A phenalenyl-based nickel catalyst for the hydroboration of olefins under ambient conditions

Article abstract of DOI:10.1039/c9dt00468h

In this report, nickel-catalyzed hydroboration of vinylarenes and aliphatic alkenes is investigated. The non-innocent phenalenyl ligand moiety in the nickel complex Ni(PLY)₂(THF)₂ (1) was utilized as an electron reservoir for the sel

Full text of DOI:10.1039/c9dt00468h

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Phenalenyl-based Nickel Catalyst for Hydroboration of Olefins
under Ambient Conditions
Received 00th January 20xx,
Accepted 00th January 20xx
Gonela Vijaykumar, a Mrinal Bhuniaa and Swadhin K. Mandal*a
In this report, nickel-catalyzed hydroboration of vinylarenes and aliphatic alkenes are investigated. The non-innocent
phenalenyl ligand moiety in the nickel complex Ni(PLY)2(THF)2 (1) was utilized as an electron reservoir for the selective
hydroboration reaction in the presence of pinacolborane under ambient conditions. The mechanistic investigations
revealed that alkene hydroboration reaction takes place through a single electron transfer (SET) from the phenalenyl
ligand backbone leading to the cleavage of B–H bond.
DOI: 10.1039/x0xx00000x
www.rsc.org/
phenalenyl moiety is the presence of an energetically accessible
empty non bonding molecular orbital (NBMO)16 in their cationic
state, which can be generated on coordination with a metal ion.17
Introduction
Transition metal complexes bearing non-innocent ligands have
attracted a great deal of interest.1 These non-innocent ligands are
able to act as redox reservoir and can play crucial role in new
catalyst design.2-3 Such a catalytic process can avoid the situation of
metals indulging to an unfavourable oxidation states and thus
enables conceptually new catalytic mechanism. In this way, redox
non-innocent ligands allow the first-row transition metals to mimic
the catalytic properties of noble metals.4-6 The first successful
application of homogeneous iron catalysts bearing non-innocent
ligands for ethylene polymerization was reported by Brookhart and
co-workers in 19987 in which a bis(imino)pyridine ligand played an
important role in the catalytic cycle by utilizing its electron storage
capacity in combination with an iron based pre-catalyst. Later on,
Chirik and co-workers developed intramolecular cyclization of
dienes and enynes via [2 + 2] cycloaddition that benefited from
the unique electronic structure of the iron complexes imposed by
the presence of a non-innocent ligand.8-9 The bis(imino)pyridine
iron complexes were also successfully applied to olefin
hydrogenation and hydrosilylation catalysis.10-12 Chirik and co-
workers also reported the addition of pinacolborane to terminal-,
1,1- and 1,2-disubstituted alkenes with the same catalyst.13
Recently, Ritter et al. reported the iminopyridine-derived iron
complexes as catalysts for the regioselective 1,4-hydroboration of
substituted 1,3-dienes.14
As a result, acceptance or transfer of electron(s) takes place
through this NBMO unlike other non-innocent ligands which
normally use their anti-bonding orbital. In fact, the use of the
NBMO of phenalenyl can be traced back to their exceptional
material properties as organic conductors,18 organic magnets,19
electronic switch,20 soft battery,21 molecular memory device22 and
cathode material.23 Recently, its application in catalytic activation of
various substrates is gaining increasing attention.24-29 Very recently,
we observed that redox participation of the PLY ligand results in
development of an excellent nickel based catalyst to perform
regioselective hydrosilylation of a wide variety of olefins.30 This
study encourages us to explore further applications in designing
base metal catalysis assisted by phenalenyl backbone. Herein we
report regioselective nickel-catalyzed hydroboration of vinylarenes
and aliphatic alkenes by using a nickel-phenalenyl Ni(PLY)2(THF)2 (1)
complex in the presence of pinacolborane at room temperature.
