Nickel-Catalyzed Stereodivergent Synthesis of E- and Z-Alkenes by Hydrogenation of Alkynes

Article abstract of DOI:10.1002/cssc.201900784

A convenient protocol for stereodivergent hydrogenation of alkynes to E- and Z-alkenes by using nickel catalysts was developed. Simple Ni(NO₃)₂?6 H₂O as a catalyst precursor formed active nanoparticles, which were effective for the semihydrogenation of several alkynes with high selectivity for the Z-alkene (Z/E>99:1). Upon addition of specific multidentate ligands (triphos, tetraphos), the resulting molecular catalysts were highly selective for the E-alkene products (E/Z>99:1). Mechanistic studies revealed that the Z-alkene-selective catalyst was heterogeneous whereas the E-alkene-selective catalyst was homogeneous. In the latter case, the alkyne was first hydrogenated to a Z-alkene, which was subsequently isomerized to the E-alkene. This proposal was supported by density functional theory calculations. This synthetic methodology was shown to be generally applicable in >40 examples and scalable to multigram-scale experiments.

Full text of DOI:10.1002/cssc.201900784

Accepted Article
Title: Nickel-catalyzed Stereodivergent Synthesis of E- and Z-Alkenes
by Hydrogenation of Alkynes
Authors: Matthias Beller, Kathiravan Murugesan, Charles Beromeo
Bheeter, Pim R. Linnebank, Anke Spannenberg, Joost N. H.
Reek, and Rajenahally V. Jagadeesh
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10.1002/cssc.201900784
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Nickel-catalyzed Stereodivergent Synthesis of E- and Z-Alkenes
by Hydrogenation of Alkynes
Kathiravan Murugesan‡[a], Charles Beromeo Bheeter‡[b], Pim R. Linnebank[b], Anke Spannenberg[a],
Joost N. H. Reek*[b], Rajenahally V. Jagadeesh*[a], and Matthias Beller*[a]
Abstract: A convenient protocol for stereodivergent hydrogenation
formation of Z-alkenes. In case of hydrogenations, over-
reduction to form the corresponding alkane is a common
pathway that lowers the chemoselectivity.
of alkynes to E-alkenes and Z-alkenes using nickel catalysts is
.
reported. Simple Ni(NO3)2 6H2O as a catalyst precursor forms active
nanoparticles, which are effective for the semihydrogenation of
several alkynes with high selectivity for the Z-alkene (Z:E>99:1).
Upon addition of specific multidentate ligands (triphos, tetraphos),
the resulting molecular catalysts are highly selective for the E-alkene
products (E:Z>99:1). Mechanistic studies reveal that the Z-alkene
selective catalyst is heterogeneous and the E-alkene selective
catalyst is homogeneous in nature. In the latter case, the alkyne first
gets hydrogenated to a Z-alkene, which is subsequently isomerized
to the E-alkene. This proposal is supported by density functional
theory (DFT) calculations. This synthetic methodology is shown to
be generally applicable in >40 examples and scalable to multi-gram
experiments.
Interestingly, a limited number of homogeneous systems are
known to transform alkynes to either E - or Z-olefins, which often
resulted in the mixtures of isomers.[6g-h],[7h-i],[11g],[16a-c],[11d],[17] In this
regard, recently Liu et al.,[12d] reported a ligand controlled
protocol for the stereodivergent synthesis of both Z- and E-
alkenes using cobalt catalysts applying NH3-BH3 as a reducing
agent. Earlier on, Grela and co-workers reported a similar
strategy using different Ru-olefin complexes to semihydrogenate
alkynes using NaH and HCOOH as reductants.[7b] Further,
Moran et al. have developed Ni-based catalysts using
stoichiometric amounts of zinc and formic acid as reductant.[11d]
All of these semi-reduction methods make use of stoichiometric
amounts of reducing agents, which generates waste. In addition
to these protocols, Ru[7g], Pd[6f] and Ir [10b] catalysts have been
reported for the synthesis of Z- and E- alkenes using transfer
hydrogenations. Regarding the reductant, the use of molecular
hydrogen offers significant advantages because it is inexpensive
and allows for 100% atom-efficient transformations. However, so
far only Rh-[8] and borane-based[16c] catalysts have been used
for stereodivergent synthesis of both E- and Z-alkenes.
