Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates

Article abstract of DOI:10.1002/chem.201904545

The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl₂–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.

Full text of DOI:10.1002/chem.201904545

A Journal of
Accepted Article
Title: Generation of Organozinc Reagents by Nickel-Diazadiene-
Complex Catalyzed Zinc Insertion into Aryl Sulfonates
Authors: Philippe Klein, Vivien Denise Lechner, Tanja Schimmel, and
Lukas Hintermann
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Generation of Organozinc Reagents by Nickel-Diazadiene-
Complex Catalyzed Zinc Insertion into Aryl Sulfonates
Philippe Klein,[a] Vivien Denise Lechner,[a] Tanja Schimmel,[a,b] and Lukas Hintermann*[a]
Abstract: The generation of arylzinc reagents (ArZnX) by direct
insertion of zinc into the C–X bond of ArX electrophiles has typically
been restricted to iodides and bromides. The insertions of zinc dust
into the C–O bonds of various aryl sulfonates (tosylates, mesylates,
triflates, sulfamates), or into the C–X bonds of other moderate elec-
trophiles (X = Cl, SMe) are catalyzed by a simple NiCl2–1,4-diaza-
diene catalyst system, where 1,4-diazadiene (DAD) stands for
diacetyl diimines, phenanthroline, bipyridine and related ligands.
Catalytic zincation in DMF or NMP solution at room temperature now
provides arylzinc sulfonates, which undergo typical catalytic cross-
coupling or electrophilic substitution reactions.
Iodolysis of the reaction mixture will transform any arylzinc
2a present to iodide 3a, recovered next to naphthalene (4a) and
homo-coupled 1,1'-binaphthyl (5a)[16] (Scheme 1).[17] Initial semi-
quantitative experiments substantiated this approach and poin-
ted, among various metal-ligand-combinations, to Ni(II)–DAD
(DAD = 1,4-diaza-1,3-diene) combinations as promising catalyst
systems (Tables S1–S5).[18] We have now reinitiated those
studies by means of a refined experimental design, and the
reaction conditions soon channelled towards those in Table 1.
Table 1. Screening of reaction conditions for catalytic zincation of 1a.[a]
1. Zn (4.0 eq.), DBE (0.2 eq.)
DMF, 60 °C, 20 min
I2
The insertion of zinc or magnesium metal (M) into the car-
bon-halogen bond (C–X) of RX affords valuable organometallic
reagents (RMX) for use in C–C- and other bond-forming reacti-
ons.[1,2] Such methods, connected with Grignard (Mg)[3] and
Frankland (Zn),[4] are widely utilized and show distinct scope and
limitation profiles. The ease of metal insertion into RX decreases
in the order I > Br > Cl for X, with alkyl > aryl/vinyl for R, and with
Mg > Zn for M. While magnesiation of ArCl demands specific
conditions and fails with certain substrates,[5] zincation of ArCl
typically fails[6] and is sluggish with unactivated ArBr.[7] Such limi-
tations can be overcome by catalysis, as shown by Bogdanović
et al for magnesiation of ArCl with iron catalysts,[8] or by
Gosmini[9] and Yoshikai[10] et al for zincation of ArBr and ArCl
under cobalt catalysis. However, metal insertion into non-halo-
genated electrophiles is less common[11,12] and not synthetically
viable for simple aryl sulfonates as obtained from phenols.[13–15]
2. NiCl2(dme)–L1 (5+10 mol%)
(4.0 eq.)
r.t., 30 min
1-NapOTs
1-NapI
1-NapZnOTs
3. Addition of 1a
r.t., 20 h
0 °C,
10 min
1a
2a
3a
Entry
Deviation from standard conditions
none
Yield[b] (%)
1
2
3
4
5
96
84
91
85
86
I2 (0.5) replacing DBE in activation
I2 (0.5) for DBE, solvent NMP
I2 (0.5) for DBE, solvent THF, 50 °C
I2 (0.5) for DBE, 10 mol% [Ni], solvent THF
I2 (0.5) for DBE, Mg (1.5) + ZnCl2 (2.0) for Zn, 10
mol% [Ni], solvent THF
6
83
To examine the feasibility of catalytic metalation of aryl
sulfonates,[13] 1-naphthyl tosylate (1a) was stirred with zinc dust
and NaI in the presence of various transition metal complexes
and ligands in hot tetrahydrofuran (THF) solution (Scheme 1).
