PhO2S
14e
Cl
6
7
81
PhO2S
14f
60a
PhO2S
CF3
14g
I
8
63
PhO2S
14h
PhO2S
9
35
72
Br
14i
N
10
PhO2S
14j
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F
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PhO2S
14k
7
8
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aProduct was contaminated with allyl phenyl sulfone, from which it could not be separated.
While these results were important, we still wanted to to find a procedure that would allow for
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cross-coupling at or below room temperature. We searched the literature carefully in order to
avoid intensive and expensive screening studies and fortunately found a methodology that
worked very well without having to resort to any optimization. A protocol developed by Weeber
and Gillman that utilized silver oxide and triphenylarsine allowed for room temperature SM
cross-coupling between aryl boronic acids and 2-halo-2,3-butadieneoates.15 In addition, this
procedure was also utilized in a SM cross-coupling reaction between a boronic ester and a
bromobutadiene in the total synthesis of (+)-fostriecin.16 We therefore adopted these conditions
in anticipation of there being a likely solution to the problem of high temperatures associated
with our other coupling reactions and in the hope that 1b could be used directly in coupling. The
results of our studies are shown in Table 3. Gratifyingly, under these new reaction conditions,
various aryl iodides coupled with boronate ester 1b to afford essentially quantitative yields of
coupling products in under 2 hours at room temperature, though the reaction slowed significantly
when a methoxy group was ortho to the iodide functionality (Table 3, entry 7).
Extension of this procedure to alkenyl electrophiles such as 8b resulted in a messy reaction
mixture (Scheme 6, equation 1). The intended coupled product, 15, was never observed.
Although there was evidence for the formation of the corresponding cyclized product, attempts to
isolate and purify the material were unsuccessful. The isolation of allylic alcohol 17 under
identical conditions may be a result of the greater stability of compound 16 versus 8b. Under the
reaction conditions, decomposition of 8b might occur at a faster rate than coupling.
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Table 3. Room Temperature SM Couplings of 1b with Aryl Iodides
ArI, 10% Pd2dba3
Bpin
20% AsPh3
3.0 Ag2O
Ar
PhO2S
PhO2S
1b
14
THF, rt, 2 h
entry
product
yield (%)
1
2
3
4
5
6
14b
14c
14f
14g
14j
99
99
63
71
99
99
14k
MeO
7
83a
PhO2S
14l
aReaction required 5 days to complete.
Scheme 6. Leaving Group Effects on SM Coupling of 10
10% Pd2dba3
20% AsPh3
SO2Ph
I
Bpin
Bpin
(1)
+
PhO2S
1b
X
Ph
8b
3.0 equiv. Ag2O
THF, rt, 2 h
Ph
15
PhO2S
Ph
I
Ph
as above
(2)
+
PhO2S
1b
74%
17
16
OH
HO
In a recent publication, we demonstrated the generation of bicyclic molecules through an
alkylation/metathesis sequence.3 We thought that similar, but unique, bicyclic structures could
be prepared through an intramolecular SM cross-coupling variant. We have, in fact, reported one
example of this approach to a polycyclic compound as shown in equation 3.4 Thus, the
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intramolecular SM coupling of 18 proceeded at room temperature under the reaction conditions
shown in Table 3 to give 19 in excellent yield.
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9
O
O
B
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10% Pd2dba3
20% AsPh3
PhO2S
I
3 equiv Ag2O
THF, rt, 2 h, 90%
(3)
18
PhO2S
19
That reaction served as part of our investigation of intramolecular SM cross-coupling
chemistry, which was initiated with the preparation of alkylated compounds bearing aryl iodide
functionality that would allow for future intramolecular cross-coupling. The results are shown in
Table 4. Using primary iodides and triflates with varying chain lengths, substrates 21a-d were
prepared in a straightforward fashion.
Table 4. Synthesis of Substrates for Intramolecular SM Coupling
I
B(pin)
n X
B(pin)
LDA
THF, -78 oC
rt, 3 h
+
PhO2S
n
I
SO2Ph
21a-d
1b
20a-d
entry
1
starting material
product
21a
yield (%)
67
20a, X = I,
n = 1
2
20b, X = I,
n = 2
21b
71
3
4
20c, X = OTf, n = 3a
20d, X = OTf, n = 4a
21c
21d
65
70
aTriflates were prepared from their corresponding alcohols.
We then applied the silver oxide-promoted SM cross-coupling conditions (Table 3), to prepare
benzo-fused bicyclic products (Table 5). With the exception of substrate 21a, the formation of
six-, seven- and even eight-membered benzo-fused bicyclics occurred within two hours in high
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yields. The formation of 22d is noteworthy, in that earlier attempts to access eight-membered
rings via cross-metathesis were unsuccessful.3 These results are interesting and apparently
unique; intramolecular SM cyclizations of this type are rather rare.17 The reaction of 21a led to
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the decomposition of starting material.
