Manganese-Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols with Sulfones: A Tool to Access Highly Substituted Vinyl Sulfones

Article abstract of DOI:10.1021/acs.joc.8b02911

The development of first-row-transition-metal catalysts that can match with the reactivities of the noble metals is considered to be challenging yet very much a desirable goal in homogeneous catalysis. It has become even more fascinating to develop processes where these metals show a unique reactivity and selectivity than their higher congeners. Herein, we report on the catalytic activity of a pincer complex of the abundant earth metal manganese for an unprecedented acceptorless dehydrogenative coupling of alkyl sulfones with alcohols. Thus, highly functionalized vinyl sulfones were obtained in moderate to good yields. Both benzylic and aliphatic alcohols could be utilized, and several functional groups including bromides and iodides are tolerated under the reaction conditions. The reaction is environmentally benign, producing dihydrogen and water as byproducts. Preliminary mechanistic experiments involving kinetic, deuterium-labeling, and NMR experiments were performed.

Full text of DOI:10.1021/acs.joc.8b02911

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Article
Manganese Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols
With Sulfones: A Tool to Access Highly Substituted Vinyl Sulfones
Satyadeep Waiba, Milan Kr Barman, and Biplab Maji
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02911 • Publication Date (Web): 27 Dec 2018
Downloaded from http://pubs.acs.org on December 27, 2018
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Manganese
Catalyzed
Acceptorless
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Dehydrogenative Coupling of Alcohols With
Sulfones: A Tool to Access Highly Substituted
Vinyl Sulfones
Satyadeep Waiba, Milan K. Barman, and Biplab Maji*
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata,
Mohanpur 741246, India
ABSTRACT. The development of first-row-transition metal catalysts that can match with the
reactivities of the noble metals is considered to be challenging yet very much desirable goal in
homogeneous catalysis. It has become even more fascinating to develop processes where these
metals show unique reactivity and selectivity than their higher congeners. Herein, we report on
the catalytic activity of a pincer complex of an earth’s abundant metal manganese for an
unprecedented acceptorless-dehydrogenative-coupling of alkyl sulfones with alcohols. Thus
highly functionalized vinyl sulfones were obtained in moderate to good yields. Both benzylic
and aliphatic alcohols could be utilized and several functional groups including bromides,
iodides are tolerated under the reaction condition. The reaction is environmentally benign
producing dihydrogen and water as byproducts. Preliminary mechanistic experiments
involving kinetic, deuterium labeling and NMR experiments were performed.
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KEYWORDS. olefination, manganese complex, vinyl sulfone, homogeneous catalysis,
acceptorless-dehydrogenative-coupling.
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INTRODUCTION
Vinyl sulfones are versatile building blocks in organic synthesis.1 In medicinal chemistry,2
they act as inhibitors for many types of cysteine proteases,3 SrtA,4 and caspase-3.5 They also
act as anti-trypanosomal agents6 and neuroprotective agents toward Parkinson’s disease
therapy.7 Recently, vinyl sulfones are also used as a fluorogenic probe for selective labeling of
live cells.8 Given its importance, considerable amounts of efforts are devoted to their synthesis
(Scheme 1A).2a, 7, 9 Classically, vinyl sulfones are synthesized via Knoevenagel condensation
of aldehydes with sulfonylacetic acids followed by decarboxylation,9c Horner–Wadsworth–
Emmons reactions of sulfonyl phosphonates and carbonyls,7 β-elimination of halo- or
selenosulfones,9d oxidation of the corresponding sulfides9e and recently by cross-coupling of a
sulfonyl source with an alkene or alkynes (Scheme 1A).9b However, most of these protocols
suffer from the limited accessibility of starting materials, use of a stoichiometric amount of
redox reagents, tedious procedures, multiple steps, harsh reaction condition, and formation of
copious byproducts.
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The homogeneous catalysis with 3d-transition metals as the alternative to the noble metals
has captivated the synthetic chemists not only due to their earth’s abundance, low price, and
less toxicity but due also to their potential novel reactivity and selectivity.10 In this context, the
first-row-transition metals such as iron,11 cobalt,12 and nickel13 have achieved much
advancement in hydrogenation and dehydrogenation reactions. Manganese, the third most
abundant transition metal in the earth’s crust has recently emerged as a valuable noble metal
replacer.14 Following the seminal work on manganese catalyzed dehydrogenative imine
synthesis by Milstein et al.,15 the Mn-complexes have been utilized in various
(de)hydrogenation and cascade reactions,16 and in some cases, they have even outperformed
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their higher congeners.17 In this regard, we have developed Mn-catalyzed direct olefination of
methyl substituted heteroarenes16i and α-alkylations of ketones16j and nitriles16m using primary
alcohols. However, despite such developments, reports exploring their potential unique
catalytic activities for the development of novel transformations are limited.16g-i
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Continuing our recent focus on base-metal catalysis, we have envisioned that the transition-
metal-catalyzed acceptorless-dehydrogenative-coupling ADC of alcohols with alkyl sulfone
might serve as a versatile „green“ tool for the synthesis of highly substituted vinyl sulfones
(Scheme 1). The protocol will be highly sustainable as a) Alcohols are largely abundant from
a variety of resources and are non-toxic alternative carbon resources.18 b) The reaction will be
highly environmentally benign as water and dihydrogen will be produced as the sole
byproducts. c) The route will versatile without the need for functional group manipulation.
However, the successful reaction development should accounts for the acceptorless liberation
of dihydrogen without the hydrogenation of the highly reactive Michael acceptors vinyl
sulfones.1d, 19 Another challenge will be the formation of byproducts via the elimination of
sulfone.
Herein, we report on a novel catalytic activity of a manganese(I)-pincer complex for the
acceptorless-dehydrogenative-coupling of primary alcohols with alkyl sulfones (Scheme 1C).
The catalyst operates under low catalyst loading and tolerates several functional groups. While
the reaction went smoothly with manganese, the cobalt and iron complexes stabilized by the
same ligand backbone failed to deliver product under these conditions and previous
homogeneous ruthenium20 and heteroeneous platinum21 catalyzed such rection produced
stilbenes with the liberation of stoichimetric amount of sulfonate as byproduct. To the best of
our knowledge, the transition-metal-catalyzed dehydrogenative coupling of alcohols with
sulfones to form vinyl sulfones with the liberation of water and H2 is not reported thus far.
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A) Synthesis of unsaturated sulfone:
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R1O2C
SO2R5
SO2R5
decarb
hydrolysis
R
R
O
CO2R1
oxylation
SO2R5
1) R5SH
2) [O]
R3
R3
R4
O
R4
elimi
[O]
n.
OH
R5SY, cat., redox reagent
SR5
R4
R3
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R3
R4
R5SX
SO2R5
SO2R5
R4
R3
[O]
R3
R4
n.
elimi
X
X
R5SY, cat., redox reagent
R6
R7
B) Noble metal catalyzed coupling of alcohols with sulfones
R'
Ru, Pt
R
R
OH
+
R'
+
XSO2R''
excess
base
SO2R''
stoichiometric
byproduct
C) This work: Manganese catalyzed direct olefination of sulfones with alcohols
R'
R'
[Mn]
R
OH
+
H2O
+
H2
+
R
catalytic
base
SO2R''
SO2R''
Advantages
Challenges
Earths' abundant catalyst
Versatile, non-toxic reagents
Environmetally benign
Acceptorless liberation of H2
Chemoselectivity
Elimination of sulfonate
Scheme 1. A) State-of-the-Art Syntheses of Vinyl Sulfones. B) Noble Metal Catalyzed Coupling of Alcohols with Sulfones. C) This Work.
RESULTS AND DISCUSSION
Dehydrogenative coupling of (benzylsulfonyl)benzene 1a with benzyl alcohol 2a was chosen
as a model system for this dehydrogenative coupling reaction (Table 1, see the Supporting
Information for details). Thus, a dry tert-amyl alcohol solution of 1a, 2a, the in situ generated
manganese complex Mn-1,16i and t-BuOK were heated at 140 C (bath temperature) under
o
argon for 24 h. GCMS analysis indicates the formation of the desired unsaturated olefin 3aa in
60% yield (56% isolated yield, entry 2)). However, the non-pincer manganese complex Mn-2,
previously been utilized for nitrile alkylation reaction16m was found to be inactive (entry 3).