It may be worth to note that, hydroboration of alkenes is the most
convenient method for the synthesis of alkylboron compounds.31-33
Alkylboranes are versatile intermediates in synthesis of alcohols,
amines, and carboxylic acids34-38 and widely employed for
carbon−carbon bond formation in the pharmaceutical industry.
Most catalytic alkene hydroborations classically required precious
metals, such as Rh39-42 and Ir.43-44 However, the low abundance,
economic constrains, and environmental issues have encouraged
the investigation of earth-abundant inexpensive base–metals as
alternatives.45 While Fe,46-48 Co,49-50 Cu51-52 catalyzed hydroboration
of terminal alkenes with pinacolborane (HBpin) has been studied,
but the hydroboration of terminal alkenes with nickel catalyst is
less-established.53 Recently, Ye and co-workers reported a base-free
hydroboration of alkenes with bis(pinacolato)diboron (B2pin2) using
Ni(cod)2/P(t-Bu)3 system at 75 C.54 Very recently, Shimada and co-
workers developed a Ni-catalyzed hydroboration of olefins with
In this context, herein, we present an odd alternant hydrocarbon
phenalenyl (PLY) ligand as the redox non-innocent ligand.15 The
major advantage of this odd alternant hydrocarbon based on
a.Department of Chemical Sciences, Indian Institute of Science Education and
Research Kolkata, Mohanpur 741246, India.
Email: swadhin.mandal@iiserkol.ac.in
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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B2pin2 and water.55 Herein we report hydroboration reaction catalyst alone (1 mol %) in absence of K gave no product (Table 1,
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DOI: 10.1039/C9DT00468H
catalysed by a Ni catalyst exhibiting both high activity and entry 4). The reaction using NiCl2 or Ni(acac)2(MeOH)2 in the
regioselectivity for allyl and vinylarenes at room temperature presence of K also gave only trace amount of product (Table 1,
(Scheme 1).
entries 5 and 6). Furthermore, to establish that the PLY-based nickel
complex is essential for the reaction, we performed catalysis with
only PLY ligand and potassium, which did not result in any
hydroborylated product (Table 1, entry 7). No hydroboration
product was observed without catalyst 1 (Table 1, entry 8). All these
results on control experiments clearly established the role of
phenalenyl ligand in the catalyst 1.
Table 2 Hydroboration of vinylarenes with HBpin catalyzed by 1.a
Yield (%)b
Scheme 1 Summary of present work.
Entry
Alkene
Product
Results and discussion
Previous studies from our laboratory have demonstrated that the
nickel phenalenyl complex 1 is a highly active catalyst for the
hydrosilylation of aliphatic alkenes.30 Catalytic hydrosilylation
proceeded with high selectivity and addition of Ph2SiH2 to terminal
alkenes furnished exclusively terminally silylated products. These
results inspired us the exploration of the phenalenyl nickel catalyst
1 for the hydroboration reaction.
Table 1 Optimization of the catalyst and solvent for the nickel
catalyzed hydroboration of styrenea
Entry Catalyst
Solvent
THF
Yield (%)b
98
1
1
2
1
DMSO
C6H6
THF
62
<5
NR
<5
3
4c
5
1
1
NiCl2
THF
6
Ni(acac)2(MeOH)2
PLY(O,O)
-
THF
THF
THF
<5
NR
NR
7
8 d
a
Reaction conditions: HBpin (0.5 mmol) and styrene (0.5 mmol) in
THF (1 mL) at 25 oC. b The reported yields are 1H NMR spectroscopic
yields. c Without potassium. d Without catalyst 1. NR = No reaction,
acac = acteylacetanato.
[a]
Reaction conditions: vinylarene (0.5 mmol), HBPin (1 equiv.),
[b]
Ni(PLY)2(THF)2 (1 mol%), K (3 mol%), THF (1 mL), RT. Yields are
reported after purification by column chromatography.