Nickel catalysts are commonly used for hydrogenations of a
wide range of unsaturated compounds in the chemical industry
and academic laboratories.[18a-f] As a result, we anticipated
defined nickel complexes should be active in alkyne
hydrogenation, too. However, preventing over-reduction to the
corresponding alkanes could be challenging.[19a-d] Herein, we
describe the first protocols for stereodivergent Ni-catalyzed
semihydrogenation of alkynes. Using convenient nickel
precursors in the presence or absence of phosphine ligands
both E- and Z- alkenes can be formed with excellent selectivity.
Introduction
C-C double bonds represent one of the most valuable functional
groups in organic chemistry.[1a-e] Hence, the development of
protocols to obtain Z- or E-alkenes selectively continues to be
important because the absolute stereochemistry of the molecule
[2a-c]
is crucial for its physical properties.[1a-d],
As an example
stilbenes were used as part of molecular motors, showing
significant differences in their photochemistry depending on the
E- and Z-configuration.[3a-d] The most common synthetic pathway
to obtain Z-alkenes is by semihydrogenation of alkynes using
Lindlar’s catalyst, which is based on expensive palladium doped
with toxic lead salts.[4] E-alkene synthesis from alkynes is more
difficult and the most commonly practiced method is Birch type
reduction[5] using Na/NH3 as a stoichiometric reducing reagent.
Both approaches suffer from low functional-group tolerance.
Because of these drawbacks, there is a continuing interest in
more general alternative catalyst systems.[1c,d] The majority of
investigations focused on noble metals such as Pd,[6a-h] Ru,[7a-h]
Results and Discussion
Rh,[8a-b] Au,[9a-b] and Ir[10a-b]. In addition, non-noble metal catalysts
Synthesis of E- alkenes
[15a-b]
based on Ni,[11a-h] Co,[12a-d] Fe,[13a-f] Cu,[14a-c] Mn
have also
At the start of our investigations we were interested in the
influence of phosphine ligands on the (chemo) selectivity of Ni-
catalyzed alkyne hydrogenations. As a benchmark system, the
reaction of diphenylacetylene with molecular hydrogen was
used. To identify suitable Ni-catalysts, we tested several
commercially available phosphines including privileged mono-,
bi-, tri-, and tetradentate ligands in the presence of nickel nitrate.
Surprisingly, in all cases the reaction gave stilbenes
selectively and only trace amounts of reduction to the
corresponding alkane was observed. Interestingly, as shown in
Table 1 simple monodentate arylphosphines (L1-L3) provided
Z-alkenes with 99:1 selectivity (Table 1, entries 1-3). Applying
bisphosphine ligands gave mixtures of E- and Z-products
(Table 1, entries 4-7). Gratifyingly, the application of some tri-
and tetradentate phosphines (L8-L10) led predominantly to E-
stilbene.
been reported. Most of these catalysts promote the selective
[a]
[b]
K. Murugesan, Dr. A. Spannenberg, Dr. R. V. Jagadeesh*
Prof. Dr. M. Beller*
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-
Einstein-Str. 29a, 18059 Rostock, Germany
*E-mail: Jagadeesh.Rajenahally@catalysis.de ;
Matthias.Beller@catalysis.de
Dr. C. B. Bheeter, P. R. Linnebank, Prof. Dr. J. N. H. Reek*
Van ‘t Hoff Institute for Molecular Sciences, University of
Amsterdam, Science Park 904, 1098 XH, Amsterdam, The
Netherlands
*E-mail: J.N.H.Reek@uva.nl
‡Authors are equally contributed
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cssc.201900784
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selectivity for the E-alkene product (E:Z selectivity >99%, Table
1, entries 9-10).
Table 1. Ligand effects in the semihydrogenation of diphenyl acetylene to
obtain stilbenes
These results are in line with the nickel-triphos system using
over-stoichiometric amounts of reducing agents (Zn+HCOOH)
reported by Moran and co-workers.[11d] To investigate this E-
selective hydrogenation in more detail, the influence of the
.
solvent was investigated with the Ni(NO3)2 6H2O/ triphos (L9)
system. When the reaction was performed in acetonitrile or
isopropyl alcohol very high (>99%) selectivity for the E-alkene
was obtained, whereas the reactions in other solvents resulted
in mixtures of the E- and the Z-product (Table S2).