Table 5. Intramolecular SM Coupling of 21a-d
SO2Ph
10% Pd2dba3
I
B(pin)
20% AsPh3
3.0 equiv Ag2O
THF, rt, 2 h
n
SO2Ph
21a-d
22a-d
entry
1
starting material
product
yield (%)
0a
21
22
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SO2Ph
21a
21b
22a
SO2Ph
2
3
96
99
22b
SO2Ph
21c
21d
22c
SO2Ph
4
93
22d
aReaction was incomplete at 2 h and was allowed to stir for an additional 20 h.
While the reasons behind the failure of substrate 21a to cyclize can only be speculated upon, it
is interesting to note that Piers reported the intramolecular Stille cyclization shown in equation
4.18 It is conceivable that different mechanisms associated with transmetalation in Stille and SM
couplings give rise to an endocyclic restriction19 that prevents cyclization in the case of 21a.
Further studies are needed to support this hypothesis.20
I
Me
CO2Me
5% Pd(OAc)2, 10% PPh3
TEA, MeCN, reflux
>80%
(4)
CO2Me
SnMe3
Me
24
23
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Conclusion
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In summary, we have discovered a mild method for both the inter- and intramolecular Suzuki-
Miyaura coupling of 2-borylated allylic sulfones. These reactions, particularly those that are
intramolecular, afford opportunities for the simple and rapid construction of polycyclic structures.
Such studies, as well as further studies in the synthesis of hexatrienes using this methodology, are
of interest to us for the construction of molecules that could be used to test concepts in
electrocyclization reactions. Further results will be reported in due course.
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Experimental Section
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All glassware and needles were oven-dried and allowed to cool in a desiccator prior to use. All glass
vessels used in metal-catalyzed coupling reactions were cleaned with aqua regia. Toluene and
tetrahydrofuran (THF) were distilled from sodium-benzophenone prior to use. Solvents used in coupling
reactions were degassed prior to use via three freeze-pump-thaw cycles. Reactions were monitored by
TLC using a UV lamp or cerium molybdate stain. All products were purified by flash chromatography
using 230-400 mesh silica and, if crystalline, were recrystallized from ethyl acetate or hexane:diethyl ether
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until a constant melting point was observed. All compounds were characterized by H and 13C Nuclear
Magnetic Resonance (NMR) spectroscopy using a 500 MHz spectrometer. Proton spectra were reported
in δ units, parts per million (ppm), relative to trimethylsilane internal standard (0.00 ppm). Carbon spectra
are reported in ppm relative to deuterated chloroform peak (77.0 ppm) or (39.52 ppm) where DMSO was
used. Infrared spectra were recorded on a FT-IR spectrometer. High-resolution mass spectra were acquired
on a FTICR-MS with an ion cyclotron resonance analyzer (ICR) by an electrospray ionization (ESI).
(Z)-(4-iodobuta-1,3-dien-2-yl)benzene (8b). To a slurry of iodomethyltriphenylphosphonium iodide (5.36
g, 10.1 mmol) in 20 mL dry THF was added NaHMDS (0.8 M in THF, 13.6 mL, 10.9 mmol,) and HMPA
(2.1 mL). The dark red solution was stirred for 5 minutes at room temperature, then cooled to -78 oC. To
the ylide was added atropaldehyde (1.11 g, 8.42 mmol), as a solution in THF (1.0 mL) dropwise. After
addition, the reaction was allowed to reach room temperature and stirred for 30 minutes before being
quenched with aqueous NH4Cl. The organic layer was separated, concentrated under rotary evaporator
and the crude oil was purified by flash chromatography (100% hexanes) resulting in a yellow oil (600 mg,
1
28%). H NMR (500 MHz, CDCl3) δ 7.39 – 7.29 (m, 5H), 6.96 (d, J = 8.5 Hz, 1H), 6.66 (d, J = 8 Hz, 1H),
5.72 (s, 1H), 5.51 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 145.1, 139.5, 138.5, 128.5, 128.0, 126.6, 116.8,
86.6; IR (film) 3062, 3027, 2978, 2931, 1447, 1423, 1330, 1305, 1214, 1143, 1084 cm-1; no molecular ion
in HRMS.
Suzuki-Miyaura Cross-Coupling Procedure A. 4-((phenylsulfonyl)methyl)-2,3-dihydro-1,1'-biphenyl
(9b). In a sealed tube containing 1.0 mL toluene and 0.1 mL water was added vinyl iodide 8b (50 mg,
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0.196 mmol), boronic ester 1a (94 mg, 0.292 mmol), palladium (II) chloride (0.70 mg, 3.9 µmol), RuPhos
(3.64 mg, 7.8 µmol), and sodium hydroxide (25 mg, 0.62 mmol). The reaction was sealed and heated to
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100 C for 17 h. The reaction was cooled to room temperature and extracted with dichloromethane. The
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organic extracts were washed with brine, dried over magnesium sulfate and concentrated under reduced
pressure. The crude was purified via column chromatography (20% ethyl acetate/hexanes) yielding a
white solid (48 mg, 76%). mp = 168 °C; 1H NMR (500 MHz, CDCl3) δ 7.77 (d, J = 8.0 Hz, 2H), 7.42 (d, J
= 8.0 Hz, 2H), 7.33 (t, J = 8.0 Hz, 4H), 7.23 (d, J = 8.0 Hz, 1H), 6.21 (d, J = 5.5 Hz, 1H), 5.76 (d, J = 5.5
Hz, 1H), 3.87 (s, 2H), 2.62 (t, J = 10.0 Hz, 2H), 2.45 (s, 3H), 2.40 (t, J = 10.0 Hz, 2H); 13C NMR (125
MHz, CDCl3) δ 144.8, 140.4, 137.7, 135.7, 129.8, 129.3, 128.8, 128.6, 127.6, 125.2, 125.1, 120.3, 64.5,
27.1, 26.0, 21.8; IR (film) 3062, 3027, 2978, 2931, 1447, 1423, 1330, 1305, 1214, 1143, 1084 cm-1;
HRMS calcd for (C20H20O2S)Na+ 347.1076; Found: 347.1079.
