Nickel-Catalyzed Coupling of Arylzinc Halides with Thioesters

Article abstract of DOI:10.1002/chem.201801887

The Pd-catalyzed Fukuyama reaction of thioesters with organozinc reagents is a mild, functional-group-tolerant method for acylation chemistry. Its Ni-catalyzed variant might be a sustainable alternative to expensive catalytic Pd sources. We investigated the reaction of S-ethyl thioesters with aryl zinc halides with hetero- and homotopic Ni precatalysts and several ligands. The results show that both homo- and heterotopic species may contribute to catalysis. The substrate scope using an operationally homogeneous defined Ni complex was established. Acyl radicals are postulated as short-lived intermediates.

Full text of DOI:10.1002/chem.201801887

A Journal of
Accepted Article
Title: Nickel-Catalyzed Coupling of Arylzinc Halides with Thioesters
Authors: Paul H. Gehrtz, Prasad Kathe, and Ivana Fleischer
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To be cited as: Chem. Eur. J. 10.1002/chem.201801887
Link to VoR: http://dx.doi.org/10.1002/chem.201801887
Supported by

10.1002/chem.201801887
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COMMUNICATION
Nickel-Catalyzed Coupling of Arylzinc Halides with Thioesters
Paul H. Gehrtz[a], Prasad Kathe[a] and Ivana Fleischer*[a]
Abstract: The Pd-catalyzed Fukuyama reaction of thioesters with
organozinc reagents is a mild, functional group tolerant method for
acylation chemistry. Its Ni-catalyzed variant might be a sustainable
alternative to expensive catalytic Pd sources. We investigated the
reaction of S-ethyl thioesters with aryl zinc halides with hetero- and
homotopic Ni precatalysts and several ligands. The results show that
both homo- and heterotopic species may contribute to catalysis. The
substrate scope using an operationally homogeneous defined Ni
complex was established. Acyl radicals are postulated as short-lived
intermediates.
one example was shown, but the study was focused mainly on
the activation of other acyl electrophiles. In addition, the cost of
Ni(cod)2 partially offsets the price advantage of bulk Ni over Pd.
Recently, ketones were accessed by Rueping et al. from the more
inert aromatic oxoesters and alkylboranes under Ni(cod)2
catalysis.[12]
Thus, there is much potential to develop more efficient Ni-
based version of the Fukuyama coupling. We were interested if
the salt effect of Knochel-type arylzinc reagents could be
employed to increase reactivity in the Ni-catalyzed Fukuyama
reaction allowing for reduced catalyst loadings and shorter
reaction times.[13] Secondly, we wanted to address various entry
points into catalysis (molecular, nanoparticulate) (Scheme 1b).
Our investigations presented herein led to development of a
method featuring the use of a defined complex as catalyst,[14]
which improves the selectivity of the reaction (Scheme 1c).
The Fukuyama reaction (FR) allows access to polyfunctional
ketones via the cleavage of thioesters by employing mild
organozinc reagents in conjunction with Pd catalysis without
formation of the corresponding alkanol (Scheme 1a).[1] Compared
to the more sensitive acyl chlorides, simple S-alkyl thioesters are
bench- and chromatography-stable acyl transfer reagents.[2] They
are most commonly prepared by active ester methods,[3] but
carbonylative transition metal catalysis offers the possibility to
forego the need for stoichiometric activating agents.[4] The FR has
certain advantages for synthetic chemists over acylation reactions
using Grignard reagents. It has been employed in the total
synthesis of various natural compounds, for example of (+)-
haplophytine by Fukuyama and of Biotin (52 mmol scale) by Seki
and co-workers using Pd/C.[5] Modern extensions of the FR are
continuously being developed, such as the enantioconvergent
variant based on a dynamic kinetic resolution of racemic benzylic
zinc reagents by chiral catalysts.[6] Besides Pd/C and the originally
employed [PdCl2(PPh3)2], the efficiency of phosphine-free
Pd2dba3 was demonstrated.[7] However, it was shown that varying
amounts of Pd nanoparticles (NPs) may be present in this
apparently homogeneous Pd(0) precursor depending on the
supplier.[8] Other studies using Pd/C and Pd(OAc)2 led to
assumption that the Fukuyama reaction might operate both in
homogeneous and heterogeneous mode.[9]
a)
The Fukuyama reaction:
XZnR''
[Pd]
- FG tolerant
O
O
- synthetic applications
- usually proceeds at RT
- up to 10 mol% Pd loading
R
SR'
R
R''
b)
c)
The Ni-cat. Fukuyama reaction:
XZnR''
O
O
[Ni]
- Few examples in the literature
- Sustainable alternative to Pd?