Entr
y
Metal precursor
Ligan
d
Conv
.
(%)
Yield
2 & 3
(%)
Select
-ivity
(E: Z)
Yield
4
(%)
Scheme 1. Ligand controlled Ni-catalyzed synthesis of E-alkenes
.
1a
Ni(NO3)2 6H2O
L1
L2
L3
L4
L5
L6
L7
L8
L9
L10
98
95
88
94
96
78
97
96
98
98
98
1:99
2
1
2
2
1
1
1
-
.
2 a
3 a
4 a
5 a
6 a
7 a
8 a
9 a
10a
Ni(NO3)2 6H2O
90
1:99
.
Ni(NO3)2 6H2O
97
1: 99
5:95
.
Ni(NO3)2 6H2O
>99
80
.
Ni(NO3)2 6H2O
10:90
40:60
50:50
65:35
>99:1
>99:1
.
Ni(NO3)2 6H2O
>99
>99
>99
>99
>99
.
Ni(NO3)2 6H2O
.
Ni(NO3)2 6H2O
.
Ni(NO3)2 6H2O
-
.
Ni(NO3)2 6H2O
-
.
Reaction conditions: a0.5 mmol alkyne, 4 mol% Ni(NO3)2 6H2O, 8 mol% bis(2-
.
Reaction conditions: a0.5 mmol diphenylacetylene, 4 mol% Ni(NO3)2 6H2O, 8
mol% ligand, 30 bar H2, 2 mL acetonitrile, 120°C, 15 h, yields were determined
by GC using n-hexadecane as standard. E:Z isomeric ratios were determined
by GC-MS and NMR.
diphenylphosphinoethyl)phenylphosphine (triphos), 30 bar H2,
2
mL
acetonitrile, 120 °C, 15 h, isolated yields. bGC yields using n-hexadecane as
standard. Values in parenthesis refer to E: Z isomeric ratio determined by GC-
MS and NMR
More
specifically,
in
the
presence
of
bis(2-
.
Having a convenient system (Ni(NO3)2 6H2O/bis(2-diphenyl-
diphenylphosphinoethyl)phenyl-phosphine (linear triphos)(L9)
and tris[2(diphenylphosphino) ethyl]phosphine (L10) the nickel
catalyst gave full conversion of diphenylacetylene and excellent
phosphinoethyl) phenylphosphine L9) in hand, we explored the
substrate scope for this in situ generated catalyst. Alkynes
containing electron-donating or -withdrawing groups were
selectively converted to obtain E-selective olefins in up to 98%
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10.1002/cssc.201900784
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yield (Scheme 1, products 5-22). Functional groups such as
hydroxy, heterocycles, halide, silyl, and boronic ester are well
tolerated (Scheme 1, products 8-11, and 13-18).
substrates were performed at 1-10 g scales (Scheme 2). In all
these cases similar yields and selectivities were obtained.
Noteworthy, the catalyst loading was decreased in gram scale
reactions; at 1 g scale 3 mol% of nickel catalyst was used (6
mol % of ligand) and at 10 g scale only 2 mol% of nickel was
applied.
Scheme 2. Practical utility of Ni-triphos system for synthesis of E-alkenes
Synthesis of Z- Alkenes
Next, we turned our interest to the selective synthesis of Z-
.
stilbene using Ni(NO3)2 6H2O in the presence of monodentate
arylphosphines. Interestingly, similar reactivity and selectivity
(93% of Z-stilbene with >99% selectivity) was observed in the
absence of phosphines (Table 2, entry 1). Thus, we evaluated
different nickel (II) salts for the benchmark hydrogenation. As
shown in Table 2, NiCl2, NiBr2 and Ni(OAc)2 did not show any
activity (Table 2, entries 2-4).
Reaction conditions: a1 g alkyne, 3 mol% Ni(NO3)2.6H2O, 6 mol% triphos, 30
bar H2, 12 mL acetonitrile, 120 °C, 15 h, isolated yields, E:Z ratio was detected
by GC-MS and NMR. bGC yields using n-hexadecane as standard. c10 g
alkyne, 2 mol% Ni(NO3)2.6H2O, 4 mol% triphos, 30 bar H2, 120 mL acetonitrile,
120 °C, 15 h, GC yields. Values in parenthesis refer to E : Z isomeric ratio
determined by GC-MS and NMR.
