Nickel(ii)-catalyzed direct olefination of benzyl alcohols with sulfones with the liberation of H2

Article abstract of DOI:10.1039/c9cc02603g

A nickel(ii)-catalyzed direct olefination of benzyl alcohols with sulfones to access various terminal and internal olefins with the liberation of hydrogen gas is reported.

Full text of DOI:10.1039/c9cc02603g

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DOI: 10.1039/C9CC02603G
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Nickel(II)-Catalyzed Direct Olefination of Benzyl Alcohols with
†
Sulfones with the Liberation of H2
Received 00th January 20xx,
Accepted 00th January 20xx
Vinod G. Landge,a‡ Vinita Yadav,a,b‡ Murugan Subaramanian,c Pragya Dangarh,a Ekambaram
Balaraman*c
DOI: 10.1039/x0xx00000x
www.rsc.org/
A nickel(II)-catalyzed direct olefination of benzyl alcohols with reported catalytic olefination of alcohols with sulfones
sulfones to access various terminal and internal olefins with the catalyzed by a well-defined Ru-PNN pincer complex (Scheme
liberation of hydrogen gas is reported.
1).12a
Prvious work
Olefins are high-value organic compounds in many research
areas because of their extensive usage in cross-coupling
reactions, synthesis of natural products, pharmaceuticals,
dyes, agro-chemicals, and production of polymers.1 Over the
past decades, considerable efforts have been devoted towards
the synthesis of olefins by employing traditional reactions such
Ph
P
H
Ru
Cl
Ph
N
N
CO
O
S
(2.5 mol%)
KOtBu
precious metal
R2
(a)
H2
R
OH
R2
R1
R
O
O
S
R
R
Me
Me
as
olefination,5 Julia olefination6 and Tebbe olefination.7
Wittig,2-3
Horner–Wadsworth–Emmons,4
Peterson
Our work
O
H2
(b)
R
OH
Ni
O
S
Sulfones are commonly utilized in the multi-step classical Julia
olefination via the formation of β-acyloxy alkyl sulfones from
aldehydes followed by the reductive elimination with sodium
amalgam to furnish the olefin. However, in some cases, the
necessary aldehydes or ketones are not readily available or
may undergo undesired side-reactions, e.g., aldol
condensation. Therefore, it is not surprising that in spite of the
existing methods the development of new versatile, and
efficient protocols for their synthesis is of continuing interest.
Nevertheless, research progress has been made for the
synthesis of olefins via oxidation of alcohols under oxygen in
the presence of palladium, rhodium, copper, ruthenium, and
also catalyst-free conditions by alcohol as a solvent and a
copious amount of base.8 The research group of Alonso
reported nickel nanoparticles promoted Wittig-type
olefination of alcohols under oxidative conditions; however, it
suffers from lack of product selectivity.8g
R2
R2
R1
O
 Earth-abundant Ni-catalyst
 Phosphine-free
 E-selective alkenes
 Drug intermediate
Scheme 1. Olefination via acceptorless dehydrogenative coupling (ADC).
Henceforth, an alternative to precious metal catalysts and to
develop a new catalytic system based on earth-abundant,
economical, low-toxic first-row transition metals is highly
demanding.13-14 In recent times, widespread applications of
nickel catalysis in chemical manufacturing and the
pharmaceutical industry have been carried out as an
alternative to noble metal catalysts.15 To date, the application
nickel catalysts for dehydrogenation and related reactions has
proven highly demanding and remains elusive.16,17c Herein we
report a Ni(II)-complex pertaining NNN-type ligand17 catalyzed
direct olefination of alcohols with sulfones to access various
terminal and internal olefins with the liberation of hydrogen
gas.
The reaction of 3,4-dimethoxyphenyl)methanol (2o) with
dimethylsulfone (1) was chosen as a model system for the
acceptorless dehydrogenative coupling to form 3o (see ESI†,
for optimization studies). We began our investigation using
dimethyl sulfone (DMS) (1) as a model substrate and (3,4-
dimethoxyphenyl)methanol (2o) as a coupling reagent in the
presence of NiCl2 (3 mol %), and KOtBu (1.1 equiv) as a base in
refluxing toluene for 12 h to yield the expected product 3o in
Acceptorless dehydrogenative coupling (ADC)9-12 has emerged
as a powerful strategy for the straightforward synthesis of
value-added chemicals. Of late, Milstein and co-workers
aOrganic Chemistry Division, Dr. Homi Bhabha Road, CSIR-National Chemical
Laboratory (CSIR-NCL), Pune - 411008, India.
bAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India.
cDepartment of Chemistry, Indian Institute of Science Education and Research –
Tirupati (IISER-T), Tirupati 517507, India. Email: eb.raman@iisertirupati.ac.in
†Electronic Supplementary Information (ESI) available: [Experimental procedures
analytical data]. See DOI: 10.1039/x0xx00000x
‡Contributed equally to this work.