[a] Reaction conditions: 1a (1 mmol), solvent (3 mL). Activation with DBE as
indicated above; activation with I2 (0.5 eq.) involved stirring at r.t. until
decoloration was reached. [b] Spectral yield of 3a by qNMR. DBE = 1,2-dibro-
moethane; NMP = N-methyl-2-pyrrolidone; DMF = N,N-dimethylformamide.
OTs
TsOZn
R
+ side
products:
a) Zn, NaI
b) [M], L
Combining the precursors NiCl2(dme) or NiCl2(diglyme) with
ligand IPr-MeDAD (L1)[19] and zinc dust in DMF solution provides
a medium that transforms aryl tosylate 1a into organozinc reag-
ent NapZnOTs (2a) at ambient temperature (entry 1). Zinc was
activated by iodine or dibromoethane. The presence of iodide is
facultative (entry 1 vs 2–6), precluding a reaction pathway via
catalytic iodination[12a] (1a®3a) and zinc insertion.[20] The
reaction is feasible in THF at 50 °C, or at room temperature with
higher catalyst loading (entries 4, 5). Amidic solvents DMF or N-
methyl-pyrrolidone (NMP; entry 3) are nevertheless preferred, as
they facilitate high conversion at ambient temperature and
suppress homocoupling to 5a. Metalation with magnesium in the
presence of ZnCl2 was also possible (entry 6).[21]
I2
4a (R = H)
5a (R = 1-Nap)
6a (R = OH)
solvent
1a
2a
3a (R = I)
Scheme 1. Reaction design to screen for catalytic zincation of aryl sulfonates.
[a]
[b]
M.Sc. P. Klein, M.Sc. V. D. Lechner, StRin T. Schimmel, Prof. Dr. L.
Hintermann
Department Chemie und Zentralinstitut für Katalyseforschung
Technische Universität München
Lichtenbergstr. 4, 85748 Garching b. München, Germany
E-mail: lukas.hintermann@tum.de
Currently at JSB Gymnasium, 91575 Windsbach, Germany
Suitable ligands were found among open-chain DADs (L1–
L4)[19] or related Schiff bases (L5, L6), whose simple syntheses
and amenability to structural variation render them more
versatile for optimization than the similarly successful
phenanthroline-type ligands (L7–L9; Figure 1, Table S9).[22]
Supporting information for this article is given via a link at the end of
the document.
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Notably, L2 and more so L7 profit from iodine activation of
zinc powder, which is not required with L1 (Figure 1).[23] The
promising catalyst incorporating L7 fully converted 1a at the
3 mol% level, but was not the first choice for subsequent
experiments in view of the iodide activation requirement.
N
N
N
N
N
N
H
H
R
R
97% (5)
13% (5)
26% (3)a
<1% (5)
L4 2% (5)
L4 1% (3)a
L1 (R = Me)
L2 (R = H)
L2 (R = H)
L3 (R = Et)
L5 19% (5)a
The substrate scope of catalytic zincation was further
explored by applying the simple NiCl2(dme)–L1 catalyst system
to a range of aryl tosylates, including functionalized ones (Table
2). The efficiency of metalation was determined through
iodolysis of the reaction mixture, with subsequent qNMR
analysis of aryl iodide 3, and the result was confirmed by
isolation of the latter in near identical yield (Table 2).
R
R
N
N
N
N
N
N
N
N
Me
L7 (R = H)
L7 (R = H)
19% (3)b
87% (3)a,b
L6 83% (5)
L8 (R = Me) 84% (3)a
L9 95% (5)
Figure 1. Ligand variation in the nickel-catalytic zincation of 1a by the standard
procedure (Table 1). The spectral yield of 3a after iodolysis and catalyst
a
loading (mol%, in brackets) are indicated. Zinc was activated with I2 (0.5
equiv.). b 1:1 ratio of [Ni]:L used; else, it was 1:2.
Table 2. Substrate scope of the nickel-diazadiene-complex catalyzed zincation of aryl tosylates with follow-up iodolysis.[a]
a) Zn (4.0 eq.), DBE (0.2 eq.)
OTs
I
b) NiCl2(dme)–L1 (1:2)
I2 (4.0 eq.)