Scheme 3. Substrate scope for the synthesis of Z-alkenes
Table 2. Hydrogenation of diphenylacetylene using different metal salts
Yield of
alkene
(%)
Selec
-tivity
(Z: E)
Yield of
alkane
(%)
Conv.
(%)
Entry
Metal precursor
.
1 a
2a
Ni(NO3)2 6H2O
99
-
93
-
99:1
6
-
.
NiBr2 XH2O
-
.
3 a
4 a
5 a
6 a
7 a
8 a
9 a
10b
11c
12d
NiCl2 DME
-
-
-
-
Ni(OAc)2.4H2O
Ni(OTf)2
-
-
-
-
65
50
-
59
45
-
99:1
99:1
-
5
4
-
Ni(acac)2
.
Co(NO3)2 6H2O
.
Fe(NO3)3 9H2O
-
-
-
-
.
Mn(NO3)2 4H2O
-
-
-
-
.
Ni(NO3)2 6H2O
99
99
70
93
93
65
99:1
99:1
99:1
6
6
5
.
Ni(NO3)2 6H2O
.
Ni(NO3)2 6H2O
Reaction conditions: a0.5 mmol of diphenylacetylene, 10 mol% of metal salt,
30 bar H2, 2 mL acetonitrile, 120°C, 15 h, yields were determined by GC using
n-hexadecane standard. b 6 mol% catalyst loading. c 4 mol% catalyst loading d
2 mol% catalyst loading. Z:E isomeric ratio were determined by GC-MS and
NMR
.
Reaction conditions: a0.5 mmol alkyne, 4 mol% Ni(NO3)2 6H2O, 30 bar H2, 2
Even substrates with substituents that are reduced easily, such
as nitrile and ketone, were converted with excellent
chemoselectivity leaving the functional groups untouched
(Scheme 1, products 12, 18, and 22). To demonstrate the
scalability of the Ni-triphos system, semi-hydrogenation of 4
mL acetonitrile, 120 °C, 15 h, isolated yields. bGC yields using n-hexadecane
as standard. with 8 mol% Ni(NO3)2 6H2O. Values in parenthesis refer to Z:E
isomeric ratio determined by GC-MS and NMR.
c
.
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.
After having found that Ni(NO3)2 6H2O is a convenient and
inexpensive pre-catalyst for Z-selective semihydrogenation of
alkynes, we evaluated its general applicability for the different
aromatic and aliphatic alkynes (Scheme 3). Gratifyingly, all the
investigated substrates were converted into the corresponding
Z-alkenes in up to 96% yields with 99% selectivity (>99% Z:E).
In contrast, the Ni/triphos (L9) catalyst system showed no
change in catalytic activity in the presence of Hg, still producing
the E-alkene with similar high selectivity, demonstrating that
under these conditions the active species is homogeneous in
nature. To understand this active catalyst in more detail, we
synthesized
a
Ni-triphos complex in quantitative yield
This simple Ni-salt also exhibits excellent chemoselectivity. Thus, (Supporting Information-S6). Crystals suitable for single crystal
the generated active catalyst is compatible with the halogen
substituents (Br, Cl, F) and no significant dehalogenation is
observed (Scheme 3, products 26-29), despite the fact that
nickel complexes are generally known to be dehalogenation
catalysts.[20a-f] In addition, alkyne groups are selectively reduced
in the presence of other sensitive groups such as silyl, boronic
esters, ketone and ester (Scheme 3, products 30 – 33 and 40).
Further, heterocyclic and aliphatic alkynes were also semi-
hydrogenated to respective Z- alkenes with excellent yield and
stereoselectivity (Scheme 3, products 34-35 and 39).
X-ray diffraction were grown after recrystallization with ethanol.
Analysis of the solid state structure shows that the complex is
pentacoordinated and all the three phosphorous atoms are
coordinated to the nickel centre (Figure 1). The 31P{1H} NMR
spectrum of this complex in CDCl3 solution (Figure S4) shows a
doublet at δP = 48 ppm and a triplet at δP = 110 ppm, in line with
a tridentate coordination to nickel in solution.