The initial screening was investigated with the styrene and HBpin in
the presence of catalyst 1 and potassium as a reductant in THF at
With the optimized conditions in hand, we examined hydroboration
of various functionalized vinylarenes under optimum reaction
conditions using complex 1 (1 mol %) and K (3 mol %) in THF for 1h
at room temperature and pinacolborane as the hydroborating
reagent (Table 2). In all cases, the regioselectivity was excellent,
exclusively Markovnikov alkylboronate product was observed, that
room temperature for 1h (Table 1). To our great delight,
a
quantitative conversion of Markovnikov hydroboration product was
observed (Table 1, entry 1). When the reaction was performed in
DMSO as solvent, lesser conversion was obtained (62% Table 1,
entry 2), and in benzene, it afforded very low conversion (<5%;
Table 1, entry 3). As a control, the hydroboration reaction using
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has been proven challenging for iron and rhodium catalysts.56-57 intermediate to synthesize nonsteroidal anti-inflammatory drug
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58
DOI: 10.1039/C9DT00468H
Vinylarenes with an electrondonating substituent at para-position Naproxen™ ((R)-2-(6-methoxynaphthalen-2-yl)propanoic acid).
on the phenyl group gave the alkylboronate product in 96% and The reaction of 4-vinylbiphenyl (Table 2, entry 9) resulted the
94% isolated yield (Table 2, entries 1-2), respectively. The halogen- product in excellent yield (95%). It may be noted that the preceding
substituted vinylarenes were compatible with the reaction result using a nickel catalyst required 60 °C for 18h while the
conditions, and the desired product was obtained without current method works under ambient conditions.53
compromising with the yield and regioselectivity; the reaction of 4-
Next, we examined hydroboration of aliphatic olefins (unactivated
alkenes) considering various functionalized alkenes with
pinacolborane using 1 as the catalyst (Table 3). When the
hydroboration of aliphatic alkenes was performed with the
optimized conditions, the anti-Markovnikov hydroboration products
were obtained (olefin isomerized product was also detected as a
side product by 1H NMR spectroscopy). This divergent
regioselectivity of vinylarenes and aliphatic alkenes was also
previously observed by using a dinuclear pincer cobalt complex.59
fluorostyrene (Table 2, entry 3) afforded the product in 95%
isolated yield. The meta-substituted vinylarenes (Table 2, entries 4 -
5) also reacted with high regioselectivity like para-substituted
vinylarenes. The electron donating group at both meta positions of
benzene ring did not diminish the yield and regioselectivity. The
reaction of 3,5-dimethoxystyrene (Table 2, entry 6) also resulted in
the desired product in 72% yield. The reaction of 2-
vinylnaphthalene (Table 2, entry 7) resulted in excellent yield (96%).
Table 3 Hydroboration of various aliphatic alkenes with HBpin The catalyst 1 successfully hydroborated the allyl benzene and
catalyzed by 1.a
substrate bearing electron donating substituent such as methyl or
methoxy on the phenyl group at para-position yielding the
corresponding alkylboronates with 78%, 77% or 76% yield (Table 3,
entries 1-3). 4-chloro allylbenzene was tolerated under the reaction
conditions giving linear boronic ester in good yield with no cleavage
of the aryl-halide bond (Table 3, entry 4). The olefin bearing
trifluoromethyl group at para position can also be hydroborated
using pinacolborane with satisfactory yield 69% (Table 3, entry 5).
Good yields were observed for allyl benzene bearing electron-
donating groups at meta position (Table 3, entries 6-7). The
reaction of 2-allylnaphthalene (Table 3, entry 8) resulted in 68%
yield. Non-functional linear terminal alkenes such as 1-hexene and
1-octene were selectively hydroborated and the corresponding
alkylboronate esters were isolated with 72-74% yields (Table 3,
entries 9 -10).
Entry
Alkene
Product
Yield (%)b
Based on our earlier report,30 we anticipated that the olefin
hydroboration may follow a radical pathway. To check this assertion
further, a radical scavenger TEMPO was added (two runs with 0.25
and 0.5 equiv.) to the reaction mixture which drastically reduced
the yield of the hydroborylated product to 58% and 24%,
respectively and no hydroborylated product was observed with 1
equiv. of TEMPO (Scheme 2)
Scheme 2 Reaction inhibition in the presence of TEMPO.