The manganse(I)-pincer complex Mn-3 was also found to be moderatly active and the product
3a was isolated in 59% yield (entry 4).2 To our delight, when the reaction was carried out with
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a triazole-based pincer catalyst Mn-4 bearing a methyl substituent at the para position,16a the
yield of the product 3aa was significantly increased to 90% (entry 5). Gratifyingly, the use of
the para phenyl substituted manganese complex Mn-516a deliver the desired product 3aa in
94% isolated yield (entry 1). With the catalyst Mn-5, the reaction condition was further
optimized. The reaction was found to be highly sensitive towards the nature of the base used
(entry 6). The change in a solvent to the nonpolar solvent toluene and the ethereal solvent 1,4-
dioxane were also noticed to be less suitable (entry 7, <61% yield). The catalyst loading could
be reduced to 2 mol% at the cost of a slight decrease in reaction efficiency (entry 8). However,
when base loading was lowered to 10 mol%, only 14% of the desired product was obtained
(entry 9). In this case, benzaldehyde was detected as the major product in TLC. The control
experiments showed that in the absence of a ligand or the manganese-precatalyst the product
3aa is not formed (entries 10,11).
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Table 1. Optimization of the Reaction Conditionsa
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Ph
Ph
Ph
Ph
Mn-5
(4 mol%)
+
+
Ph
OH
SO2Ph
3aa'
+
Ph
SO2Ph
t-BuOK (20 mol%)
t-AmOH, argon, 140 oC, 24 h
SO2Ph
Ph
2a
1a
3aa
Ph
4a
 H2O  H2
3aa
3aa' 4a
Entry
deviation from above
Yield of
(%) Yield of (
+
) (%)
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1
2b
none
Mn-1
Mn-2
Mn-3
94
<5
<5
<5
<5
56
<5
59
3
4b
5
6
7
Mn-4
90
<5
t-BuOLi, t-BuONa or Cs2CO3 as base
<27
<61
85
n.d.
<5
PhMe, 1,4-dioxane as solvent
8
9c
Mn-5
(2 mol%)
<5
t-BuOK (10 mol%)
14
<5
<5
<5
n.d.
0
10
11
12d
13d
14d
Mn(CO)5Br
-
0
Fe-1
0
Fe-2
Co-1
<5
<5
0
0
R
H
H
N
N
X
X
Br
Me
N
+
N
N
MnI
N
N
S
HN
(i-Pr)2P
OC
N
NH
OC
MnI(CO)5Br
MnI P(i-Pr)2
CO
CO
Mn-2
Ph
Br
Mn-1
CO
Mn-3
Mn-4
Mn-5
; X = CH, R = H
; X = N, R = Me
; X = N, R = Ph
R
X
X
N
N
HN
(i-Pr)2P
Br
N
NH
HN
N
NH
FeII P(i-Pr)2
(i-Pr)2P
CoII P(i-Pr)2
Br
Cl
Cl
CO
Fe-1
Fe-2
Co-1
; X = CH, R = H
; X = N, R = Ph
aReaction conditions: Pre-catalyst (4 mol%), t-BuOK (20 mol%), 1a (0.15 mmol), 2a (0.1
mmol), t-AmOH (0.5 mL), 140 oC, 24 h under Ar. Isolated yields. b The catalyst was generated
in situ. Benzaldehyde was detected as the major product. >90% of benzyl alcohol was
recovered. n.d. = not determined.
c
d
The manganese(I)-catalyzed reaction was found to be highly selective. The NMR analysis of
the product 3aa indicates the exclusive formation of thermodynamically stable (E)-isomer. The
undesired olefination product stilbene 4a or the borrowing hydrogenation product (1-
(phenylsulfonyl)ethane-1,2-diyl)dibenzene 3aa‘ was not detected. On the other hand, the iron
complexes Fe-1,216h,22 and the cobalt complex Co-116h derived from similar ligand
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environments were found to be inactive, where the benzyl alcohol remained largely unreactive
and traces of benzaldehyde was detected (entries 12-14, Table 1 and Table S1). It is of
noteworthy that the existing homogeneous ruthenium-20 and the heterogeneous platinum-
catalyzed21 reaction of alcohols with sulfones exhibits different selectivity to deliver stilbene
by eliminating sulfonate as a byproduct in the presence of an excess amount of base.
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With this sets of optimized conditions in hand, the generality of this novel ADC reaction was
then explored. We are pleased to find that the reactivity displayed by the pincer complex Mn-
5 in the model system can also be applied to a large variety of primary alcohols with different
steric and electronic properties (Table 2). In all cases, the (E)-isomer was selectively obtained
and the undesired stilbene or the C=C hydrogenation products were not detected. The use of
electron-rich benzyl alcohols (2b-e) as a coupling partner resulted in the formation of the
desired vinyl sulfones 3ab-3ae in 71-92% yield. Importantly, a sterically demanding ortho-
tolylmethanol 2c could be accommodated and the vinyl sulfone 3ac was obtained in 72% yield.
A series of functional groups were found to be compatible with the alcohol substrates. Benzylic
alcohols with halides (2f-l) at ortho-, meta- or para-position of the phenyl ring were found to
be viable coupling partner delivering the desired olefins 3af-3al in 46-89% yield. More
importantly, in all these cases, the halide functionalities were retained in the product although
dihydrogen is liberated in the reaction. Alcohols containing hetero-aromatic groups such as
pyridyl- (2n), thiophenyl- (2o), and furyl-groups (2p) that can bind to the manganese catalyst
and thereby could potentially poison the catalyst were successfully reacted with 1a. The
heteroarene substituted vinyl sulfones 3an-3ap were obtained in 47-84% yield. Aliphatic
alcohols (2q-s) were also noticed to be viable coupling partners. The reaction of strained
cyclopropane methanol (2q) delivered the unsaturated sulfone (3aq) in 77% yield without
opening the strained three-membered ring. Linear alcohols e.g. n-butanol (2r) and n-hexanol
(2s) could also be used although the yields are poor. Absolute configuration of 3ar was
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confirmed by NOESY experiment (see the Supporting Information). However, methanol (2t)
and a secondary alcohol 1-phenylethanol (2u) were found to be unsuitable.
Table 2. Manganese(I)-Catalyzed Olefination of Various Primary Alcohols 2
with(Benzylsulfonyl)benzene 1aa
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Ph
Ph
Mn-5
(4 mol%)
R
OH
+
 H2O  H2
R
SO2Ph
t-BuOK (20 mol%), t-AmOH
SO2Ph
argon, 140 oC, 24 h
2
1a
3
Ph
Ph
Ph
SO2Ph
, 94%
SO2Ph
, 78%
SO2Ph
3aa
3ab
3ae
3ac
, 72%
MeO
Ph
F
Ph
Ph
Ph
SO2Ph
SO2Ph
SO2Ph
3ad
3af
, 92%
Ph
, 71%
, 46%
Cl
Cl
Br
Cl
Ph
Ph
SO2Ph
SO2Ph
, 81%
SO2Ph
3ag
3ah
3ai
, 81%
Ph
, 65%
I
F3C
Ph
Ph
SO2Ph
SO2Ph
SO2Ph
3aj
3ak
3an
3al
, 89%
, 52%
, 58%
Ph
N
S
Ph
Ph
SO2Ph
3ao
, 74%
SO2Ph
SO2Ph
3am
, 81%
Ph
, 47%
O
Ph
Ph
SO2Ph
SO2Ph
, 77%
SO2Ph
, 37%
Ph
3ap
3aq
3ar
, 84%
Ph
Ph
Ph
SO2Ph
, <5%
SO2Ph
3au
, <5%
SO2Ph
3as
3at
, 26%
aReaction conditions: Mn-5 (4 mol%), t-BuOK (20 mol%), 1a (0.15 mmol), 2 (0.1 mmol), t-
AmOH (0.5 mL), 140 oC, 24 h under Ar. Isolated yields.
Next, we have studied the reactions of differently substituted sulfones with primary alcohols
(Table 3). A benzylic sulfone containing a sterically demanding ortho-methyl group 1b was
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converted into the vinyl sulfone 3ba in 90% yield. Similarly, the reactions of 4-methoxy- (1c),
and phenyl-substituted benzylic sulfone (1d) with primary alcohols went smoothly to deliver
vinyl sulfones in 73-94%yield. The X-ray crystal structure analysis of 3ch underlined the
thermodynamically more stable E-configuration of the product.23 Sulfones with halogen
substituents such as fluoro (1e), chloro (1f), bromo (1g), iodo (1h) and trifluoromethyl (1i)
could also be utilized as coupling partner. Importantly, likewise for primary alcohols, in all
these cases the reducible halogen functional groups were retained in the products. A sulfone
containing a naphthyl group (1j) also took part in this ADC reaction and the product 3ja was
obtained in 86% yield. However, the use of n-butyl phenyl sulfone (1k) was unsuccessful as a
complex mixture as formed.