R
SR'
R
R''
Ni loading?
Ph
Scope?
Mechanism?
Our Method
Cat. topicity?
Ph
Ni
P
P
- defined complex as catalyst
- air stable, easy to handle
- homogeneous nature
Cl
O
Ph
Ph
Scheme 1. a) The Fukuyama reaction. b) The respective catalytic reaction with
Ni and its associated open questions. c) Our method using a defined Ni-complex
as catalyst.
Despite the usefulness of this transformation, two major
issues emerge especially at larger scale: a) Contamination of
potentially bioactive products with metals and b) the recovery of
Pd metal. To address point b), Ni(II) precursors have been
investigated briefly by Seki as a potential substitute for the
expensive Pd catalysts in the FR, but a large excess (4 eqv.) of
the organozinc reagent was required in combination with long
reaction times (20 h).[10] Rovis has shown a more active system
for the Ni-catalyzed FR going to completion within 2 h.[11] In this
case, pyrophoric Ph2Zn in combination with the air-sensitive
Ni(cod)2 and 4-F-styrene as an additive was required and only
We began our investigation by employing thioester 1 and 1.5
eqv. LiCl-adducted phenyl zinc chloride (4) as coupling partners
and NiCl2 as catalyst (Table 1). As expected, this reaction does
not proceed in the absence of a catalyst (Table 1, Entry 4).
Ni(acac)2, described by Seki to be active in the Ni-catalyzed
Fukuyama reaction, showed good activity towards product 2
(Table 1, entry 6) comparable to the least expensive Ni source,
NiCl2 (obtained by dehydration of the hexahydrate salt). This salt
was reported to be inactive in a previous report.[10] Both catalysts
produced significant amounts of biphenyl (3), which should be
suppressed in order to facilitate the purification. While we were
pleased that the reaction proceeds with simple NiCl2, we were
curious about the actual catalytic mode since NiCl2 is insoluble in
THF. Thus, at the beginning of the reaction, the reaction mixture
is heterogeneous. Less zinc reagent, slow addition of the zinc
reagent, or lower reaction temperatures had a detrimental effect
on the obtained yields (Table 1, entries 1-3). Nickel salts other
than NiCl2 and Ni(acac)2 performed worse (see SI), and Fe(acac)3
was inactive (Table 1, entry 8). Interestingly, Fe(acac)3 was
[a]
P.H. Gehrtz, P. Kathe, Prof. Dr. I. Fleischer (corresponding author)
Institute of Organic Chemistry
Faculty of Mathematics and Natural Sciences,
Eberhard-Karls University Tübingen
Auf der Morgenstelle 18, 72076 Tübingen, Germany
Corresponding author e-mail: ivana.fleischer@uni-tuebingen.de
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201801887
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COMMUNICATION
reported to be an active catalyst in the reaction of Grignard
and noted dark particles upon aqueous acidic workup, which
separated to the organic phase. Additionally, these particles
complicated purification of the final products, leading to a black
appearance of otherwise NMR-pure products after column. This
led us to assume that the catalytically active species or a reservoir
for molecular catalysis may be of high molecular weight or
nanoparticulate, which was confirmed by successful employment
of NiB nanoparticles (10 mol%) as the catalyst (Table 1, Entry
9).[17]
reagents with S-phenyl thioesters.[15]
Table 1. Selected optimization and control experiments of coupling thioester 1
with nucleophile 4 under Ni catalysis.
PhZnCl・LiCl
(1.5 eqv., 4)
NiCl2 (5 mol%)
O
O
Ph
Ph
+
SEt
0.14 M THF
Ph
Ni
RT, 30 min
Standard conditions
2
84%
3
15%
1
97% conv.