[a]
Based on these preliminary data and our understanding on
mechanism of nickel-catalyzed alkene hydrosilylation processes,29
we propose the mechanism of nickel-catalyzed alkene
hydroborations involving a radical pathway. The two electron
reduction of 1 with potassium metal gives a biradical nickel complex
2. A single electron transfer (SET) occurs from 2 to HBpin to
Reaction conditions: alkene (0.5 mmol), HBPin (1 equiv.),
[b]
Ni(PLY)2(THF)2 (1 mol%), K (3 mol%), THF (1 mL), RT. Yields are
reported after purification by column chromatography.
In the case of 6-methoxy-2-vinylnaphthalene (Table 2, entry 8), the
hydroborylated product was obtained in 92% yield, which is an
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generate a boryl radical which subsequently adds to the olefin phenalenyl ligand centered radicals upon reduction of 1 plays a key
View Article Online
DOI: 10.1039/C9DT00468H
resulting in the formation of a borylated alkyl radical (I). The role during this hydroboration reaction.
generation of boryl radical during this hydroboration has been
unambiguously authenticated by trapping the TEMPO-adduct of the
putative radical 4 and characterized by mass spectrometry (Scheme
Experimental
3).
General methods and instrumentation. All manipulations were
performed under a dry and oxygen free atmosphere (argon) using
standard Schlenk line techniques or inside a glovebox maintained
below 0.1 ppm of O2 and H2O levels, utilizing oven-dried (130 oC)
glassware after evacuation while hot prior to use. All solvents were
distilled from Na/benzophenone prior to use. All other chemicals
were purchased from Sigma–Aldrich and used as received. The
HRMS data were obtained using a Finnigan MAT 8230 instrument.
Analytical TLC was performed on a Merck 60 F254 silica gel plate
(0.25 mm thickness). 1H, 13C and 11B NMR spectra were recorded on
a JEOL ECS 400 MHz spectrometer and on a Bruker Avance III 500
MHz spectrometer. All chemical shifts were reported in ppm using
tetra methyl silane as a reference. Chemical shifts (δ) downfield
from the reference standard were assigned positive values.
Ni(PLY)2(THF)2 (1) was prepared according to the literature
procedure.30
Scheme 3 Reaction of trapping boryl radical in the presence of
TEMPO.
Upon SET, 2 transforms into an anionic monoradical species
comprising nickel hydride, 3 (Scheme 4). Multiple attempts to
capture such Ni-H species failed and we do not fully discard the
possibility of a hydride transfer from B-H bond to phenalenyl
backbone. The boryl radical subsequently adds to the olefin
resulting in the formation of a borylated alkyl radical (I). Upon
subsequent hydrogen atom transfer (HAT), the borylated alkyl
radical transforms into the hydroborylated product and regenerates
the active catalyst 2.
General procedure for the hydroboration of vinylarenes with
catalyst 1. To a stirred solution of Ni(PLY)2(THF)2 (3 mg. 0.005
mmol) and K (0.6 mg, 0.015 mmol) in THF (1 mL), the pinacolborane
(0.5 mmol) and vinylarene (0.5 mmol) were added at room
temperature. The solution was stirred at room temperature for 1 h,
and the progress of the reaction was monitored by 1H NMR
spectroscopy using 1,3,5-trimethoxybenzene as internal standard.
The 1H NMR spectroscopic analysis of the resulting solution
revealed the formation of product. The solution was concentrated
under vacuum, and the residue was purified by column
chromatography using hexane as an eluent. The final product was
characterized by 1H, 13C and 11B NMR spectroscopy.
General procedure for the hydroboration of aliphatic alkenes
with catalyst 1. To a stirred solution of Ni(PLY)2(THF)2 (3 mg. 0.005
mmol) and K (0.6 mg, 0.015 mmol) in THF (1 mL), the pinacolborane
(0.5 mmol) and aliphatic alkene (0.5 mmol) were added at room
temperature. The solution was stirred at room temperature for 1 h,
and the progress of the reaction was monitored by 1H NMR
spectroscopy using 1,3,5-trimethoxybenzene as internal standard.