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In addition to the sulfones containing a secondary carbon atom, we also have also tested the
ADC reactions of primary sulfones (1l,m). Thus, methyl phenyl sulfone (1l) was reacted with
the primary alcohols 2a,d under the standard reaction conditions. In these cases, the manganese
catalyzed dehydrogenation process has to be compatible with the activation of the weakly
acidic CH-bond of the methyl sulfones pKa(DMSO) = 29.0 for 1l vs 23.4 for 1a.24 To our
delight, the ADC reaction underwent in equally efficient manner and the di-substituted olefins
3la, 3ld were obtained in 72% and 82% yields, respectively with perfect (E)-selectivity. The
later reaction could also be performed in gram scale without significant loss in reaction
efficiency (1.10 gm, 80%). Thus, demonstrating the synthetic utility and practicality. Similarly,
dimethyl sulfone (1m) could also be utilized and the products 3ma, 3md were obtained in
moderate yields.
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Table 3. Manganese(I)-Catalyzed Olefination of Various Primary Alcohols 2 with
Sulfones 1a
7
8
9
R1
R1
Mn-5
(4 mol%)
R
OH
+
 H2O  H2
R
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
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42
43
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60
SO2R2
SO2R2
t-BuOK (20 mol%), t-AmOH
argon, 140 oC, 24 h
2
1
3
OMe
SO2Ph
SO2Ph
SO2Ph
3ca
, 94%
3aa
3ba
, 94%
OMe
, 90%
OMe
Cl
SO2Ph
SO2Ph
, 80%
b
3cq
3ch
, 73%
Ph
Cl
F
SO2Ph
, 76%
Br
SO2Ph
SO2Ph
, 74%
3da
3ga
3ea
3fa
3ia
, 74%
CF3
I
SO2Ph
, 36%
SO2Ph
, 50%
SO2Ph
, 41%
3ha
SO2Ph
, 72%
SO2Ph
, <5%
SO2Ph
, 86%
3ja
3ka
3la
MeO
MeO
SO2Ph
SO2Me
, 50%
SO2Me
c
3ld
3ma
3md
, 52%
, 82%; 1.10 gm (80%)
aReaction conditions: Mn-5 (4 mol%), t-BuOK (20 mol%), 1 (0.15 mmol), 2 (0.1 mmol), t-
AmOH (0.5 mL), 140 oC, 24 h under Ar. Isolated yields. b Ref.23. c 5.0 mmol scale.
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To get insight into the reaction mechanism, several control experiments were then performed
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(Scheme 2). The reaction of 1a with [α,α-D2]biphenyl methanol 2e-d2 (94% D) resulted in the
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formation of 3ae-d in 32% yield after 8 h. The H NMR analysis of 3ae-d revealed 86%
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deuterium incorporation at the vinyl-position (Scheme 2a). A kinetic isotope effect (kH/kD) of
1.6 was then determined by a parallel experiment. The small magnitude suggests that the
alcohol dehydrogenation step is a moderately slow step for the overall ADC reaction.
Ph
(a)
Ph
SO2Ph
1a
Mn-5
(4 mol%)
Ar
OH
Ar
+
SO2Ph
t-BuOK (20 mol%), t-AmOH
argon, 140 oC, 8 h
Ar = biphenyl
(94% D)
D
D
(86% D)
D
2e
3ae
-d2
-d, 32%
Ph
Ph
(b)
(c)
Mn-5
(4 mol%)
O
Ph
+
Ph
t-BuOK (20 mol%), t-AmOH
SO2Ph
3aa
, 51%
SO2Ph
argon, 140 oC, 30 min
2
1a
a'
without [Mn]; 39%
no t-BuOK; trace
Ar = biphenyl
Ar
Ph
1a 2e
, t-BuOK
+
Chamber 1
Chamber 2
Mn-5
SO2Ph
, 71%
3ae
H2
Pd/C (cat.)
+
Ph
Ar
Ph
60%
Ph
Ph
(d)
Mn-5
(4 mol%)
+
Ph
Ph
t-BuOK (20 mol%), t-AmOH
argon, 140 oC, 20 h
Ar = 4-OMeC6H4
SO2Ph
SO2Ph
3aa
96% recovery
OH
3aa
2d
Scheme 2. Mechanistic Experiments.
Previously, we and others have demonstrated that a dehydrogenation catalyst also took part
in the CC-bond forming step.16i, 25 Milstein et al. have described the activation of nitrile by a
pincer manganese-complex for the CC-bond forming Michael reaction.26 To probe whether the
manganese complex Mn-5 also participates in aldol reaction, the condensation between
benzaldehyde and 1a was carried out in presence and absence of Mn-5 (Scheme 2b). Only a
1.3-fold rate acceleration is observed in presence of Mn-5. However, 3aa is not formed in the
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absence of t-BuOK. In situ NMR study indicates that Mn-5 does not activate 1a in presence of
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t-BuOK (see the ESI for details). This suggests that, in contrast to the previous reports,25-26
a
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base mediated aldol condensation is operative as a major process.16h
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To probe the acceptorless liberation of dihydrogen, Pd/C-catalyzed hydrogenation of α-
methyl styrene was performed using the liberated H2 from the olefination reaction in an H-
shaped bridged tube (Scheme 2c, see the ESI for details). In such an experiment, the manganese
catalyzed ADC reaction of 1a with 2e was performed in one chamber. α-Methyl styrene and
catalytic Pd/C were placed in the other. The observed 60% yield of cumene in the second
chamber conclusively prove the acceptorless liberation of dihydrogen.
A probable mechanism is depicted in Scheme 3. The base mediated salt elimination of the
precatalyst Mn-5 generates the active catalyst I which dehydrogenates the primary alcohol 2
in a moderately slow step to yield an aldehyde via the alkoxy complex II. Similar, manganese-
alkoxy complexes have previously been isolated by Liu,17b Milstein,16f Yu,16k and us.16i The
liberated aldehyde 2’ then underwent t-BuOK or I mediated aldol condensation to deliver the
vinyl sulfone 3a. The Mn-hydride complex III then liberate H2 to close the catalytic cycle.
Previously, the hydride complex III was in situ generated by the dehydrogenation of benzyl
alcohol.16h In a recent study, Kempe and workers have shown that a manganese hydride
complex III undergo double deprotonation in the presence of t-BuOK and that potassium
manganate hydride react fast with an imine to selectively deliver an amine.16m Considering this,
we have attempted hydrogenation of the vinyl sulfone 3a using the benzylic alcohol 2d as the
hydrogen source in presence of t-BuOK. This resulted in 96% recovery 3a after 24 h (Scheme
2d). It suggests that the nucleophilicity of the putative potassium manganate hydride
intermediate is not sufficient to reduce 3a. The high selectivity for vinyl sulfone could thus be
explained by the preferential acceptorless dihydrogen liberation than the hydrogenation of the
Michael acceptor.
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N
PiPr2
t-BuOK
N
N
Mn-5
Ph
H
N
Mn CO
CO
HO
R
R
2
HN P
iPr2
H2
I
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O
HN
PiPr2
HN
N
PiPr2
N
N
Ph
N
Mn CO
Ph
Mn CO
N
N
HN P
HN P
CO
iPr2
CO
iPr2
III
II
Ph
R
Ph
2'
O
H2O +
R
SO2Ph
SO2Ph
I
t-BuOK or
3
1a
Scheme 3. Proposed mechanism.
CONCLUSION
In conclusion, we have presented an unprecedented acceptorless-dehydrogenative-coupling
of alcohols with alkyl sulfones for the efficient synthesis of highly substituted vinyl sulfones.
The reaction is catalyzed by a pincer complex of an earth’s abundant metal manganese. The
iron and cobalt complexes were found to be inactive under identical conditions. The observed
selectivity complements to the existing Ru- and Pt-catalyzed coupling of alcohols with sulfones
which produced stilbene eliminating sulfonate as a byproduct. A broad range of highly
substituted vinyl sulfones produced in moderate to good yields in an environmentally benign
manner. The selectivity toward vinyl sulfone can be attributed to the lower reactivity of the
manganese hydride intermediate under these conditions.
The development of earth’s abundant metal catalysts that can match with the reactivity of
their higher congeners is considered as a highly challenging task in homogeneous catalysis. It
is mostly due to the unfavorable properties of these metals. However, through proper reaction
development, these unique properties could potentially lead to novel reactivity and selectivity.
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We believe that the developed procedure will set forth further evolution in base-metal catalysis
for novel reaction developments.
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EXPERIMENTAL SECTION
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General Considerations. Unless otherwise stated, all reactions were carried out under an
inert atmosphere of argon in oven-dried glassware. Reaction temperatures are reported as the
temperature of the bath surrounding the vessel. Dry solvents were prepared according to the
standard procedure and degassed prior to use. Manganese catalysts Mn-1,16i Mn-2,16m Mn-3,22
Mn4,516a cobalt catalyst Co-116h and iron catalysts Fe-1,216h,22 were prepared by following the
reported procedure. 1H, 13C NMR spectra were recorded on Bruker (1H: 500 MHz, 13C {1H}:
126 MHz) and JEOL (1H: 400 MHz, 13C {1H}: 101 MHz) and were referenced to the
resonances of the solvent used. Multiplicities are indicated as: br (broad), s (singlet), d
(doublet), t (triplet), dd (doublet of doublet), or m (multiplet). Coupling constants (J) are
reported in Hertz (Hz). FT-IR spectra were recorded by Perkin–Elmer FT–IR Spectrometer.