Our conclusion from these experiments was to employ other
well-defined complexes to avoid the complicating factor of
possible heterogeneous catalysis. Therefore, we also studied the
influence of the relatively (compared to diimine-type ligands)
strong-field wide-bite angle ligand xantphos (L2) in the Fukuyama
reaction (Table 1, entry 10) in complex C1, but the result was
moderate. Jamison has prepared a series of well-defined, air-
stable organometallic NiII-phosphine precatalysts, including C2
which is easily prepared from C1. These complexes generally
display enhanced solubility in organic solvents compared to
L2NiCl2 complexes.[14] At the beginning of the reaction, C2 is
activated by a transmetalation/reductive elimination sequence to
give a molecular Ni0 species. In our case, C2 gave homogeneous
solutions in THF with the thioester present, no black particles
upon workup and generally higher product selectivity (Table 1,
entries 11 and 13). In this case a distinct ligand effect was noted
by comparison to commercially available C3 (Table 1, entry 12).
tBu
PPh2
PPh2
PPh2
Z
N
N
P
P
Fe
O
Cl
PPh2
tBu
P2 = L2 Z = Cl
C1
P2 = L2 Z = 2-tolyl C2
P2 = L3 Z = 2-tolyl C3
dtbbpy
L1
Xantphos
dppf
L3
L2
Entry
Deviation
conditions
from
standard
Conv.
[%][a]
1
Yields [%][a]
2
3[b]
1
1.2 eqv. 4 instead
Dropwise addn. of 4
0 °C, 2 h instead
No metal, no ligand
Addn. of 1 to 4
82
70
79
0
77
54
63
0
14
7
2
3
10
0
Next, the substrate scope was investigated using catalyst C2
with the aim to evaluate the steric and electronic requirements for
effective catalysis (Scheme 2). The thioesters were prepared by
Steglich’s method and typically isolated before use.[3b] Initially, the
effect of steric bulk proximal to the reactive centre on catalytic
activity was studied. Activity increases with decreasing steric
hindrance at the thioester moiety (tert. < sec. < prim.), leading to
the exemplary products 2 (gram-scale reaction), 19 and 27.
4
5
86
95
95
1
70
87
83
1
16
15
19
6
6
5 mol% Ni(acac)2 instead
+ 5 mol% dtbbpy (L1)
7
8
5 mol% Fe(acac)3 instead
10 mol% Ni-NP instead
Cyclic secondary or tertiary thioesters performed significantly
worse in catalysis (leading to product 26 and no formation of 28)
than their acyclic counterparts (leading to 19 and 27 for
comparison). The performance of the aryl substituted thioester
(leading to 29) was similar to the cyclic secondary thioester. This
effect cannot be solely explained by the thermodynamic trend of
product stability, but also by kinetic differentiation during catalysis.
By employing NiCl2/terpy mixtures as a model catalyst for weak-
field ligands, a decreased sensitivity to steric bulk was found (see
SI); meaning that the preference for primary thioesters is
characteristic for C2. Next, the functional group tolerance of the
various primary thioesters was investigated. We found that
despite the high reactivity of putative Ni0 states, electrophilic (e.g.
leading to 9, 10) and Lewis basic functional groups were generally
well-tolerated (e.g. leading to product 11). Notably, also thioesters
containing double bond reacted to corresponding products 15 and
17 in good to excellent yields and the reaction was also applied
to convert dehydrocholic acid thioester to 14. In case of 17,
isomerization to the thermodynamically more stable alkene
isomer occurred most likely by alkene coordination to zerovalent,
coordinatively unsaturated (Xant)Ni. Furthermore, steric
hindrance on b-carbon atom did not hamper the production of
ketone 18.
9
94
61
89
76
61
81
12
11
9
10
11
5 mol% Ni(xant)Cl2 (C1) instead
5
mol% Ni(xant)(oTol)Cl (C2)
instead
12
13
5
mol% Ni(dppf)(oTol)Cl (C3)
72
97
59
91
10
5
instead
As entry 11, 1.5 h, 1.86 eqv. 4
Reagents and conditions for standard run: 1 (63 mg, 333 µmol, 1 eqv.),
PhZnCl•LiCl (1.5 eqv. based on titre [typically 0.25 M], in THF), anhydrous NiCl2
(2.2 mg, 16.6 µmol, 5 mol%), dry THF (300 µL), RT, 30 min. [a] Determined by
quantitative GC-FID analysis. [b] Based on 0.5*nPhZnCl. Acac: Acetylacetonate.
dppf: 1,1’-Diphenylphosphinoferrocene. dtbbpy: 4,4’-Di-tert-butyl-2,2’-dipyridyl.