The 1H NMR spectroscopic analysis of the resulting solution
revealed the formation of product. The solution was concentrated
under vacuum, and the residue was purified by column
chromatography using hexane as an eluent. The final product was
characterized by 1H, 13C and 11B NMR spectroscopy.
Scheme 4 A plausible mechanism for catalytic hydroboration of
olefin by 1 through PLY based radical initiation.
Conclusions
In conclusion, we have shown that [Ni(PLY)2(THF)2] complex can be
an effective catalyst for hydroboration of alkenes using
pinacolborane at room temperature. Notably, the catalyst is equally
active for the hydroboration of vinylarenes and aliphatic alkenes
with high selectivity of boronate esters. The generation of
Procedure for reaction inhibition in presence of radical
scavenger TEMPO. Ni(PLY)2(THF)2 (0.005 mmol) and K (0.015 mmol)
in THF (1 mL) were taken and HBpin (0.5 mmol), styrene (0.5 mmol)
and TEMPO (0.25/0.5/1 mmol) were added to it at room
temperature. The reaction was stirred at room temperature for 1 h
and then quenched by exposing the reaction mixture to air. The
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21 Y. Morita, S. Nishida, T. Murata, M. Moriguchi, A. Ueda, M.
solution was concentrated under vacuum and the product was
purified by column chromatography using hexane as an eluent.
View Article Online
Satoh, K. Arifuku, K. Sato and T. Takui, Nat. Mater., 2011, 10
,
DOI: 10.1039/C9DT00468H
947−951.
22 K. V. Raman, A. M. Kamerbeek, A. Mukherjee, N. Atodiresei,
T. K. Sen, P. Lazic, V. Caciuc, R. Michel, D. Stalke, S. K.
Mandal, S. Blugel, M. Munzenberg and J. S. Moodera,
Nature, 2013, 493, 509-513.
Procedure for trapping of pinacolboryl radical (4). Ni(PLY)2(THF)2
(0.5 mmol) and K (1.5 mmol) in THF (1 mL) were taken and HBpin
(0.5 mmol) and TEMPO (0.5 mmol) were added to it at room
temperature. The reaction was stirred at room temperature for 2 h
and then the reaction mixture was subjected to HRMS
characterization in acetonitrile solvent.
23 A. Pariyar, G. Vijaykumar, M. Bhunia, S. K. Dey, S. K. Singh, S.
Kurungot and S. K. Mandal, J. Am. Chem. Soc., 2015, 137
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25 J. Ahmed, S. P, G. Vijaykumar, A. Jose, M. Raj and S. K.
Conflicts of interest
There are no conflicts to declare
Mandal, Chem. Sci., 2017, 8, 7798–7806.
26 A. Banik, R. Paira, B. K. Shaw, G. Vijaykumar and S. K.
Mandal, J. Org. Chem., 2018, 83, 3236-3244.
27 J. Ahmed, S. Chakraborty, A. Jose, S. P, and S. K. Mandal, J.
Am. Chem. Soc., 2018, 140, 8330−8339.
28 S. Chakraborty, J. Ahmed, B. K. Shaw, A. Jose and S. K.
Mandal, Chem. Eur. J., 2018, 24, 17651-17655.
29 P. K. Vardhanapu, J. Ahmed, A. Jose, B. K. Shaw, T. K. Sen, A.
Acknowledgements
We thank SERB (DST), India (Grant No EMR/2017/000772) for
financial support. GV thanks UGC for a research fellowship and
Invictus Oncology Pvt Ltd, Delhi, for a research scientist position.
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DOI: 10.1039/C9DT00468H
Catalytic hydroboration of alkenes are reported using the redox active phenalenyl ligand assisted
nickel complex Ni(PLY)2(THF)2 in the presence of pinacolborane under ambient conditions.