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(3-(phenylsulfonyl)prop-1-en-2-yl)potassium trifluoroborate (10). The pinacol ester 1b (3.0 g, 9.7 mmol)
was dissolved in methanol (80 mL) and treated with an aqueous solution of potassium hydrogen fluoride
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(5.3 g, 67.9 mmol). The slurry was stirred for 2 h at 25 C and the solvent was removed under reduced
pressure. The crude product was dissolved in boiling acetonitrile and hot-filtered to remove excess
potassium hydrogen fluoride. The acetonitrile was removed under reduced pressure and the resulting
white solid could be purified by rinsing with ethyl acetate leaving behind a fluffy white solid (2.37 g,
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85%). mp = 214 - 215 °C; H NMR (500 MHz, Acetone-d6) δ 7.89 (d, J = 7.0 Hz, 2H), 7.65 (t, J = 7.0
Hz, 1H), 7.56 (t, J = 7.0 Hz, 2H), 5.26 (s, 1H), 4.96 (s, 1H), 3.89 (s, 2H); 13C NMR (500 MHz, CD3CN)
141.1, 134.1, 129.8, 129.4, 124.3, 118.3 (CN + buried peak?), 62.8; HRMS calcd for (C9H9BF3KO2S)Na+
310.9897; Found: 310.9895.
(3-(phenylsulfonyl)prop-1-en-2-yl)boronic acid (11). Potassium trifluoroborate 10 (100 mg, 0.347 mmol)
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was dissolved in 5 mL water (0.07 M) and stirred with excess silica for 4 h at 25 C. Once the reaction
was complete, the silica was filtered and the filter cake was washed several times with ethyl acetate. The
filtrate was added to a separatory funnel and the aqueous phase was extracted with ethyl acetate (3 x 10
mL). The organic layers were collected and dried over magnesium sulfate. The solvent was removed
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leaving behind a white solid that became an oil (90 mg, 98%). H NMR (500 MHz, Acetone-d6) δ 7.86 (d,
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J = 7.0 Hz, 2H), 7.72 (d, J = 7.5 Hz, 1H), 7.62 (t, J = 7.0 Hz, 2H), 6.94 (s, 2H), 5.99 (d, J = 3.0 Hz, 1H),
5.57 (s, 1H), 4.07 (s, 2H); 13C NMR (125 MHz, Acetone-d6) δ 140.1, 136.1, 134.4, 129.8, 129.5, 62.1; IR
(film) 3062, 3027, 2978, 2931, 1447, 1423, 1372, 1305, 1214, 1143, 1084 cm-1; HRMS calcd for
(C9H11BO4S)Na+ 249.0363; Found: 249.0363.
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6-methyl-2-(3-(phenylsulfonyl)prop-1-en-2-yl)-1,3,6,2-dioxazaborocane-4,8-dione (12). Boronic acid 11
(134 mg, 0.592 mmol) and N-methyliminodiacetic acid (96 mg, 0.651 mmol) were dissolved in 5 mL
toluene/DMSO (1:1). The solution was heated to 120 oC for 17 h and diluted with dichloromethane. The
organic layer was separated and washed with water, brine and dried over magnesium sulfate. The solvent
was removed under reduced pressure resulting in a solid that could be purified by washing with boiling
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hexanes and decanting (159 mg, 80%). mp = 184 C. H NMR (500 MHz, DMSO-d6) δ 7.86 (d, J = 7.5
Hz, 2H), 7.74 (t, J = 7.5 Hz, 1H), 7.65 (t, J = 7.5 Hz, 2H), 5.73 (t, J = 7.5 Hz, 2H), 5.70 (s, 1H), 4.25 (d, J
= 17.0 Hz, 2H), 4.01 (d, J = 17.0 Hz, 2H), 4.02 (s, 2H), 2.82 (s, 3H); 13C NMR (500 MHz, CDCl3) δ 169.1,
139.3, 133.7, 133.6, 129.3, 127,8, 62.4, 59.2, 47.2; HRMS calcd for (C14H16BNO6S)Na+ 360.0683; Found:
360.0684.