NP: Nanoparticles. oTol: ortho-Tolyl, Xant: Xantphos
Except dtbbpy (L1, Table 1, Entry 7), addition of other diimine
ligands lowered the yields (see SI). Such insensitivity to ligand
variation can be interpreted as a hint that a heterotopic catalyst is
active.[16] Interestingly, preformed Ni-diimine complexes
performed significantly worse than salt/ligand mixtures (see SI),
further hinting at catalysis by a heterotopic Ni catalyst under this
regime. Furthermore, we observed the formation of dark solutions
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10.1002/chem.201801887
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COMMUNICATION
ArZnCl•LiCl (1.86 eqv.)
R'SH, DIC,
cat. DMAP
O
O
sec.
C2 (5 mol%)
19 R=C6H5: 51%
20 R=4-OMe-C6H4: 61%
21 R=4-F-C6H4: 47%
22 R=4-SEt-C6H4: 47%[c]
23 R=3-OMe-C6H4: 68%
24 R=2-OMe-C6H4: 74%
25 R=thiophen-2-yl: 64%
RCO2H
DCM, 0 °C to RT
R
SR'
R
Ar
THF, 1.5 h, RT
Et
Bu
O
R': ethyl, heptyl
[yield]
O
prim.
O
EtO2C
R
O
O
TsN
26: 23%
O
O
R'
R
5 R'=H, R=H: 81%
6 R'=3-F, R=H: 42%
2: 88% (1 g scale)
10: 64%[b]
O
tert.
9: 53%
7 R'=H, R=OMe: 88%
8 R'=OMe, R=H: 72%
O
27: 27%
O
O
O
O
O
HN
N
28: 0%
11: 95%
O
13: 67%[b]
12: 70%[a]
O
O
Ph
O
H
aryl
15: 52%
O
O
Ph
O
Ph
Ph
F
O
F
F F F F
F
F
F
Ph
2Np
H
H
O
29: 24%[d]
O
F
F F F F F F
16: 48%
F
O
alkene
migration
1:1 (E):(Z)
17: 95%
18: 88%
14: 67%
Scheme 2. Scope of the Ni-catalyzed Fukuyama reaction of S-alkyl thioesters with aryl zinc halides. Yields given are isolated unless stated otherwise. Reagents
and conditions for standard run: Thioester (333 µmol, 1 eqv.), ArZnCl•LiCl (1.86 eqv. based on titre [typically 0.25 M], in THF), C2 (12.7 mg, 16.6 µmol, 5 mol%),
dry THF (300 µL), RT, 1.5 h. [a]: 2.86 eqv. of 4 were employed. [b]: The thioester could not be isolated in pure form. Hence, the yield given is over two steps. [c]
From 4-Cl-C6H4ZnCl under standard conditions. [d] NMR yield.
Next, the effect of organozinc nucleophile on the overall
activity was studied using product 19 as a convenient reference
point (Scheme 2). While coupling with unhindered, electron rich
nucleophiles proceeded well (products 20 to 25), a clear effect of
steric bulk on catalytic activity was observed again. No reactions
took place with more bulky arylzinc reagents (ferrocenyl-, tolyl-, 1-
naphthyl zinc halides). Transmetalation is being invoked as the
slowest step in the thioester-to-ketone transformation.[10] Thus,
the performance of several electronically differentiated aryl zinc
halides was studied. Here, relatively electron-poor nucleophiles
gave no appreciable product formation (e.g. 3-CF3-, 4-cyano-
phenyl zinc chlorides). The possible negative influence of
heteroatoms via coordination was ruled out, since highly
coordinating heterocyclic zinc reagents gave the same result.