Mass spectra were recorded on Bruker micrOTOF-Q II Spectrometer. Electrospray ionization
(ESI) mass spectra were recorded by QTOF Micro YA263 instrument. For thin-layer
chromatography (TLC) analysis Merck pre-coated TLC plates (silica gel 60 F254 0.25 mm)
were used. Visualization was accomplished by UV light (254 nm), I2, KMnO4, and cerium
molybdate.
General Procedure for the Preparation of Alkyl Sulfones 1. Sodium benzene sulfinate (3
mmol, 1 equiv.) and tetrabutylammonium iodide (10 mol%) were dissolved in CH3CN (0.5 M)
in a round bottom flask. To this solution, corresponding alkyl bromide (3 mmol, 1 equiv.) was
slowly added and the mixture was refluxed overnight under argon atmosphere. The reaction
was then quenched with water and the organics were extracted with ethyl acetate (3 x 10 mL),
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purified by column chromatography and/or recrystallized in Hexane/EtOAc solution. No
attempts were made to optimize the yields.
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(benzylsulfonyl)benzene (1a):27a Yield 530 mg (2.28 mmol, 76%). H NMR (400 MHz,
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CDCl3) δ 7.64 – 7.55 (m, 3H), 7.43 (t, J = 7.7 Hz, 2H), 7.32 – 7.21 (m, 3H), 7.08 – 7.04 (m,
2H), 4.29 (s, 2H).
1
1-methyl-2-((phenylsulfonyl)methyl)benzene (1b):27a Yield 567 mg (2.16 mmol, 72%). H
NMR (400 MHz, CDCl3) δ 7.66 – 7.56 (m, 3H), 7.43 (dd, J = 10.8, 4.7 Hz, 2H), 7.21 – 7.16
(m, 1H), 7.11 – 7.04 (m, 2H), 6.99 (d, J = 7.6 Hz, 1H), 4.35 (s, 2H), 2.08 (s, 3H).
1-methoxy-4-((phenylsulfonyl)methyl)benzene (1c):27a Yield 637 mg (2.43 mmol, 81%). 1H
NMR (400 MHz, CDCl3) δ 7.65 – 7.54 (m, 3H), 7.43 (dd, J = 16.1, 8.4 Hz, 2H), 7.01 – 6.94
(m, 2H), 6.79 – 6.74 (m, 2H), 4.23 (s, 2H), 3.78 (d, J = 3.8 Hz, 3H).
1
4-((phenylsulfonyl)methyl)-1,1'-biphenyl (1d):27b Yield 703 mg (2.28 mmol, 76%). H NMR
(400 MHz, CDCl3) δ 7.68 – 7.64 (m, 6H), 7.61 – 7.56 (m, 3H), 7.54 (dd, J = 5.3, 3.3 Hz, 6H),
7.47 (dd, J = 8.5, 2.0 Hz, 8H), 7.44 – 7.39 (m, 10H), 7.36 – 7.30 (m, 3H), 7.13 (d, J = 8.2 Hz,
6H), 4.32 (s, 6H).
1
1-fluoro-4-((phenylsulfonyl)methyl)benzene (1e):27c Yield 518 mg (2.07 mmol, 69%). H
NMR (400 MHz, CDCl3) δ 7.61 (dd, J = 11.9, 7.7 Hz, 3H), 7.45 (t, J = 7.7 Hz, 2H), 7.05 (dd,
J = 8.4, 5.4 Hz, 2H), 6.94 (t, J = 8.7 Hz, 2H), 4.26 (s, 2H).
1
1-chloro-4-((phenylsulfonyl)methyl)benzene (1f):27c Yield 584 mg (2.19 mmol, 73%). H
NMR (400 MHz, CDCl3) δ 7.65 – 7.54 (m, 1H), 7.45 (t, J = 7.8 Hz, 1H), 7.24 – 7.18 (m, 1H),
7.01 – 6.97 (m, 1H), 4.24 (s, 1H).
1
1-bromo-4-((phenylsulfonyl)methyl)benzene (1g):27d Yield 653 mg (2.10 mmol, 70%). H
NMR (400 MHz, CDCl3) δ 7.64 – 7.57 (m, 3H), 7.45 (t, J = 7.8 Hz, 2H), 7.36 (t, J = 5.3 Hz,
2H), 6.95 – 6.90 (m, 2H), 4.22 (s, 2H).
1
1-iodo-3-((phenylsulfonyl)methyl)benzene (1h):27e Yield 784 mg (2.19 mmol, 73%). H
NMR (400 MHz, CDCl3) δ 7.64 – 7.58 (m, 4H), 7.46 (t, J = 7.9 Hz, 2H), 7.32 (d, J = 1.4 Hz,
1H), 7.07 (d, J = 7.7 Hz, 1H), 6.98 (t, J = 7.8 Hz, 1H), 4.19 (s, 2H).
1-((phenylsulfonyl)methyl)-4-(trifluoromethyl)benzene (1i):27a Yield 613 mg (2.04 mmol,
68%). 1H NMR (400 MHz, CDCl3) δ 7.65 – 7.57 (m, 3H), 7.50 (d, J = 8.2 Hz, 2H), 7.46 (dd,
J = 10.8, 4.7 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 4.32 (s, 2H).
1
1-((phenylsulfonyl)methyl)naphthalene (1j):27b Yield 609 mg (2.16 mmol, 72%). H NMR
(400 MHz, CDCl3) δ 7.80 – 7.76 (m, 1H), 7.73 – 7.65 (m, 2H), 7.63 – 7.59 (m, 2H), 7.58 –
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7.53 (m, 1H), 7.49 (d, J = 4.8 Hz, 1H), 7.48 – 7.43 (m, 2H), 7.43 – 7.35 (m, 2H), 7.16 (dd, J =
5
6
8.4, 1.9 Hz, 1H), 4.44 (s, 2H).
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Optimization Studies for the Manganese Catalyzed Synthesis of Vinyl Sulfones 3 (Table
1, Table S1 – S7). In a 15 mL Schlenk tube, a base (0 – 20 mol%) and a base metal catalyst (0
– 4 mol%) were suspended in a solvent (0.5 mL). The alkyl sulfone 1a (0.1 – 0.15 mmol) and
benzyl alcohol 2a (0.1 –0.15 mmol) were then added. The tube was closed and stirred in a
preheated oil bath at 120 – 140 oC under argon for 24 h. The reaction was quenched with water
(2 mL) and the organics were extracted with ethyl acetate (3 x 10 mL). The combined organic
layers were dried over Na2SO4, filtered, concentrated, and the residue was purified by column
chromatography over silica gel (100–200 mesh) with hexane/ethyl acetate mixture as eluent.
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General Procedure for the Manganese Catalyzed Synthesis of Vinyl Sulfones 3. In a 15
mL Schlenk tube, t-BuOK (2.2 mg, 0.02 mmol) and Mn-5 (2.4 mg, 0.004 mmol, 4 mol%) were
suspended in t-AmOH (0.5 mL). The alkyl sulfone 1 (0.15 mmol) and the primary alcohol 2
(0.1 mmol) were then added. The tube was closed and stirred in a preheated oil bath at 140 oC
under argon for 24 h. The reaction was quenched with water (2 mL) and the organics were
extracted with ethyl acetate (3 x 10 mL). The combined organic layers were dried over Na2SO4,
filtered, concentrated, and the residue was purified by column chromatography over silica gel
(100–200 mesh) with hexane/ethyl acetate mixture as eluent to deliver the vinyl sulfones 3.
(E)-(1-(phenylsulfonyl)ethene-1,2-diyl)dibenzene (3aa):29 Yield 30 mg (0.094 mmol, 94%).
1
Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 24:1). H NMR (400
MHz, CDCl3) δ 7.96 (s, 1H), 7.61 (d, J = 7.4 Hz, 2H), 7.51 (t, J = 7.6 Hz, 1H), 7.40 – 7.32 (m,
3H), 7.28-7.21 (m, 3H), 7.15 (t, J = 7.6 Hz, 2H), 7.06 (d, J = 7.6 Hz, 2H), 7.01 (d, J = 7.2 Hz,
2H). 13C NMR (101 MHz, CDCL3) δ 141.4, 138.7, 137.7, 133.3, 132.8, 131.3, 130.8, 130.6,
130.2, 129.3, 128.9, 128.8, 128.7, 128.6. Selected IR (ATR)  (cm-1): 1632, 1441, 1247, 1280,
1018, 906. MS (ESI) m/z 321.1 (M)+.