8-(3-(phenylsulfonyl)prop-1-en-2-yl)hexahydro-[1,3,2]oxazaborolo[2,3-b][1,3,2]oxazaborol-4-ium-8-
uide (13). Pinacol boronate 1b (614 mg, 1.99 mmol) was dissolved in 16 mL dry diethyl ether and treated
with diethanolamine (202 µL, 2.19 mmol) dropwise. Stirring was continued for 2 h and the white
precipitate was filtered and washed with diethyl ether. The crude solid was recrystallized from ethyl
acetate (469 mg, 80%). mp = 154 – 155 oC. 1H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 7.7 Hz, 2H), 7.66
(t, J = 7.7 Hz, 1H), 7.56 (t, J = 7.7 Hz, 2H), 6.15 (s(br), 1H), 5.83 (d, J = 3.5 Hz, 1H), 5.22 (d, J = 2.0
Hz) 1H), 4.07 (ddd, J = 5.5 Hz, J = 9.5 Hz, J = 9.5 Hz, 2 H), 4.01-3.97 (m, 4H), 3.43-3.36 (m, 2H), 2.91 –
2.86 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 138.8, 133.9, 131.9, 129.2, 128.3, 63.7, 62.5, 51.3; IR (film)
3062, 3027, 2978, 2931, 1447, 1423, 1372, 1305, 1214, 1143, 1084 cm-1; HRMS calcd for
(C13H18BNO4S)Na+ 318.0942; Found: 318.0940.
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1-(4-(3-(phenylsulfonyl)prop-1-en-2-yl)phenyl)ethanone (14a). A 25 mL sealed tube was oven dried and
allowed to cool under an argon atmosphere. The vessel was charged with 4.8 mL toluene, aryl iodide (153
mg, 0.693 mmol), [1,1’-Bis(diphenylphosphinoferrocene) dichloropalladium (II) (28.0 mg, 34 µmol),
potassium trifluoroborate 10 (219 mg, 0.762 mmol), and cesium carbonate (677 mg, 2.07 mmol). The
mixture was stirred vigorously and 2.0 mL water was added. The tube was purged with argon before
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being sealed and placed in an oil bath at 80 C for 8 h. Once consumption of the iodide was determined
via TLC, the reaction was transferred to a separatory funnel and diluted with 10 mL of ethyl acetate. The
organic layer was separated and dried over magnesium sulfate. After removal of solvent, the crude
product was dry loaded onto a silica column and eluted with 20% EtOAc/Hexanes to give the product as a
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solid (122 mg, 59%). mp = 134 °C; H NMR (500 MHz, CDCl3) δ 7.85 (d, J =8.5 Hz, 2H), 7.80 (d, J =
8.0 Hz, 2H), 7.58 (t, J = 8.0 Hz, 1H), 7.46 (t, J = 8.0 Hz, 2H), .39 (d, J = 8.5 Hz, 2H), 5.70 (s, 1H), 5.32
(s, 1H), 4.28 (s, 2H), 2.58 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 197.5, 143.4, 138.2, 136.6, 135.9, 134.0,
129.2, 128.8, 128.6, 126.6, 124.0, 61.9, 26.8; IR (film) 3061, 2977, 2934, 1643, 1447, 1423,1372, 1305,
1145 cm-1; HRMS calcd for (C17H16O3S)Na+ 323.0712; Found: 323.0714.
1-nitro-4-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (14b). (Cross-Coupling Procedure A) mp = 134 -
135 °C; 1H NMR (500 MHz, CDCl3) δ 8.13 (d, J = 9.0 Hz, 2H), 7.81 (d, J = 8.0 Hz, 2H), 7.61 (t, J = 7.5
Hz, 1H), 7.51–7.47 (m, 4H), 5.75 (s, 1H), 5.40 (s, 1H), 4.28 (s, 2H); 13C NMR (125 MHz, CDCl3) δ
147.5, 145.3, 138.3, 135.2, 134.2, 129.3, 128.7, 127.3, 125.5, 123.9, 61.9; IR (film) 2978, 2931, 1492,
1447, 1423, 1305 cm-1 ; HRMS calcd for (C15H13NO4S)Na+ 326.0457; Found: 326.0454.
1-(3-(phenylsulfonyl)prop-1-en-2-yl)-4-(trifluoromethyl)benzene (14e). (Cross-Coupling Procedure A).
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mp = 64 °C; H NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.0 Hz, 2H), 7.57 (t, J = 7.5 Hz, 1H), 7.49 (d, J
= 9.0 Hz, 2H), 7.44 (t, J = 7.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 5.67 (s, 1H), 5.33 (s, 1H), 4.27 (s, 2H);
13C NMR (125 MHz, CDCl3) δ 142.4, 138.4, 135.7, 134.0, 130.0 (q, JC-F = 32.5 Hz), 129.2, 128.7, 126.8,
125.5 (q, J = 3.8 Hz), 124.0, 123.9 (q, JC-F = 271.1 Hz), 62.1; IR (film) 3062, 3027, 2978, 2931, 1447,
1372, 1305, 1214, 1143, 1084 cm-1; HRMS calcd for (C16H13F3O2S)Na+ 349.0480; Found: 349.0477.