While the electron-rich thiophen-2-yl zinc chloride furnished 25 in
64% yield, the electron-deficient 6-methylpyrid-2-yl zinc chloride
provided no product. This is a first experimental indication that
transmetalation might be the rate-determining step in the Ni-
catalyzed FR. Couplings with less reactive alkyl-, alkenyl- or
alkynyl zinc halides did not proceed under our optimized
conditions. Interestingly, keto-thioether 22 was formed with para-
chlorophenyl zinc chloride, most likely from the liberated zinc
thiolate under Ni catalysis. Stambuli noted a similar effect in the
Pd-catalyzed FR, albeit with bromoarenes.[18] Schönebeck also
found wide-bite angle diphosphines to be active in the Ni-
catalyzed trifluoromethylthiolation of chloroarenes.[19]
complex might lead to fragmentation resulting in a thiolate and a
neutral acyl radical. A ketyl radical anion equivalent has been
postulated by Skrydstrup in a SmI2-mediated C-C bond-forming
reaction of thioesters with electron-deficient alkenes.[20]
Interestingly, a Ni(I)-Me terpyridine complex has been reported to
have a reducing power similar to SmI2.[21] If an acyl radical is
formed, a decarbonylative pathway can be envisioned. The
decomposition of benzylic acyl radicals compared to primary ones
is thermodynamically favoured and fast.[22] Thus, we employed
benzylic thioester 30 under a) our reaction conditions using C2
and b) under conditions that have been optimized for the
decarboxylative coupling of redox active esters (RAE) under Ni-
catalysis (Scheme 3a).[23] Under RAE conditions, an appreciable
amount of decarbonylated product 32 is formed whereas under
our conditions, only small amount of 32 was formed together with
the expected 31. Our initial conclusion from these experiments
was that C2 operates by a 2-valence electron redox classical
cross-coupling mechanism which is distinct of the mechanism
under RAE conditions. However, a catalytic reaction of the model
substrate in the presence of TEMPO (75 mol% relative to the
thioester) and C2 or NiCl2 showed only minimal product formation,
implying radical pathways operative with both catalysts. The
adduct from these experiments could not be detected. However,
in the presence of ethyl acrylate (2 eqv. relative to the thioester),
the putative acyl radical was trapped, as shown by the detection
of product 33 (see SI for details) of
a formal hybrid
Fukuyama-Giese reaction either with C2 or NiCl2 (Scheme 3b),
which however proceeded sluggishly and also produced 2.
Next, we investigated the possible radical character of the
reaction. Single electron reduction of thioesters by a low-valent Ni
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10.1002/chem.201801887
Chemistry - A European Journal
COMMUNICATION
O
SEt
PhZnCl•LiCl (3 eqv.)
a)
O
Ph
In conclusion, we have shown that an operationally
homogeneous precatalyst C2 is an efficient and functional group
tolerant catalyst for the Ni-catalyzed Fukuyama reaction. Both
homogeneous precatalysts such as C2 and Ni nanoparticles can
be entry points into catalysis. Thus, a picture similar to the Pd-
catalyzed FR emerges where hetero- and homotopic catalytic
cycles may coexist.[26] We provide the first experimental proof that
the Ni-catalyzed FR proceeds via acyl radical intermediates
(and/or synthons thereof), which were previously accessible from
thioesters only by neutral photo- and thermolysis as well as
reductive electrolysis and in a catalytic manner by photoredox
catalysis.[27] We wish to harness these catalytically generated
reactive intermediates in related Ni-catalyzed transformations to
gain further proof of this concept.
Ph
[Ni]
+
Ph
Ph
Ph
RT, 4 h
30
31
32
"Fukuyama"
48% conv.
17%
3%
5 mol% C2,
THF
"RAE"
100% conv.
b)
32%
20%
20 mol% NiCl2(H2O)6,
40 mol% di-tBu-bpy,
THF:DMF 3:2
(2 eqv.)
CO2Et
17-20%
conv.
1
PhZnCl•LiCl (1.86 eqv.),
O
Ph
CO2Et
NiCl2 or C2 (5 mol%)
2
n-Pent
THF, RT, 30 min
10%
33
[Ni]
GC/MS(EI)
O
O
n-Pent
c)
CO2Et
not quantified
Acknowledgements
n-Pent
CO2Et
[Ni]
We are thankful to M. Sindlinger and V. Geiger for technical
assistance. Financial support from Fonds der Chemischen
Industrie (Liebig fellowship IF), the DAAD (PhD fellowship PK)
and the University of Tübingen (Institutional Strategy of the
University of Tübingen: Deutsche Forschungsgemeinschaft ZUK
63) is gratefully acknowledged.
O
Ar-(oTol) (5 mol%)
0
R''
SR'
L2Ni(Ar)(oTol)
L2Ni
O
+ ArZnCl - ZnCl2
prim.
<
sec.
<
tert.
<
benzylic
C2
R''
34
I
R''COR
L2Ni(SR')
kDCO
Keywords: Nickel catalysis • Acyl radicals • Fukuyama coupling
L2Ni(R''CO)(R)
R''CO
or R''
• Thioester • Ketones
II
L2Ni(R''CO)(SR')
R'SZnX
[1]
a) H. Tokuyama, S. Yokoshima, T. Yamashita, T. Fukuyama,
Tetrahedron Lett. 1998, 39, 3189-3192; b) H. Tokuyama, S. Yokoshima,
T. Yamashita, L. Shao-Cheng, L. Leping, T. Fukuyama, J. Braz. Chem.
Soc. 1998, 9, 381-387.