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32% isolated yield. Interestingly, by employing NNN-Ni(II) The stereoselective synthesis of olefins is very demanding
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DOI: 10.1039/C9CC02603G
complexes A and B under optimal conditions, the product 3o because of (E)-olefinic structures are widely found in many
was obtained in 76% and 72% yield, respectively (Scheme 2). biologically and pharmaceutically active molecules.
Notably, the liberated hydrogen gas was detected on gas Delightfully, the Ni-catalyzed selective synthesis of E-stilbenes
chromatography and quantified.
from easily available alcohols using benzyl phenyl sulfone has
been successfully addressed (Table 2). Under the optimized
reaction conditions, the electron-donating substituents on
benzyl alcohols offered higher yield than the electron-
withdrawing substituents. Thus, p-Me, and m-OMe benzyl
alcohols gave higher E-selective products in good yields (5b in
70%, and 5c in 66% yields). In particular, functionalized
alcohols with halide (-F, and -Br) groups were well tolerated
(products 5d-5e) under optimal reaction reactions. Various
ortho-, and meta-substituted alcohols were highly tolerated
and offered the corresponding olefins with complete E-
selectivity (products 5f in 68%, 5g in 60%, 5h in 80%, 5i in 60%,
and 5j in 70% yields). Significantly, the alcohols featuring
naphthyl and di/tri-substituted groups were efficiently reacted
and gave the corresponding alkenes in good yields with
complete E-selectivity (products 5k-5p). Importantly, we were
able to extend our catalytic system for the synthesis of
symmetrical E-selective stilbenes in good yields (5q in 66%,
and 5r in 76% yield). Furthermore, substrates featuring pyridyl
and furyl, which are challenging to undergo olefination due to
their coordinating ability to the metal centre, also exhibited
good yields with excellent E-selectivity under our reaction
conditions (products 5s-5t). However, the reaction using
unactivated aliphatic alcohol (1-hexanol) didn’t yield the
expected olefin under our Ni-catalysis. A similar reactivity was
observed in the case of Ru(II)-catalyzed olefination reaction.12a
Me
O
S
O
1
MeO
MeO
MeO
MeO
MeO
MeO
OH
cat. A or B
H2
KOtBu, Toluene
110 oC, 12 h
Me
Me
3o
2o
3o'
N
N
N
Ni
N
N
Ni
N
Cl
OH2
Cl
Br
Br
OH2
O
O
O
O
A
(
)
(B)
Scheme 2. Ni-catalyzed olefination of alcohols via ADC.
After having optimized conditions in hand, the general
applicability of the present NNN-Ni(II)-catalyzed olefination of
alcohols were investigated (Table 1). Thus, a variety of benzylic
alcohols with electron-neutral, electron-deficient, and
electron-rich substituents led to the corresponding olefins in
good yields with excellent selectivity. The para-substituted
benzyl alcohols pertaining a range of functional groups, such
as ether, aryl, alkyl, fluoro, bromo, and chloro were well
tolerated and gave the corresponding styrene derivatives (3a-
3i) in good yields (up to 70% isolated yield). Gratifyingly, the
unprotected amine group such as 3-aminobenzyl alcohol (2j)
underwent the ADC reaction smoothly and gave 3-
aminostyrene as
a single product in 45% yield. The
methenylation of ortho-substituted benzyl alcohols, and
extended benzyl alcohols (1-naphthyl, and 2-naphthyl)
proceeded efficiently and yielded the corresponding olefins in
very good yields (products 3k in 72%, 3l in 70%, 3m in 65%,
and 3n in 70% isolated yields). Notably, the reaction was found
to be compatible with disubstituted alcohols (2o and 2p) and
afforded the methenylated products in excellent yields
(products 3o in 76% and 3p in 73%).
Table 2. Olefination of alcohols: Scope of alcohols and sulfone.a,b
O
R2
R2
S
OH
A
cat.