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1-chloro-2-methyl-4-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (14f). (Cross-Coupling Procedure A). mp
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= 61 °C; H NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.5 Hz, 2H), 7.57 (t, J = 7.0 Hz, 1H), 7.45 (t, J = 7.5
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Hz, 2H), 7.19 (d, J = 8 Hz, 1H), 7.06 (s, 1H), 7.03 (dd, J = 1.5 Hz, J = 8 Hz, 1H), 5.57 (s, 1H), 5.21 (s,
1H), 4.23 (s, 2H), 2.29 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 138.5, 137.4, 136.1, 135.8, 134.4, 133.8,
129.2, 129.0, 128.9, 128.8, 125.1, 122.3, 62.2, 20.2; IR (film) 2978, 2931, 1492, 1447, 1423, 1380, 1372,
1305, 1214, 1143, 1084 cm-1; HRMS calcd for (C16H15ClO2S)Na+ 329.0373; Found: 329.0372.
1-(3-iodopropyl)-2-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (14h). (Cross-Coupling Procedure A, oil).
1H NMR (500 MHz, CDCl3) δ 7.82 (dd, J = 7.5, 1.5 Hz, 2H), 7.60 (t, J = 7.0 Hz, 1H), 7.49 (t, J = 7.5 Hz,
2H), 7.18 (dt, J = 1.5, 7.0 Hz, 1H), 7.12 (d, J = 8.0 Hz, 1H), 7.07 (dt, J = 1.5, 7.0 Hz, 1H), 6.97 (dd, J =
1.0. 7.5 Hz, 1H), 5.55 (s, 1H), 5.31 (d, J = 1.0 Hz, 1H), 4.16 (s, 2H), 3.16 (t, J = 7.0 Hz, 2H), 2.65-2.62
(m , 2H), 2.04 (p, J = 7.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 140.3, 139.2, 137.4, 136.4, 133.8,
129.4, 129.2, 129.2, 128.4, 128.1, 126.2, 124.8, 63.7, 34.9, 33.8, 6.6; IR (film) 3072, 2977, 2931, 1640,
1447, 1423, 1380, 1372, 1306, 1213, 1143, 1085, 1024 cm-1; HRMS calcd for (C18H19IO2S)Na+ 449.0042;
Found: 449.0037.
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1-bromo-2-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (14i). (Cross-Coupling Procedure A). mp = 67 °C;
1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 7.5 Hz, 2H), 7.58 (t, J = 7.0 Hz, 1H), 7.47 (t, J = 8.0 Hz, 2H),
7.43 (d, J = 8.0 Hz, 1H), 7.19 (t, J = 7.0 Hz, 1H), 7.11–7.08 (m, 2H), 5.49 (s, 1H), 5.39 (s, 1H), 4.32 (s,
2H); 13C NMR (125 MHz, CDCl3) δ 141.0, 139.0, 137.4, 133.7, 132.7, 131.6, 129.5, 129.2, 128.5, 127.51,
125.8, 121.5, 62.3; IR (film) 2978, 2954, 1493, 1442, 1425, 1305, 1002 cm-1; HRMS calcd for
(C15H13BrO2S)Na+ 358.9711; Found: 358.9708.
3-(3-(phenylsulfonyl)prop-1-en-2-yl)pyridine (14j). (Cross-Coupling Procedure A). mp = 88 °C; 1H NMR
(500 MHz, CDCl3) δ 8.51 (d, J = 2.5 Hz, 1H), 8.46 (d, J = 5.0 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.62 (d,
J = 7.5 Hz, 1H), 7.58 (t, J = 7.5 Hz, 1H), 7.47 (t, J = 7.5 Hz, 2H), 7.18 (dd, J = 4.5, 7.5 Hz, 1H), 5.66 (s,
1H), 5.32 (s, 1H), 4.26 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 149.2, 147.6, 138.2, 134.9, 134.0, 133.8,
133.6, 129.3, 129.2, 128.6, 128.5, 123.7, 123.2, 61.8; IR (film) νmax = 2978, 2931, 1492, 1447, 1623, 1455,
1385, 1356, 1454, 1143, 1085 cm-1; HRMS calcd for (C14H13NO2S)Na+ 282.0559; Found: 282.0556.
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2-fluoro-5-(3-(phenylsulfonyl)prop-1-en-2-yl)pyridine (14k). (Cross-Coupling Procedure A). mp = 96 °C;
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1H NMR (500 MHz, CDCl3) δ 8.12 (d, J = 2.0 Hz, 1H), 7.81 (d, J = 7.5 Hz, 2H), 7.76 (dt, J = 2.5, 8.0 Hz,
1H), 7.62 (d, J = 7.0 1H), 7.51 (t, J = 7.5 Hz, 2H), 6.84 (dd, J = 3.0, 8.5 Hz, 1H), 5.62 (s, 1H), 5.30 (s,
1H), 4.22 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 163.2 (d, JC-F = 238.8 Hz), 143.6 (d, JC-F = 15 Hz),
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139.1 (d, JC-F = 8.7 Hz), 138.3, 134.2, 132.7 (d, JC-F = 5.0 Hz), 132.6 129.3, 128.7, 123.9, 109.1 (d, JC-F
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37.5 Hz), 62.1; IR (film) 3060, 1591, 1490, 1447, 1371, 1309, 1295, 1256, 1140, 1084 cm-1; HRMS calcd
for (C14H12FNO2S)Na+ 300.0464; Found: 300.0463.