RZnX
Scheme 3. a) Testing for decarbonylative pathways by generation of benzylic
acyl radicals from benzylic thioesters. b) Trapping acyl radicals by a hybrid
Fukuyama-Giese reaction. c) Proposed mechanism.
[2]
[3]
V. Hirschbeck, P. H. Gehrtz, I. Fleischer, Chem. Eur. J., early view DOI:
10.1002/chem.201705025.
a) J. N. deGruyter, L. R. Malins, L. Wimmer, K. J. Clay, J. Lopez-Ogalla,
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In our proposed mechanism, activation of C2 by ArZnCl leads
to a zerovalent Ni species (Scheme 3c),[14] which undergoes a
single electron transfer-type stepwise oxidative addition into the
thioester. A short-lived acyl radical 34, which can undergo capture
by radical acceptors or decomposition by decarbonylation, is
formed. The acyl or alkyl radical recombines with the Ni(I) species,
providing a Ni(II) oxidative addition complex (Scheme 3c). This is
followed by the classical steps of transmetalation and reductive
elimination to close the cycle. Thus, an apparent classical 2-
valence electron cross-coupling mechanism involves SET steps
as proven by capture or decarbonylation of acyl radical
intermediates. Other mechanisms such as a Ni(I/II/III) cycle may
be possible as well.[24] The difference in the propensity to
decarbonylate 30 (to give 32) between C2 and other Ni/diimine
ligand combinations can be accounted to a lower tendency of
Xantphos-ligated Ni acyl species to undergo migratory deinsertion
of CO (non-radical on-metal decarbonylation). Stoichiometric
experiments by the groups of Love and Riordan on the oxidative
addition of defined, bidentate-phosphine ligated Ni0 complexes
into thioesters have shown that decarbonylation of the resulting
acylnickel(II) thiolates occurs readily to give alkylnickel(II)
thiolates.[25]
[4]
[5]
a) M. Seki, M. Hatsuda, Y. Mori, S.-i. Yoshida, S.-i. Yamada, T. Shimizu,
Chem. Eur. J. 2004, 10, 6102-6110; b) H. Ueda, H. Satoh, K. Matsumoto,
K. Sugimoto, T. Fukuyama, H. Tokuyama, Angew. Chem. Int. Ed. 2009,
48, 7600-7603.
[6]
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4590.
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2011, 47, 12679-12681.
[8]
[9]
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Y. Mori, M. Seki, Adv. Synth. Catal. 2007, 349, 2027-2038.
[10] T. Shimizu, M. Seki, Tetrahedron Lett. 2002, 43, 1039-1042.
[11] Y. Zhang, T. Rovis, J. Am. Chem. Soc. 2004, 126, 15964-15965.
[12] A. Chatupheeraphat, H.-H. Liao, W. Srimontree, L. Guo, Y. Minenkov, A.
Poater, L. Cavallo, M. Rueping, J. Am. Chem. Soc. 2018.
[13] a) F. M. Piller, P. Appukkuttan, A. Gavryushin, M. Helm, P. Knochel,
Angew. Chem. Int. Ed. 2008, 47, 6802-6806; b) F. M. Piller, A. Metzger,
M. A. Schade, B. A. Haag, A. Gavryushin, P. Knochel, Chem. Eur. J.
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[14] E. A. Standley, S. J. Smith, P. Müller, T. F. Jamison, Organometallics
2014, 33, 2012-2018.
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[15] C. Cardellicchio, V. Fiandanese, G. Marchese, L. Ronzini, Tetrahedron
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[23] J. Cornella, J. T. Edwards, T. Qin, S. Kawamura, J. Wang, C.-M. Pan, R.
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10.1002/chem.201801887
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Paul H. Gehrtz, Prasad Kathe and Ivana
Fleischer*
Ph
O
Ph
Ni
P
P
O
O
Cl
+
ArZnCl
Page No. – Page No.
R
Ar
R
SR
Ph
The Ni-Catalyzed Coupling of Arylzinc
Halides with Thioesters
Ph
Herein, we report coupling of thioesters with arylzinc reagents using a defined
bidentate phosphine ligand-based nickel complex as catalyst. A discussion on
mechanism using different homo- and heterotopic Nickel precursors is included.
This article is protected by copyright. All rights reserved.