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(E)-1-methyl-4-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ab): Yield 26 mg (0.078
mmol, 78%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 19:1). 1H
NMR (400 MHz, CDCl3) δ 7.94 (s, 1H), 7.62 (d, J = 8.5 Hz, 2H), 7.52 (t, J = 7.3 Hz, 1H), 7.42
– 7.33 (m, 3H), 7.31 – 7.26 (m, 2H), 7.02 (d, J = 5.8 Hz, 2H), 6.97 (d, J = 1.9 Hz, 4H), 2.27 (s,
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3H). C NMR (101 MHz, CDCl3) δ 140.7, 140.2, 138.9, 137.8, 133.2, 131.6, 130.9, 130.7,
130.1, 129.4, 129.2, 128.9, 128.8, 128.7, 21.5. Selected IR (ATR)  (cm-1): 1633, 1506, 1291,
1250, 1146, 1029. HRMS calcd for C21H18O2SNa [M + Na]+ 357.0920, found 357.0945.
(E)-1-methyl-2-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ac): Yield 24 mg (0.072
1
mmol, 72%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H
NMR (400 MHz, CDCl3) δ 8.21 (s, 1H), 7.66 (d, J = 7.7 Hz, 2H), 7.53 (t, J = 7.4 Hz, 1H), 7.40
(t, J = 7.8 Hz, 2H), 7.30-7.26 (m, 1H), 7.22-7.15 (m, 3H), 7.11 (t, J = 7.2 Hz, 1H), 7.02 (d, J =
13
7.2 Hz, 2H), 6.83 (t, J = 7.5 Hz, 1H), 6.75 (d, J = 7.8 Hz, 1H), 2.46 (s, 3H). C NMR (126
MHz, CDCl3) δ 142.4, 139.0, 138.3, 136.5, 133.2, 132.0, 131.1, 131.0, 130.4, 129.5, 129.2,
129.0, 128.8, 128.6, 128.6, 125.7. Selected IR (ATR)  (cm-1): 1632, 1446, 1300, 1143, 1086,
760. HRMS calcd for C21H18O2SNa [M + Na]+ 357.0920, found 357.0939.
(E)-1-methoxy-4-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ad): Yield 32 mg (0.092
1
mmol, 92%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H
NMR (400 MHz, CDCl3) δ 7.89 (s, 1H), 7.60 (d, J = 7.2 Hz, 2H), 7.50 (t, J = 7.7 Hz, 1H), 7.39
– 7.32 (m, 3H), 7.29 – 7.24 (m, 2H), 7.03 – 6.97 (m, 4H), 6.67 (d, J = 8.9 Hz, 2H). 13C NMR
(101 MHz, CHLOROFORM-D) δ 161.1, 139.1, 138.5, 137.5, 133.1, 132.4, 131.7, 131.0,
129.1, 129.0. 128.7, 128.6, 128.6, 125.4, 114.1. 55.3. Selected IR (ATR)  (cm-1): 1603, 1512,
1445, 1258, 1303, 941. HRMS calcd for C21H18O3SNa [M + Na]+ 373.0869, found 373.0881.
(E)-4-(2-phenyl-2-(phenylsulfonyl)vinyl)-1,1'-biphenyl (3ae): Yield 28 mg (0.071 mmol,
1
71%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 8.00 (s, 1H), 7.64 (d, J = 8.1 Hz, 2H), 7.57 – 7.49 (m, 3H), 7.43 – 7.38
(m, 6H), 7.37 – 7.28 (m, 4H), 7.14 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 7.0 Hz, 2H). 13C NMR (126
MHz, CDCl3) δ 142.88 (s), 141.2, 140.0, 138.8, 137.3, 133.3, 131.8, 131.5, 131.2, 130.9, 129.3,
129.0, 128.9, 128.8, 128.7, 128.0, 127.2, 127.1. Selected IR (ATR)  (cm-1): 1626, 1486, 1304,
1146, 1085, 942. HRMS calcd for C26H21O2SH [M + H]+ 397.1257, found 397.1278.
(E)-1-fluoro-4-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3af): Yield 16 mg (0.046 mmol,
1
46%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 7.91 (s, 1H), 7.60 (d, J = 7.8 Hz, 2H), 7.52 (t, J = 7.6 Hz, 1H), 7.38 (t, J
= 8.1 Hz, 3H), 7.27 (t, J = 7.6 Hz, 2H), 7.07 – 7.03 (m, 2H), 6.99 (d, J = 7.0 Hz, 2H), 6.84 (t,
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J = 8.7 Hz, 2H). 13C NMR (101 MHz, CHLOROFORM-D) δ 163.6 (d, JC-F = 306.1 Hz), 141.1,
5
6
7
8
141.0, 138.6, 136.4, 133.0 (d, J = 83.1 Hz), 132.7, 131.1, 130.8, 129.4, 129.1, 128.8 (d, JC-F
=
9.0 Hz), 115.8 (d, JC-F = 27.7 Hz). 19F NMR (471 MHz, CDCl3) δ -109.1. Selected IR (ATR)
 (cm-1): 1632, 1503, 1303, 1225, 1147, 1086, 780. HRMS calcd for C20H15FO2SNa [M + Na]+
361.0669, found 361.0644.
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(E)-1-chloro-4-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ag): Yield 29 mg (0.081
1
mmol, 81%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H
NMR (400 MHz, CDCl3) δ 7.91 (s, 1H), 7.61 (d, J = 8.5 Hz, 2H), 7.54 (t, J = 7.6 Hz, 1H), 7.42
13
– 7.34 (m, 3H), 7.28 (t, J = 7.6 Hz, 2H), 7.14 (d, J = 8.5 Hz, 2H), 7.03 – 6.97 (m, 4H). C
NMR (126 MHz, CDCl3) δ 142.1, 138.5, 136.3, 136.2, 133.4, 131.8, 131.4, 130.7, 129.5, 129.1,
129.9, 129.88, 129.8. Selected IR (ATR)  (cm-1): 1632, 1488, 1304, 1146, 1085, 1014. HRMS
calcd for C20H15ClO2SNa [M + Na]+ 377.0373, found 377.0384.
(E)-1-chloro-3-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ah): Yield 23 mg (0.065
1
mmol, 65%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H
NMR (400 MHz, CDCl3) δ 7.89 (s, 1H), 7.62 (d, J = 7.6 Hz, 2H), 7.54 (t, J = 7.6 Hz, 1H), 7.43
– 7.36 (m, 3H), 7.29 (t, J = 7.6 Hz, 2H), 7.23 – 7.19 (m, 1H), 7.09 (t, J = 8.0 Hz, 1H), 7.05 –
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6.98 (m, 3H), 6.93 (d, J = 8.1 Hz, 1H). C NMR (126 MHz, CDCl3) δ 143.1, 138.4, 136.1,
134.7, 134.5, 133.5, 130.8, 130.7, 130.4, 130.0, 129.8, 129.6, 129.1, 128.9, 128.8, 128.6,
Selected IR (ATR)  (cm-1): 1636, 1303, 1147, 1082, 688. HRMS calcd for C20H15ClO2SNa
[M + Na]+ 377.0373, found 377.0364.
(E)-1-chloro-2-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ai): Yield 29 mg (0.081 mmol,
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81%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 8.29 (s, 1H), 7.67 (d, J = 7.4 Hz, 2H), 7.53 (t, J = 7.2 Hz, 1H), 7.42 – 7.36
(m, 3H), 7.31 – 7.27 (m, 1H), 7.24 – 7.18 (m, 2H), 7.17 – 7.11 (m, 1H), 7.05 (d, J = 7.1 Hz,
2H), 6.88 (t, J = 7.6 Hz, 1H), 6.77 (d, J = 9.5 Hz, 1H). 13C NMR (126 MHz, CDCl3) δ 144.0,
138.7, 135.5, 134.9, 133.4, 131.7, 130.9, 130.62, 130.61, 129.8, 129.3, 129.0, 128.9, 128.7.
128.7 126.5. Selected IR (ATR)  (cm-1): 1624, 1465, 1284, 1144, 1038, 902. HRMS calcd for
C20H15ClO2SNa [M + Na]+ 377.0373, found 377.0391.
(E)-1-bromo-4-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3aj): Yield 36 mg (0.089
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mmol, 89%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H
NMR (500 MHz, CDCl3) δ 7.89 (s, 1H), 7.61 (d, J = 7.7 Hz, 2H), 7.53 (t, J = 7.4 Hz, 1H), 7.38
(dd, J = 14.6, 6.9 Hz, 3H), 7.29 (dd, J = 8.1, 3.7 Hz, 4H), 7.00 (d, J = 7.4 Hz, 2H), 6.91 (d, J =
8.6 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 142.3, 138.5, 136.3, 133.4, 131.9, 131.9, 131.8,
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131.0, 130.7, 129.5, 129.1, 128.88, 128.8. Selected IR (ATR)  (cm-1): 1632, 1249, 1211, 1015,
936, 716. HRMS calcd for C20H15BrO2SNa [M + Na] + 420.9868, found 420.9887.