Suzuki-Miyaura Cross-Coupling Procedure B.
1-methoxy-2-(3-(phenylsulfonyl)prop-1-en-2-
yl)benzene (14l). Boronate 1b (100 mg, 0.324 mmol), o-iodoanisole (46 µL, 0.340 mmol),
tris(dibenzylideneacetone)dipalladium(0) (15 mg, 47 µmol), triphenylarsine (20 mg, 65 µmol), and silver
oxide (225 mg, 0.972 mmol) were added to a flask and placed under vacuum. The reaction vessel was
backfilled with argon and charged with degassed THF (3.24 mL). The black mixture was stirred for 2
hours at room temperature, and the solvent was removed under reduced pressure. The crude mixture was
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dry loaded onto a flash column and eluted using 20% EtOAc/Hexanes (oil, 77 mg, 83%). H NMR (500
MHz, CDCl3) δ 7.67 (d, J = 8.0 Hz, 2H), 7.49 (t, J = 8.0 Hz, 1H), 7.36 (t, J = 8.0 Hz, 2H), 7.17 (t, J = 8.0
Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 6.83 (t, J = 8.0 Hz, 1H), 6.63 (d, J = 8.0 Hz, 1H), 5.35 (s, 1H), 5.30 (s,
1H), 4.44 (s, 2H), 3.71 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 155.9, 138.8, 136.7, 133.1, 130.6, 129.4,
128.5, 128.3, 123.9, 120.7, 110.2, 62.1, 55.2; IR (film) νmax = 2978, 2954, 1493, 1442, 1425, 1305, 1002
cm-1; HRMS calcd for (C16H16O3S)Na+ 311.0712; Found: 311.0712.
(Z)-3-phenyl-4-((phenylsulfonyl)methyl)penta-2,4-dien-1-ol (17). (Cross-Coupling Procedure B, oil). 1H
NMR (500 MHz, CDCl3) δ 7.82 (d, J = 7.5 Hz, 2H), 7.65 (t, J = 7.5 Hz, 1H), 7.54 (t, J = 7.5 Hz, 2H), 7.31
– 7.28 (m, 3H), 7.23 – 7.21 (m, 2H), 6.11 (t, J = 7.5 Hz, 1H), 5.46 (s, 1H), 5.36 (s, 1H), 4.37 (d, J = 7.5 Hz,
2H), 3.79 (s, 2H), 3.24 (s(br), 1H); 13C NMR (125 MHz, CDCl3) δ 142.8, 139.2, 138.5, 133.8, 132.9,
130.0, 129.3, 128.7, 128.3, 128.1, 127.3, 126.8, 61.6, 59.7; IR (film) νmax = 3509, 3060, 3024, 2925, 1491,
1447, 1307, 1246, 1153, 1128, 1085 cm-1; HRMS calcd for (C18H18O3S)Na+ 337.0868; Found: 337.0868.
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General Preparation of Triflates. 3-(2-iodophenyl)propyl trifluoromethanesulfonate (20c). To a solution
of 3-(2-iodophenyl)propan-1-ol (440 mg, 1.7 mmol) in dichloromethane (17 mL) at -78 oC was added 2,6-
lutidine (312 µL, 3.4 mmol) followed by dropwise addition of trifluoromethanesulfonic anhydride (386
µL, 1.9 mmol). The solution was stirred for 1 h at -78 oC before being quenched with water slowly. The
reaction was diluted with dichloromethane, and washed with brine. The organic layer was dried over
magnesium sulfate and concentrated under reduced pressure. The crude oil was purified on a flash
column (100% hexanes) affording a yellow oil (283 mg, 43%). 1H NMR (500 MHz, CDCl3) δ 7.83 (d, J =
8.0 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H), 7.20 (d, J = 8.0 Hz, 1H), 6.93 (t, J = 7.5 Hz, 1H), 4.58 (t, J = 6.0 Hz,
2H), 2.88 (t, J = 7.5 Hz, 2H), 2.17 – 2.12 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 142.4, 140.0, 129.7,
128.8, 128.6, 118.8 (q, JC-F = 317.5 Hz), 100.3, 76.6, 36.4, 29.7; IR (film) 2978, 2931, 1492, 1447, 1423,
1372, 1305, 1214, 1143, 1084 cm-1; no molecular ion in HRMS.