R1
H2
R1
O
KOtBu, Toluene
110 oC, 12 h
2
4
5
Me
OMe
5a
5b
5c
, 66%
, 70%
, 70%
, 51%
Table 1. Olefination of alcohols: Scope of benzyl alcoholsa,b
F
Br
Me
c
5d
5g
5e
5f
, 70%
, 68%
N
N
Ni
N
Cl Cl
H2O
Me
O
O
O
S
Me
Cl
OH
OMe
, 60%
H2
R
R
KOtBu, Toluene
110 oC, 12 h
Me
Me
R
5h
5i
, 80%
, 60%
O
3'
1
2
3
OMe
5l
, 60%
OMe
5j
5k
, 70%
, 45%
Me
tBu
MeS
MeO
O
c
c
3a
, 65% (5%)
3b
, 60%
3c
, 65% (8%)
3d
, 70%
OMe
OMe
OMe
OMe
OMe
Me
Me
Ph
Cl
tBu
F
Br
c
c
5m
5n
5q
5o
, 70%
, 85%
O
, 90%
3e
3f
3g, 68%
OMe
3h
, 55% (12%)
Me
, 65% (20%)
, 65%
, 40%
H2N
OMe
O
OMe
Me
3i
, 45%
3j
3k
, 72%
3l
, 70%
MeO
5p
5r
, 75%
, 66%
, 76%
MeO
MeO
MeO
O
O
N
Ph
c
c
3m
, 65% (11%)
3n
, 70% (7%)
3o
, 76%
3p
, 73%
5s
5t
5u
, 0%
, 72%
, 70%
aReaction conditions: 1 (0.5 mmol), alcohol (0.5 mmol), cat. A (3 mol%), KOtBu (0.55
mmol), and toluene (1 mL), 110 °C, 12 h. bIsolated yields. c-methyl substituted product
(3’) was observed by GC.
aReaction conditions: 4 (0.5 mmol), 2 (0.5 mmol), cat. A (3 mol%), KOtBu (0.55 mmol),
and toluene (1 mL), 110 °C, 12 h. bIsolated yields. c10% dehalogenated product.
2 | J. Name., 2012, 00, 1-3
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The utility of the present ADC strategy is further demonstrated experimental findings are in agreement with theVpieawrAtirtcicipleaOtniloinne
DOI: 10.1039/C9CC02603G
for the E-selective synthesis of pharmaceutically relevant of Ni-H species during the initial dehydrogenation step.
molecules. To our delight, one-step synthesis of DMU-212 (8), Importantly, treatment of (E)-(1-(phenylsulfonyl)ethene-1,2-
a drug used for breast cancer treatment has been achieved.18 diyl)dibenzene (11) in the absence of 2a led to 5a in 14% yield.
Furthermore, we have successfully synthesized a prominent However, the same reaction in the presence of 2a the product
biological activity molecule Resveratrol by two steps protocol. 5a was observed in 87% yield. These experiments showed that
The E-selective 9 was accomplished by employing 6 and 3,5- the present NNN-Ni(II) catalyst has a crucial role in the final
dimethoxybenzyl alcohol (7b) under nickel-catalyzed olefination step also. Based on experimental results, we
conditions followed by demethylation of 9 to offer the propose that the present Ni-catalysed strategy consists of a
Resveratrol (10) in 70% yield (Scheme 3).
multi-step process, and the initial step is the dehydrogenation
of benzyl alcohol 2o to the corresponding aldehyde with the
liberation of H2, where a transient Ni-H species is generated.
Subsequently, Julia-type olefination of intermediate aldehyde
with sulfone (4a) led to the expected olefin 5a.
Finally, to confirm the homogenous nature of present nickel-
catalysis, the benchmark reaction was carried out in the
presence of excess mercury (50 equiv.) and the expected
product (3o) was observed in 74% yield. Performing the
reaction in presence of radical scavenger 2,2,6,6-
tetramethylpiperidine-1-oxyl (TEMPO; 2 equiv.) didn’t affect
the yield of the product. This result indicates that the radical
reaction pathway could be ruled out. The progress of the
reaction studied with the kinetic analyses and revealed that
the olefination reaction is first order with respect to sulfone
and catalyst, and fractional order in alcohol and the base
OMe
OMe
OMe
OMe
O
MeO
S
O
6
OH
OH
cat.
A
(a)
(b)
H2
KOtBu, Toluene
110 oC, 12 h
MeO
7a
MeO
MeO
8
(65%)
OMe
OMe
OMe
OMe
MeO
O
S
A
OMe
cat.
H2
O
KOtBu, Toluene
110 oC, 12 h
9
(55%)
7b
6
BBr3, DCM,
-30 °C to r.t., 5 h
OH
OH
10
(70%)
HO
Scheme 3. Application in synthesis of DMU-212 (8), and Resveratrol (10).