(E)-1-iodo-3-(2-phenyl-2-(phenylsulfonyl)vinyl)benzene (3ak): Yield 23 mg (0.052 mmol,
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52%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
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(400 MHz, CDCl3) δ 7.83 (s, 1H), 7.60 (d, J = 8.5 Hz, 2H), 7.53 (t, J = 9.2 Hz, 2H), 7.40-7.36
(m, 4H), 7.28 (t, J = 7.6 Hz, 2H), 7.00 – 6.95 (m, 3H), 6.86 (t, J = 7.9 Hz, 1H); 13C NMR (101
MHz, CDCl3) δ 143.0, 139.6, 138.8, 138.4, 135.9, 135.0, 133.5, 130.9, 130.7, 130.2, 129.6,
129.4, 129.1, 128.9, 128.8, 94.2.Selected IR (ATR)  (cm-1): 1633, 1416, 1340, 1123, 1012,
860. HRMS calcd for C20H15IO2SNa [M + Na]+ 468.9730, found 468.9743.
(E)-1-(2-phenyl-2-(phenylsulfonyl)vinyl)-4-(trifluoromethyl)benzene (3al): Yield 23 mg
(0.058 mmol, 58%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate =
1
24:1). H NMR (400 MHz, CDCl3) δ 7.96 (s, 1H), 7.61 (d, J = 9.1 Hz, 2H), 7.53 (t, J = 7.6
Hz, 1H), 7.42 – 7.34 (m, 5H), 7.27 (t, J = 7.6 Hz, 2H), 7.16 (d, J = 8.2 Hz, 2H), 6.99 (d, J =
8.6 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 144.0, 138.1, 136.2, 135.6, 133.4, 131.5, 131.2,
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130.6, 130.5, 130.4, 129.5, 129.0, 128.8, 128.7, 125.35 (dd, J = 7.4, 3.7 Hz); F NMR (471
MHz, CDCl3) δ -63.06.Selected IR (ATR)  (cm-1): 1632, 1415, 1304, 1085, 1016, 907. HRMS
calcd for C21H15F3O2SNa [M + Na]+ 411.0637, found 411.0623.
(E)-1-(2-phenyl-2-(phenylsulfonyl)vinyl)naphthalene (3am): Yield 30 mg (0.081 mmol,
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81%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 8.14 (s, 1H), 7.71 (d, J = 7.2 Hz, 2H), 7.67 (d, J = 7.2 Hz, 3H), 7.53 (dd,
J = 8.0, 6.1 Hz, 2H), 7.49 – 7.37 (m, 5H), 7.31 (t, J = 7.6 Hz, 2H), 7.08 (d, J = 7.0 Hz, 2H),
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6.99 (d, J = 8.9 Hz, 1H). C NMR (126 MHz, CDCl3) δ 141.4, 138.9, 137.9, 133.8, 133.3,
133.0, 132.2, 131.5, 131.0, 130.5, 129.3, 129.0, 128.8, 128.7, 128.7, 128.1, 127.68, 127.62,
126.6, 126.2. Selected IR (ATR)  (cm-1): 1624, 1445, 1304, 1145, 1085, 942. HRMS calcd
for C24H18O2SNa [M + Na]+ 393.0920, found 393.0917.
(E)-3-(2-phenyl-2-(phenylsulfonyl)vinyl)pyridine (3an): Yield 15 mg (0.047 mmol, 47%).
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Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 2.3:1). H NMR (400
MHz, CDCl3) δ 8.47 – 8.42 (m, 2H), 7.94 (s, 1H), 7.63 (d, J = 7.9 Hz, 2H), 7.55 (t, J = 7.4 Hz,
1H), 7.43 – 7.35 (m, 3H), 7.30 (t, J = 7.6 Hz, 2H), 7.21 (d, J = 8.2 Hz, 1H), 7.07-7.04 (m, 1H),
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7.02 (d, J = 7.2 Hz, 2H). C NMR (126 MHz, CDCl3) δ 151.8, 150.7, 144.0, 138.2, 136.5,
134.0, 133.6, 130.7, 130.5, 129.7, 129.2, 129.0, 128.9, 128.8, 123.3. Selected IR (ATR)  (cm-
1): 1636, 1449, 1306, 1150, 1086, 698. HRMS calcd for C19H15NO2SNa [M + Na]+ 344.0716,
found 344.0732.
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(E)-3-(2-phenyl-2-(phenylsulfonyl)vinyl)thiophene (3ao): Yield 24 mg (0.074 mmol, 74%).
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Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 4:1). H NMR (500
MHz, CDCl3) δ 8.14 (s, 1H), 7.64 (d, J = 7.7 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.44-7.39 (m,
5.2 Hz, 3H), 7.34 (t, J = 7.6 Hz, 2H), 7.26-7.22 (m, 2H), 7.01 (d, J = 7.4 Hz, 2H), 6.98 – 6.93
(m, 1H). 13C NMR (126 MHz, CDCl3) δ 138.9, 138.1, 136.6, 134.2, 133.3, 131.5, 131.3, 131.2,
130.6, 129.8, 129.2, 128.8, 128.7, 127.0. Selected IR (ATR)  (cm-1): 1617, 1489, 1373, 1304,
1145, 1085. HRMS calcd for C18H14O2S2Na [M + Na]+ 349.0327, found 349.0349.
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(E)-3-(2-phenyl-2-(phenylsulfonyl)vinyl)furan (3ap): Yield 26 mg (0.084 mmol, 84%).
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Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 4:1). H NMR (400
MHz, CDCl3) δ 7.83 (s, 1H), 7.62 (d, J = 7.3 Hz, 2H), 7.56-7.52 (m, 1H), 7.42-7.36 (m, 4H),
7.31 (t, J = 7.6 Hz, 2H), 7.02 (d, J = 7.7 Hz, 2H), 6.28 – 6.23 (m, 1H), 5.89 (d, J = 3.4 Hz, 1H).
13C NMR (126 MHz, CDCl3) δ 149.3, 145.1, 138.9, 138.1, 133.3, 131.4, 130.5, 129.3, 128.8,
128.8, 128.6, 126.0, 115.5, 112.3. Selected IR (ATR)  (cm-1): 1628, 1471, 1305, 1246, 1146,
963. HRMS calcd for C18H14O3SNa [M + Na]+ 333.0556, found 333.0530.
(E)-(2-cyclopropyl-1-(phenylsulfonyl)vinyl)benzene (3aq): Yield 22 mg (0.077 mmol,
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77%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 7.58 (d, J = 7.4 Hz, 2H), 7.50 (t, J = 7.6 Hz, 1H), 7.37 (t, J = 7.7 Hz, 2H),
7.27 (ddd, J = 8.9, 4.4, 2.1 Hz, 3H), 7.13 (dd, J = 7.9, 1.7 Hz, 2H), 6.54 (d, J = 10.7 Hz, 1H),
1.31 (dtd, J = 11.0, 8.0, 4.2 Hz, 1H), 0.94 – 0.88 (m, 2H), 0.79 – 0.75 (m, 2H). 3C NMR (101
MHz, CHLOROFORM-D) δ 148.0, 139.5, 133.0, 131.14, 131.1, 129.1, 128.8, 128.7, 128.4,
128.3, 12.3, 9.2. Selected IR (ATR)  (cm-1): 1636, 1449, 1306, 1150, 1086, 698. HRMS calcd
for C17H16O2SNa [M + Na]+ 307.0763, found 307.0769.
(E)-((1-phenylpent-1-en-1-yl)sulfonyl)benzene (3ar): Yield 11 mg (0.037 mmol, 37%).
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Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR (400
MHz, CDCl3) δ 7.58 (d, J = 7.7 Hz, 2H), 7.52 (t, J = 7.6 Hz, 1H), 7.38 (t, J = 7.7 Hz, 2H), 7.30
(d, J = 7.1 Hz, 1H), 7.26 (s, 1H), 7.20 (t, J = 7.6 Hz, 1H), 6.97 (d, J = 7.1 Hz, 2H), 2.00 (q, J =
7.5 Hz, 2H), 1.47 (dd, J = 14.7, 7.4 Hz, 2H), 0.88 (d, J = 7.4 Hz, 3H). 13C NMR (126 MHz,
CDCl3) δ 142.9, 139.2, 133.1, 130.8, 128.9, 128.8, 128.5, 128.3, 31.1, 21.9, 13.8. Selected IR
(ATR)  (cm-1): 1636, 1449, 1306, 1147, 1086, 719. HRMS calcd for C17H18O2SNa [M + Na]+
309.0920, found 309.0917.