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4-(2-iodophenyl)butyl trifluoromethanesulfonate (20d). (Triflate Procedure, oil). 1H NMR (500 MHz,
CDCl3) δ 7.82 (d, J = 8 Hz, 1H), 7.28 (t, J = 8.0 Hz, 1H), 7.19 (dd, J = 1.5, 7.5 Hz, 1H), 6.90 (t, J = 1.5,
8.0 Hz, 1H), 4.57 (t, J = 6.5 Hz, 2H), 2.78 (t, J = 7.5 Hz, 2H), 1.95 – 1.89 (m, 2H), 1.78 – 1.72 (m, 2H);
13C NMR (125 MHz, CDCl3) δ 143.7, 139.6, 129.3, 128.5, 128.1, 118,6 (q, JC-F = 319.7 Hz) 100.4, 39.8,
28.7, 25.7; IR (film) 2978, 2931, 1492, 1447, 1423, 1372, 1305, 1214, 1143, 1084 cm-1; no molecular ion
in HRMS.
General Alkylation Procedure.
2-(4-(2-iodophenyl)-3-(phenylsulfonyl)but-1-en-2-yl)-4,4,5,5-
tetramethyl-1,3,2-dioxaborolane (21a). To a solution of diisopropylamine (60 µL, 0.42 mmol) in THF
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(2.2 mL) was added n-butyllithium (2.04 M in THF, 174 µL, 0.35 mmol) at -78 C and stirred for one
hour. The solution of lithium diisopropylamide was then treated with a solution of 1b (100 mg, 0.324
mmol) in 1.0 mL THF and stirred for an additional hour before addition of electrophile (0.356 mmol).
After dropwise addition of electrophile, the reaction was removed from cold bath and allowed to warm to
room temperature over 3 h. The reaction was quenched with a saturated solution of aqueous NH4Cl and
the mixture was extracted with EtOAc (3 x 10 mL). The combined organic layers were dried over MgSO4,
filtered and concentrated in vacuo. The residue was absorbed onto silica and purified via flash
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chromatography (20% EtOAc in Hexanes) affording the corresponding mono-alkylated product as an oil
(113 mg, 67%). 1H NMR (500 MHz, CDCl3) δ 7.88 (d, J = 8.2 Hz, 2H), 7.75 (d, J = 8.0 Hz, 1H), 7.59 (t, J
= 7.5 Hz, 1H), 7.51 (t, J = 8.0 Hz, 2H), 7.20 – 7.16 (m, 2H), 6.86 – 6.83 (m, 1H), 6.06 (d, J = 2.0 Hz, 1H),
5.94 (s, 1H), 4.39 (dd, J = 4.0, 10.5 Hz, 1H), 3.61 (dd, J = 3.5, 14.0 Hz, 1H), 3.43 (dd, J = 12.0, 14.0 Hz,
1H), 1.12 (s, 6H), 1.09 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 139.7, 139.6, 138.4, 137.4, 133.3, 131.2,
129.57, 128.7, 128.3, 127.9, 100.7, 83.9, 67.0, 38.1, 24.79, 24.4; IR (film) 2973, 2930, 1447, 1423, 1305,
1216, 1145, 1085 cm-1; HRMS calcd for (C22H26BIO4S)Na+ 547.0582; Found: 547.0577.
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2-(5-(2-iodophenyl)-3-(phenylsulfonyl)pent-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(21b).
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(Alkylation Procedure, oil). H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 8.0 Hz,
1H), 7.59 (t, J = 8.0 Hz, 1H), 7.49 (t, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 1H), 7.18 (dd, J = 1.5, 8.0 Hz,
1H), 6.89 (dt, J = 1.5, 8.0 Hz, 1H), 6.23 (d, J = 2 Hz, 1H), 6.00 (s, 1H), 3.99 (dd, J = 3.5, 11.5 Hz, 1H),
2.78-2.72 (m, 1H), 2.66-2.60 (m, 1H), 2.45 (dddd, J = 3.5, 6.0, 10.0, 13.5 Hz, 1H), 2.30-2.22 (m, 1H),
1.183 (s, 6H), 1.177 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 143.4, 139.5, 138.0, 136.8, 133.2, 129.6,
129.5, 128.6, 128.3, 128.0, 100.3, 83.9, 67.3, 37.80, 27.3, 24.7, 24.6; IR (film) 2973, 2930, 1447, 1423,
1305, 1216, 1145, 1085 cm-1; HRMS calcd for (C23H28BIO4S)Na+ 561.0744; Found: 561.0733.
2-(7-(2-iodophenyl)-3-(phenylsulfonyl)hept-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(21d).
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(Alkylation Procedure, oil). H NMR (500 MHz, CDCl3) δ 7.79 (t, J = 8.5 Hz, 3H), 7.58 (t, J = 7.5 Hz,
1H), 7.49 (t, J = 8.0 Hz, 2H), 7.24 (t, J = 7.5 Hz, 1H), 7.15 (d, J = 7.5 Hz, 1H), 6.86 (t, J = 8.0 Hz, 1H),
6.14 (d, J = 2.0 Hz, 1H), 5.89 (s, 1H), 3.92 (dd, J = 3.5, 11.5, 1H), 2.71–2.61 (m, 2H), 2.23 (dddd, J = 3.5,
6.0, 10.0, 13.5 Hz, 1H), 2.11–2.03 (m, 1H), 1.60–1.52 (m, 2H), 1.47–1.40 (m, 1H), 1.37–1.31 (m, 1H),
1.14 (s, 6H), 1.13 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 144.8, 139.4, 138.2, 136.5, 133.2, 129.6, 129.2,
128.6, 128.2, 127.6, 100.5, 83.8, 68.0, 40.4, 29.7, 26.5, 26.4, 24.65, 24.57; IR (film) 2973, 2930, 1447,
1423, 1305, 1216, 1145, 1085 cm-1; HRMS calcd for (C25H32BIO4S)Na+ 589.1051; Found: 589.1045.