To gain insight into the reaction mechanism, several control
experiments were performed (Scheme 4). Under optimal
reaction conditions, in the absence of 1 the formation of
aldehyde product and H2 gas were observed (by gas
chromatography analysis). Performing the reaction using
aldehyde, the reaction proceeded excellently and provided 5a
in 70% yield. Next, the reaction using [D3]-2o under optimal
conditions showed the deuterium incorporation at the α-
position of the styrene (3o). Similarly, the reaction of
deuterated sulfone [D2]-4 with 2o proceeded smoothly and the
deuterium incorporation at the α-position of stilbene was
observed. These results described that the reaction proceeds
via aldehyde intermediate. It was proposed that the Ni-H
species is originated from the benzylic proton of the alcohol
during the dehydrogenation reaction to benzaldehyde.[19a]
There are also reports on the generation of nickel hydride
species in presence of hydride donors such as sodium
concentration (see ESI).
H
MeO
MeO
MeO
OH std. conditions
O
(a)
H2
MeO
2o
80%
O
S
O
std. conditions
(b)
(c)
O
+
Ph
H
4a
5a
(70%)
95%
77%
D
D
D
O
MeO
MeO
MeO
MeO
OD std. conditions
S
O
1
Me
Ph
Me
[D3]-2o
[D]-3o
(70%)
D
OMe
OMe
41%
O
MeO
MeO
std. conditions
OH
S
Ph
(d)
O
D
D
[D]-5m
(70%)
2o
[D2]-4
(87%)
MeO
std. conditions
Hg (50 eq.)
O
S
MeO
MeO
OH
(e)
(f)
Me
Me
O
MeO
std. conditions
3o,
Hg (74%)
TEMPO (72%)
TEMPO (2 eq.)
1
2o
Ph
A
cat.
Ph
5a
borohydride.[19b]
In
this
regard,
performing
the
SO2Ph
KOtBu, toluene
110 oC, 12 h
2a
2a
in presence of
in absence of
= 87%
= 14%
11
dehydrogenation reaction of alcohol under NNN-Ni(II) catalysis
in the presence of a catalytic amount of NaBH4 as a hydride
donor showed the formation of aldehyde (by GC-MS). Next, an
attempt to prepare the Ni-H species of Cat. A in combination
with alcohol (2o) was invoked. However, the experimental
results evidence that the generation of Ni-H species of Cat. A
or Cat. B is extremely unstable to detect even at low
temperature (the formation of aldehyde was only observed).
To get further insights, we had chosen an electron-rich
tricyclohexyl phosphine derived complex NiBr2(PCy3)2 and the
Ni-hydride species (PCy3)2NiBrH for our studies.16c,16e
Interestingly, both the complexes yielded the desired olefin in
46% and 37% yields, respectively. Gratifyingly, performing the
catalytic dehydrogenation of alcohol (2o) using (PCy3)2NiBrH
gave the corresponding aldehyde in 23% yield. These
Scheme 4. Mechanistic investigations.
Based on preliminary experimental results,
a plausible
mechanism for the NNN-Ni(II) catalyzed direct olefination of
alcohol is shown in scheme 5. In the presence of alkoxide, the
precatalyst A undergoes displacement reaction to give the
complex C. The complex C undergoes β-hydride elimination (of
alkoxide) to lead to the corresponding aldehyde and with the
formation of Ni-H species D. Subsequently, Julia-type
olefination of intermediate aldehyde with sulfone to yield the
expected olefin. The complex F generated from complex E with
the liberation of H2. Finally, the complex F reacts with alcohol
to regenerate the catalyst A. The isolation of proposed
intermediates is under progress in our laboratory and will be
communicated in due course.
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RCH2OH
KOtBu
View Article Online
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Ni
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RN
Cl
NR
Cl
OH2
A
R =
O
N
RN
Ni
NR
XO
O
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X = OtBu, OCH2
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Scheme 5. A plausible mechanism.
In summary, an efficient nickel-catalyzed direct olefination of
benzyl alcohols with sulfones to access various terminal and
internal olefin via ADC is reported. The present protocol has
been successfully employed for the synthesis of
pharmaceutically important compounds.
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Conflicts of interest
“There are no conflicts to declare”.
Acknowledgements
This work is supported by the SERB, India (CRG/2018/002480).
EB acknowledges CSIR-NCL, Pune and IISER-Tirupati. VY and MS
acknowledge UGC, India for fellowship.
Notes and references
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