(E)-((1-phenylhept-1-en-1-yl)sulfonyl)benzene (3as): Yield 8 mg (0.026 mmol, 26%).
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Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR (400
MHz, CDCl3) δ 7.56 (d, J = 7.7 Hz, 2H), 7.50 (t, J = 7.3 Hz, 1H), 7.36 (t, J = 7.8 Hz, 2H), 7.29
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(t, J = 7.2 Hz, 1H), 7.24 (d, J = 7.6 Hz, 2H), 7.18 (t, J = 7.7 Hz, 1H), 6.95 (d, J = 7.0 Hz, 2H),
1.99 (t, J = 7.5 Hz, 2H), 1.44 – 1.38 (m, 2H), 1.19 (m, 4H), 0.82 (t, J = 6.7 Hz, 3H); 13C NMR
(101 MHz, CDCl3) δ 143.2, 142.8, 139.2, 133.2, 130.8, 130.8, 128.9, 128.8, 128.6, 128.4,
31.42, 29.85, 28.26, 22.46, 14.02. Selected IR (ATR)  (cm-1): 1630, 1321, 1165, 1098, 939,
737. HRMS calcd for C19H22O2SNa [M + Na]+ 337.1233, found 337.1230.
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(E)-1-methyl-2-(2-phenyl-1-(phenylsulfonyl)vinyl)benzene (3ba): Yield 30 mg (0.090
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mmol, 90%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H
NMR (400 MHz, , CDCl3) δ 7.98 (s, 1H), 7.60 (d, J = 5.8, 2H), 7.54 (t, J = 7.2 Hz, 1H), 7.39
(m, 2H), 7.31 – 7.22 (m, 2H), 7.18-7.10 (m, 4H), 7.05 – 7.01 (m, 2H), 6.95 (d, J = 7.6, 1H),
1.70 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 140.1 , 138.8 , 138.5 , 138.2 , 133.4 , 133.2, 131.3,
130.7, 130.4, 130.1, 129.7, 129.1, 128.9, 128.8, 126.3, 9.10.Selected IR (ATR)  (cm-1):
1632,1421, 1265, 1148, 909, 737. HRMS calcd for C21H18O2SNa [M + Na]+ 357.0920, found
357.0918.
(E)-1-methoxy-4-(2-phenyl-1-(phenylsulfonyl)vinyl)benzene (3ca): Yield 33 mg (0.094
mmol, 94%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 24:1). 1H
NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.62 (d, J = 8.2 Hz, 2H), 7.51 (t, J = 7.9 Hz, 1H), 7.38
(t, J = 7.4 Hz, 2H), 7.25 – 7.20 (m, 1H), 7.16 (t, J = 7.7 Hz, 2H), 7.09 (d, J = 8.1 Hz, 2H), 6.93
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(d, J = 9.3 Hz, 2H), 6.79 (d, J = 8.5 Hz, 2H), 3.79 (s, 3H). C NMR (126 MHz, CDCl3) δ
160.3, 141.1, 138.9, 137.7, 133.2, 133.1, 132.1, 130.6, 130.1, 128.8, 128.7, 128.6, 123.1, 114.4,
55.3. Selected IR (ATR)  (cm-1): 1633, 1446, 1247, 1289, 1028, 916. HRMS calcd for
C21H18O3SNa [M + Na]+ 373.0869, found 373.0890.
(E)-1-chloro-3-(2-(4-methoxyphenyl)-2-(phenylsulfonyl)vinyl)benzene (3ch): Yield 28 mg
(0.073 mmol, 73%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate =
9:1). 1H NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.62 (d, J = 8.9 Hz, 2H), 7.54 (t, J = 7.3 Hz,
1H), 7.40 (t, J = 7.7 Hz, 2H), 7.21 (d, J = 7.5 Hz, 1H), 7.10 (t, J = 7.9 Hz, 2H), 6.94 (t, J = 7.9
Hz, 3H), 6.81 (d, J = 8.6 Hz, 2H), 3.81 (s, 3H). 13C NMR (101 MHz, CHLOROFORM-D) δ
160.5, 142.8, 138.6, 136.0, 134.9, 134.5, 133.4, 132.0, 130.5, 129.9, 129.8, 128.9, 128.7, 128.4,
122.5, 114.6, 100.0, 55.4. Selected IR (ATR)  (cm-1): 1632, 1509, 1303, 1292, 1146, 1029.
MS (ESI) m/z 386.05 (M)+.
(E)-1-(2-cyclopropyl-1-(phenylsulfonyl)vinyl)-4-methoxybenzene (3cq): Yield 25 mg
(0.080 mmol, 80%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate =
9:1). 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.8 Hz, 2H), 7.49 (t, J = 7.6 Hz, 1H), 7.37 (t,
J = 7.7 Hz, 2H), 7.06 (d, J = 8.9 Hz, 2H), 6.79 (d, J = 8.7 Hz, 2H), 6.51 (d, J = 10.8 Hz, 1H),
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3.77 (s, 3H), 1.39 – 1.30 (m, 1H), 0.92 – 0.86 (m, 2H), 0.78 – 0.71 (m, 2H). C NMR (101
MHz, CHLOROFORM-D) δ 159.9, 147.9, 139.6, 139.1, 132.8, 132.3, 128.7, 128.2, 123.0,
113.8, 55.3, 12.2, 9.1. Selected IR (ATR)  (cm-1): 1632,1446, 1144, 1030, 963, 845. HRMS
calcd for C18H18O3SNa [M + Na]+ 337.0869, found 337.0874.
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(E)-4-(2-phenyl-1-(phenylsulfonyl)vinyl)-1,1'-biphenyl (3da): Yield 30 mg (0.076 mmol,
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76%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 7.98 (s, 1H), 7.68 – 7.64 (m, 2H), 7.62 – 7.59 (m, 2H), 7.55 – 7.50 (m,
3H), 7.47 – 7.33 (m, 5H), 7.27 – 7.23 (m, 1H), 7.21 – 7.06 (m, 6H).13C NMR (101 MHz,
CHLOROFORM-D) δ 141.8, 141.1, 140.0, 138.8, 137.9, 133.3, 132.9, 131.3, 130.7, 130.2,
129.3, 129.0, 128.8, 128.7, 128.6, 127.9, 127.5, 127.1. Selected IR (ATR)  (cm-1): 1632, 1486,
1304, 1145, 1085, 921. HRMS calcd for C26H20O2SNa [M + Na]+ 419.1076, found 419.1061.
(E)-1-fluoro-4-(2-phenyl-1-(phenylsulfonyl)vinyl)benzene (3ea): Yield 25 mg (0.074 mmol,
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74%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 7.98 (s, 1H), 7.63 (d, J = 7.1 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H), 7.41 (t, J
= 7.7 Hz, 2H), 7.29-7.25 (m, 1H), 7.20 (t, J = 7.6 Hz, 2H), 7.08 (d, J = 7.4 Hz, 2H), 7.02 – 6.98
(m, 3H). 13C NMR (126 MHz, CDCl3) δ 164.3, 162.3, 139.6 (d, JC-F =223 MHz),138.2, 133.4,
132.9 (d, JC-F =7.56 MHz), 132.7, 130.6, 130.3, 128.9, 128.7,128.7, 127.3 (d, J = 3.5 Hz), 116.2
(d, JC-H =21.42MHz). Selected IR (ATR)  (cm-1): 1633, 1300, 1144, 1085, 958, 818. HRMS
calcd for C20H15FO2SNa [M + Na]+ 361.0669, found 361.0680.
(E)-1-chloro-4-(2-phenyl-1-(phenylsulfonyl)vinyl)benzene (3fa): Yield 26 mg (0.074 mmol,
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74%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 7.96 (s, 1H), 7.62 (d, J = 8.2 Hz, 2H), 7.55-7.52 (m, 1H), 7.40 (t, J = 7.3
Hz, 2H), 7.25 (d, J = 7.0 Hz, 3H), 7.19 (t, J = 7.3 Hz, 2H), 7.06 (d, J = 8.1 Hz, 2H), 6.96 (d, J
= 8.4 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 140.2, 138.6, 138.4, 135.6, 133.5, 132.6, 132.3,
130.6, 130.4, 129.9, 129.3, 129.0, 128.7, 128.71. Selected IR (ATR)  (cm-1): 1636, 1490,
1306, 1143, 1086, 722. HRMS calcd for C20H15ClO2SNa [M + Na]+ 377.0379, found 377.0369.