After these successful semihydrogenations of internal alkynes,
we evaluated the semi- hydrogenation of terminal alkynes
(Scheme 4). For these substrates the selectivity issue is more
challenging as terminal alkenes are easier to hydrogenate
compared to the internal ones. Nevertheless, all the terminal
alkynes studied, were converted to the corresponding alkenes
with good selectivity (Scheme 4, products 44 to 50) (entries 45
and 50 have 15% and 17% overhydrogenation product
respectively).
Figure 1. Molecular structure of Complex A obtained by X-ray analysis.
Displacement ellipsoids are drawn at the 30% probability level. Hydrogen
atoms are omitted for clarity.
.
Scheme 4. Selective hydrogenation of terminal alkynes by Ni(NO3)2 6H2O
To investigate if the Ni complex A is active in isomerization,
we added Z-stilbene to Ni complex A (6 mol %) at 120°C under
30 bar of H2. In this experiment, Z-stilbene is completely
isomerized to E-stilbene within 15 h (Scheme 5, entries 1-2).
Remarkably, not even traces of alkane are observed under
these conditions.
Scheme 5. Isomerization of Z- to E-stilbene
.
Reaction conditions: a0.5 mmol alkyne, 3 mol% Ni(NO3)2 6H2O, 30 bar H2, 2
mL acetonitrile, 120 °C, 15 h, isolated yields along with alkene:alkane ratio.
bGC yields using n-hexadecane as standard.
Entry
Substrate H2
Selectivity
(Z:E)
Yield of
3
Mechanistic Studies:
To determine if the catalyst is
(mmol)
(bar)
homogeneous or heterogeneous in nature, we performed
mercury tests[12c-d] for both the Z- and E-alkene selective catalyst
systems. The ligand-free Ni(NO3)2 6H2O catalyst system showed
1
0.5
30
30
0
0:100
0:100
80:20
100:0
>99
>99
20
.
2
5
no conversion in the presence of a drop of Hg under otherwise
identical conditions, showing that the active catalyst is
heterogeneous in nature. This is in line with the work of Bai et
al.[11e] who reported the formation of nickel nanoparticles from
nickel salts during the reduction of alkynes to Z-alkenes using
NaBH4. In general, semihydrogenation of alkynes gives Z-olefins
due to syn-addition of adsorbed hydrogen on the surface of
heterogeneous catalyst.[4]
3
0.5
0.5
4b
30
0
Reaction conditions: a0.5 mmol Z-stilbene, 6 mol% complex A, 30 bar H2, 2 mL
acetonitrile, 120 °C, 15 h, GC yields using n-hexadecane as standard. bsame
as a but without catalyst.
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Surprisingly, the same experiment without H2 gave 20% of E-
stilbene and without catalyst isomerization was not observed
(Scheme 5, entries 3-4).
detected (Scheme 6). All these observations are line with a
mechanism in which the alkyne is first converted to the Z-alkene
which is subsequently isomerized to the E-alkene by
homogeneous nickel complex.
a
Scheme 6. Hydrogenation of diphenylacetylene/Z-stilbene mixture using
complex A
Reaction conditions: a0.03 mmol alkyne and 3 mmol of alkene, complex A 6
.
mol% or 4 mol% Ni(NO3)2 6H2O, 8 mol% triphos , 30 bar H2, 2 mL acetonitrile,
120 °C, 15 h, isolated yields. bGC yields using n-hexadecane as standard.
Interestingly, cobalt catalysts which have been used also for
E-selective alkyne semihydrogenations showed similar
isomerization behavior.[12d] In another control experiment a
mixture of diphenyl acetylene and Z-stilbene (1:100 ratio) was
hydrogenated to mimic reaction conditions in which most of the
alkyne has been converted but no isomerization has taken place
yet.
Figure 3. DFT calculations for hydrogenation of diphenylacetylene to Z-
stilbene. 1 set at 0,0 kcal mol-1. All energies presented are in kcal mol-1
Figure 4. DFT calculations for isomerization of Z-stilbene to E-stilbene.
Intermediate 6 was set at 0,0 kcal mol-1. All energies presented are in kcal
mol-1
Hence, we propose the following mechanism for the formation of
E-alkenes, which consists of two cycles that both start with a
Ni(II)monohydride species (Figure 2). Initially, the Ni-hydride
species inserts into the alkyne and after subsequent
hydrogenolysis the Z-alkene is formed. In the second cycle, the
molecular Ni-H complex inserts into the formed Z-alkene leading
to a nickel alkyl species. A similar insertion was reported for
alkene hydrogenation using nickel(II) phosphine based
systems.[18b] Contrary to such hydrogenations, the triphos-ligated
complex undergoes bond rotation and ß-hydride elimination to
yield the E-alkene.