1-methylene-2-(phenylsulfonyl)-1,2,3,4-tetrahydronaphthalene (22b). (Cross-Coupling Procedure B, oil).
1H NMR (500 MHz, CDCl3) δ 7.83 (d, J = 7.6 Hz, 2H), 7.59 (t, J = 7.5 Hz, 1H), 7.52 – 7.47 (m, 3H),
7.21-7.14 (m, 2H), 7.06 (d, J = 7.0 Hz, 1H), 5.72 (s, 1H), 4.92 (s, 1H), 4.12 (t, J = 5.0 Hz, 1H), 3.21 (ddd,
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J = 5.5, 10.0, 16.0 Hz, 1H), 2.73 (dt, J = 16.5, 5.5 Hz, 1H), 2.54 (dq, J = 15.0, 5.0 Hz, 1H), 2.27–2.19 (m,
1H); 13C NMR (125 MHz, CDCl3) δ 137.7, 136.1, 135.2, 133.7, 133.5, 132.7, 129.3, 128.7, 128.3, 126.5,
124.5, 118.0, 67.0, 26.2, 23.0; IR (film) 2973, 2930, 1447, 1423, 1305, 1216, 1145, 1085 cm-1; HRMS
calcd for (C17H16O2S)Na+ 307.0763; Found: 307.0762.
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5-methylene-6-(phenylsulfonyl)-6,7,8,9-tetrahydro-5H-benzo[7]annulene
(22c).
(Cross-Coupling
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Procedure B, oil). H NMR (500 MHz, CDCl3) δ 7.82 (d, J = 8.0 Hz, 2H), 7.62 (t, J = 8.0 Hz, 1H), 7.51 (t,
J = 8.0 Hz, 2H), 7.18 (t, J = 8.0 Hz, 1H), 7.10 (t, J = 8.0 Hz, 1H), 7.03 (d, J = 7.0 Hz, 1H), 6.85 (d, J = 7.5
Hz, 1H), 5.57 (s, 1H), 5.30 (s, 1H), 3.95 (d, J = 8.0 Hz, 1H), 2.78–2.72 (m, 1H), 2.69–2.65 (m, 1H), 2.32 –
2.13 (m, 1H), 1.94–1.87 (m, 1H), 1.85–1.76 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 142.4, 140.1, 137.8,
133.5, 130.0, 129.4, 128.8, 128.3, 128.2, 128.1, 126.6, 122.8, 68.5, 32.2, 26.0, 23.4; IR (film) 2978, 2931,
1492, 1447, 1423, 1372, 1305, 1214, 1143, 1084 cm-1; HRMS calcd for (C18H18O2S)Na+ 321.0919;
Found: 321.0917.
5-methylene-6-(phenylsulfonyl)-5,6,7,8,9,10-hexahydrobenzo[8]annulene (22d).
(Cross-Coupling
Procedure B, oil). 1H NMR (500 MHz, CDCl3) δ 7.92 (d, J = 7.5 Hz, 2H), 7.65 (t, J = 7.5 Hz, 1H), 7.57 (t,
J = 7.5 Hz, 2H), 7.25–7.16 (m, 3H), 7.10 (d, J = 7.5 Hz, 1H), 5.28 (s, 2H), 3.81 (dd, J = 2.5, 12.0 Hz, 1H),
2.72–2.63 (m, 2H), 2.23–2.18 (m, 1H), 2.07–1.94 (m, 2H), 1.59–1.52 (m, 1H), 1.51–1.43 (m, 1H), 1.31–
1.24 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 141.1, 141.0, 138.2, 138.0, 133.7, 133.4, 130.0, 129.1, 128.9,
128.2, 125.6, 124.9, 74.9, 34.2, 30.4, 27.9, 24.3; IR (film) 2978, 2931, 1492, 1447, 1423, 1372, 1305,
1214, 1143, 1084 cm-1; HRMS calcd for (C19H20O2S)Na+ 335.1076; Found: 335.1078.
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Acknowledgements
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This work was supported by the Department of Chemistry, University of Missouri-Columbia and
by the National Science Foundation (We thank Dr. Carissa S. Hampton (University of Missouri-
Columbia) and Ms. Gail Harmata (Columbia, Missouri) for proofreading the manuscript. We
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thank Dr. Wei Wycoff (University of Missouri-Columbia) for assistance with NMR spectroscopy.
We thank Frontier Scientific for a gift of compound 7.
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Supporting Information
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Proton and carbon NMR data for new compounds. This material is available free of charge via
the Internet at http://pubs.acs.org.
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