(E)-1-bromo-4-(2-phenyl-1-(phenylsulfonyl)vinyl)benzene (3ga): Yield 20 mg (0.050
mmol, 50%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 24:1). 1H
NMR (400 MHz, CDCl3) δ 7.96 (s, 1H), 7.65 – 7.58 (m, 2H), 7.54 (t, J = 7.5 Hz, 1H), 7.43 –
7.38 (m, 4H), 7.29 – 7.25 (m, 1H), 7.19 (t, J = 7.6 Hz, 2H), 7.06 (d, J = 7.5 Hz, 2H), 6.90 (t, J
= 5.3 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 140.3, 138.7, 138.4, 133.5, 132.6,132.5, 132.3,
130.7, 130.5, 129.0, 128.8, 124.0. Selected IR (ATR)  (cm-1): 1630, 1342, 1203, 1127, 1016,
648. HRMS calcd for C20H15BrO2SNa [M + Na]+ 420.9868, found 420.9860.
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(E)-1-iodo-3-(2-phenyl-1-(phenylsulfonyl)vinyl)benzene (3ha): Yield 16 mg (0.036 mmol,
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36%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate =4 :1). H NMR
(400 MHz, CDCl3) δ 7.95 (s, 1H), 7.73 – 7.69 (m, 1H), 7.63 (d, J = 7.7 Hz, 2H), 7.60-7.56 (m,
1H), 7.44 (t, J = 7.8 Hz, 2H), 7.32 – 7.27 (m, 2H), 7.21 (t, J = 7.7 Hz, 2H), 7.08 (d, J = 7.6 Hz,
2H), 7.03 (d, J = 6.9 Hz, 2H).13C NMR (126 MHz, CDCl3) δ 139.9, 139.3, 138.4, 138.3, 138.2,
133.6, 132.5, 130.7, 130.6, 130.5, 130.2, 130.0, 129.0, 128.84, 128.8, 94.2. Selected IR (ATR)
 (cm-1): 1631, 1246, 1201, 1045, 1015, 716. HRMS calcd for C20H15IO2SNa [M + Na]+
468.9730, found 468.9745.
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(E)-1-(2-phenyl-1-(phenylsulfonyl)vinyl)-4-(trifluoromethyl)benzene (3ia): Yield 16 mg
(0.041 mmol, 41%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate =
24:1). 1H NMR (400 MHz, CDCl3) δ 8.01 (s, 1H), 7.61 (d, J = 7.7 Hz, 2H), 7.55 (dd, J = 11.7,
4.8 Hz, 3H), 7.41 (t, J = 7.8 Hz, 2H), 7.29 – 7.24 (m, 1H), 7.21 – 7.14 (m, 4H), 7.03 (d, J = 7.5
Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 140.1, 138.8, 138.5, 135.5, 133.7, 132.4, 131.4, 131.3,
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130.7, 130.6, 129.0, 128.9, 128.7, δ 125.9 (q, JC-F = 3.5 Hz), 125.0; F NMR (471 MHz,
CDCl3) δ -62.77.Selected IR (ATR)  (cm-1): 1634, 1445, 1305, 1144, 1065, 725. HRMS calcd
for C21H15F3O2SNa [M + Na]+ 411.0637, found 411.0635.
(E)-2-(2-phenyl-1-(phenylsulfonyl)vinyl)naphthalene (3ja): Yield 32 mg (0.086 mmol,
1
86%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). H NMR
(400 MHz, CDCl3) δ 8.05 (s, 1H), 7.82 (d, J = 7.9 Hz, 1H), 7.71 (t, J = 8.5 Hz, 2H), 7.62-7.60
(m, 3H), 7.55 – 7.44 (m, 3H), 7.34 (t, J = 7.9 Hz, 2H), 7.23 – 7.18 (m, 1H), 7.13 – 7.06 (m,
4H), 7.03-7.01 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 141.3, 138.8, 138.1, 133.3 (3C), 132.9,
130.7,130.6, 130.3, 128.9, 128.8,128.7,128.5, 127.9,127.8, 127.2, 126.5.1634, 1446,1304,
1145, 1085, 746. HRMS calcd for C24H18O2SNa [M + Na]+ 393.0920, found 393.0938.
(E)-(2-(phenylsulfonyl)vinyl)benzene (3la):30 Yield 15.1 mg (0.062 mmol). Column
Chromatography on silica gel (Eluent; hexane:ethyl acetate = 9:1). 1H NMR (400 MHz, CDCl3)
δ 7.94 (d, J = 7.3 Hz, 2H), 7.67 (d, J = 15.4 Hz, 1H), 7.60-7.58 (m, 1H), 7.55-7.53 (m, 2H),
7.48-7.46 (m, 2H), 7.38 (d, J = 6.7 Hz, 3H), 6.85 (d, J = 15.6 Hz, 1H); 13C NMR (101 MHz,
CDCl3) δ 142.6, 140.7, 133.5, 132.4, 131.3, 129.5, 129.2, 128.7, 127.8, 127.4.Selected IR
(ATR)  (cm-1): 1632,1633, 1447, 1306, 1265, 1146, 973. MS (ESI) m/z 245.0 (M)+.
(E)-1-methoxy-4-(2-(phenylsulfonyl)vinyl)benzene (3ld):29 Yield 22.4 mg (0.082 mmol,
1
82%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 4:1). H NMR
(400 MHz, CDCl3) δ 7.93 (d, J = 7.5 Hz, 2H), 7.65- 7.57 (m, 2H), 7.52 (t, J = 7.5 Hz, 2H), 7.42
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(d, J = 14.1 Hz, 2H), 6.88 (d, J = 8.7 Hz, 2H), 6.69 (d, J = 15.4 Hz, 1H), 3.81 (s, 3H).Selected
IR (ATR)  (cm-1): 1632, 1514, 1449, 1300, 1147, 1086.MS (ESI) m/z 274.06 (M)+.
(E)-(2-(methylsulfonyl)vinyl)benzene (3ma): Yield 9 mg (0.05 mmol, 50%). Column
Chromatography on silica gel (Eluent; hexane:ethyl acetate = 4:1). 1H NMR (400 MHz, CDCl3)
δ 7.62 (d, J = 15.5 Hz, 1H), 7.52 – 7.49 (m, 2H), 7.43 (m, 3H), 6.90 (d, J = 15.3 Hz, 1H), 3.02
(s, 3H); 13C NMR (126 MHz, CDCl3) δ 144.2, 132.2, 131.6, 129.3, 128.7, 126.3, 43.4.Selected
IR (ATR)  (cm-1): 1632,1633, 1447, 1306, 1265, 1146, 973. HRMS calcd for C14H12O2S [M
+ H]+ 245.0631, found 245.0641.
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(E)-1-methoxy-4-(2-(methylsulfonyl)vinyl)benzene (3md): Yield 22 mg (0.082 mmol,
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82%). Column Chromatography on silica gel (Eluent; hexane:ethyl acetate = 4:1). H NMR
(400 MHz, CDCl3) δ 7.57 (d, J = 15.4 Hz, 1H), 7.46 (d, J = 8.7 Hz, 2H), 6.93 (d, J = 8.8 Hz,
2H), 6.76 (d, J = 14.9 Hz, 1H), 3.85 (s, 3H), 3.02 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 162.3,
143.8, 130.5, 124.8, 123.5, 114.7, 55.6, 43.6. Selected IR (ATR)  (cm-1): 1602, 1510, 1293,
1126, 1028, 977. HRMS calcd for C10H12O3SNa [M + Na]+ 235.0399, found 235.0368.
Experimental Procedure for the Gram Scale Synthesis of 3ld: In a 100 mL round bottom
flask with gas inlet t-BuOK (112 mg, 1.0 mmol) and Mn-5 (50 mg, 0.1 mmol) was suspended
in t-AmOH (10 mL) under an argon atmosphere. To the solution 4-methoxybenzyl alcohol 2d
(620 µL, 5 mmol) and methyl phenyl sulfone 1l (1170 mg, 7.5 mmol) was added and the flask
was sealed properly and placed in a preheated oil bath at 140 oC for 24 h. After the completion
of reaction it was quenched with 5 mL water and the organics was extracted with EtOAc (3×10
mL) and dried over Na2SO4. The crude product was purified by column chromatography giving
3ld (1.10 gm, 80%).
ASSOCIATED CONTENT
Supporting Information. Detailed optimizations Table S1-7, mechanistic experiments,X-ray
crystallographic analysis for 3ch,and copies of NMR spectra. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Email: bm@iiserkol.ac.in
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Funding Sources
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This research was supported by SERB (ECR/2016/001654).
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The authors declare no competing financial interest.
ACKNOWLEDGMENT
The author thanks SERB (ECR/2016/001654) for financial support. For fellowship S.W. thanks
CSIR and M. K. B. thanks SERB (PDF/2016/001952). This work is dedicated to Professor
Helmut Schwarz on the occasion of his 75th birthday.
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Catalyzed α‐Alkylation of Ketones with Primary Alcohols and Friedländer Quinoline
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