Figure 2. Proposed mechanism for the E-selective nickel-catalyzed
hydrogenation of alkynes.
Under standard experimental conditions using complex A 100%
of E-stilbene was formed and no over hydrogenated product was
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In order to validate the proposed mechanism, DFT
in high yields with excellent chemo- and stereoselectivity. The Z-
alkenes are selectively formed when simple Ni(NO3)2 was used
as a catalyst precursor. The presence of triphos as tridentate
ligand is needed to yield the corresponding E-alkenes (>99:1
selectivity). Mechanistic studies showed that the Ni(NO3)2
system is heterogeneous in nature, whereas the E-selective Ni-
calculations were conducted (see Supporting Information for
details, S10) [21a-b]. All energy values are given in kcal mol-1. A
tricoordinated Ni(II)-Hydride is used as the common intermediate
for both cycles.
triphos system operates as
a
homogeneous catalyst.
Furthermore, it was shown that the latter catalyst initially
produces the Z-alkene, which subsequently isomerizes to the E-
alkene in a separate catalytic cycle. Notably, both nickel
nanoparticles and the molecular-defined Ni-triphos catalyst
tolerate a broad scope of internal and terminal alkynes bearing
different substituent and functional groups. Both these catalyst
systems are compatible with benchtop set up and can be
applied to multi gram scale reactions.
Experimental Section
Experimental details and spectra can be found in the Supporting
Information. CCDC 1869414 contains the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data
Centre.
Figure 5. Comparison of the alkene hydrogenation step and ß-hydride
elimination step towards the E-stilbene product. Energies presented relative to
intermediate 6 set at 0,0 kcal mol-1. All energies presented are in kcal mol-1
Acknowledgements
Also for the calculations we used the benchmark substrate
diphenyl acetylene. Insertion of the nickel monohydride into the
alkyne moiety (II), has a low energy barrier, leading to
intermediate (III). Coordination of hydrogen to the nickel moiety
(IV) is slightly uphill, and after the hydrogenolysis step (V), the Z-
alkene is formed and the nickel hydride species (VI) is
regenerated. No transition state was found that directly forms
the Z-alkene from hydrogenolysis, as this would involve rotation
around a double bond. For the isomerization cycle, the Z-
stilbene coordinates to the nickel hydride, which subsequently
inserts into the double bond (VII) to form intermediate (VIII). The
alkyl species is able to rotate freely around its axis and via a β-
hydride elimination transition state (IX) the E-alkene (X) is
formed. The barriers of isomerization were low and therefore
explain the high chemoselectivity obtained for the E-alkene
using this system. Additionally, we computed hydrogen
coordination to the nickel alkyl specie (XI) and subsequent
hydrogenolysis (XII) towards the alkane product (XIII) (Figure 5).
The barrier for hydrogenation is almost 6 kcal/mol higher in
energy compared to the β-hydride elimination leading to the E-
product, in line with the high chemoselectivity as the alkane
product is not formed in significant amounts.
We gratefully acknowledge the European Research Council (EU
projects 670986-NoNaCat and 339 786-NAT_CAT), the state of
Mecklenburg-Vorpommern, the University of Amsterdam for the
financial and general support. We thank the analytical staff of
the Leibniz-Institute for Catalysis, Rostock for their excellent
service.
Keywords: Nickel catalysis. alkyne semihydrogenation.
Stereoselectivity. molecular hydrogen.
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In conclusion, we present the first nickel-based catalysts for
stereodivergent semi-hydrogenation of alkynes with molecular
hydrogen. Protocols for the preparation of both E- and Z-alkenes
are reported, forming these products in an atom-efficient manner
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FULL PAPER
Kathiravan
Murugesan,
Charles
Beromeo Bheeter, Pim R. Linnebank,
Anke Spannenberg , Joost N. H. Reek*,
Rajenahally
V.
Jagadeesh*,
and
Matthias Beller*
Page No. – Page No.
Nickel-catalyzed Stereodivergent
Synthesis of E- and Z-Alkenes by
Hydrogenation of Alkynes
Text for Table of Contents
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