0 °C, 10 min
Iodolysis
ZnOTs
R
R
R
c) 1, DMF; r.t., 20 h
Metalation
1
2
3
Entry
1
Substrate
OTs
[Ni] (mol%)
Yield of 3 (%)[b]
Entry
Substrate
[Ni] (mol%)
10
Yield of 3 (%)[b]
Me
96[c] (96)
11
77 (77)
Me
5
Me OTs
OTs
OTs
2
3
5
5
88[d] (92)
98 (99)
10
5
0
12
13
tBu
tBu
OTs
83 (88)
MeO
OTs
14[e]
15
5
96 (99)
96 (96)
OTs
4
5
5
5
(21)
Et2N
OTs
CO2Me
OTs
85 (88)
10
OTs
OTs
OTs
Me
6
7
5
5
95 (96)
85 (90)
16
17
10
5
75 (78)
86 (85)
MeO2C
CN
Me
OTs
OTs
OMe
N
OTs
OTs
8
9
5
90 (93)
76 (80)
18
19
10
5
56 (54)
Me
OTs
OTs
10
77[f] (77)
tBu
Cl
OTs
OTs
10
10
80 (85)
20[g]
15
88 (89)
iPr
TsO
[a] Reaction conditions: Zn (4.0 equiv.) and DBE (0.2 equiv.) activated for 20 min at 60 °C in DMF (3 L/mol); NiCl2(dme) and L1 ([Ni]:L1 = 1:2) added at r.t. and
stirred for 30 min; ArOTs added and mixture stirred for 20 h. [b] ArZnOTs was quantified as ArI after iodolysis (I2, 0 °C, 10 min); isolated yields of
chromatographically purified material; numbers in brackets are spectroscopic yields by quantitative 1H-NMR against internal standard. [c] ArI/ArH = 98:2. [d]
ArI/ArH = 95:5. [e] 1.2 equiv. of I2 used for quenching with short (1 min) stirring at 0 °C. [f] IC6H4Cl/C6H4I2/PhI 91:6:3. [g] NMP was used as solvent.
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Like 1a, the regioisomeric 2-naphthyl- (entry 2) and ortho-
biphenyl- (entry 3) derived sulfonates show excellent zincation
yields. The low yield of the p-biphenyl derivative is due to the
low solubility of both starting material and the zinc reagent,
which stopped the conversion (entry 4). Core-alkylated aryl
sulfonates were efficiently metalated (entries 5–9), although a
larger group like isopropyl next to the reaction center diminishes
the reaction efficiency (entries 10, 11), and tert-butyl blocks it
entirely (entry 12). Electron-rich substrates (entries 13, 14) were
well tolerated, as were acceptor substrates of the nitrile and
ester type (entries 15–17), whose functional groups remained
untouched. The potentially coordinating quinolinyl sulfonate
reacted moderately well (entry 18). With 4-chlorophenyl tosylate,
the catalyst prefers C–OTs over C–Cl activation, and a trace of
para-diiodobenzene stems from double metalation (entry 19).
Twofold zincation was pursued and obtained with naphthalene-
1,5-ditosylate (entry 19).
activated 1- and 2-methylthionaphthyl ethers were also zincated
by the Ni–DAD catalyst,[28] pointing to new reaction opportunities
for accessing organometallic reagents from less activated
electrophiles.[29]
Table 3. Reactions of ArZnOTs with electrophiles.[a]
1. Zn (4.0 eq.), DBE (0.2 eq.)
DMF, 60 °C, 20 min
2. NiCl2(dme)–L1 (5+10 mol%)
r.t., 30 min
E+
1
ArZnOTs
Ar
E
(cat.)
3. Addition of 1
DMF, r.t., 20 h
2
3
Entry
1
ArOTs
E+ (equiv.)
Conditions
Product
Yield[b]
0 °C®r.t.
45 min.
91[c]
(92)
Although the organozinc reagents were most conveniently
quantified after iodolysis, we wished to support the generation of
ArZnOTs (2) reagent by its direct observation in solution. Hence,
a catalytic metalation of 1a was performed in (D7)-DMF, and the
solution scrutinized with 2D NMR methods. The presence of zinc
D
1a
D2O (xs)
Br
0
min.
°C, 10
96
(>99)
2
4
5
1b
1b
1b
NBS (4.0)
AllBr (4.0)
13CH3I (2.0)
1
insertion product 2a was revealed by complete H and 13C NMR
signal sets, including a quaternary signal at dC 156.3 (C–Zn)
(Table S10). Minor amounts of naphthalene and ligand L1 were
observed in the reaction mixture,[24] and the former rose in
intensity after addition of a little water to the sample, with those
of 2a disappearing.
[Pd] (3)[d]
0 °C ®r.t.,
92[e]
(93)
2 d
13CH3
[Pd] (3)[d]
r.t., 4 h
94[f]
(90)
Since counter-ions X affect the reactivity of arylzinc reagents
ArZnX,[25] evaluation of the synthetic utility of the new arylzinc
sulfonates beyond iodolysis was vital. 1-Naphthyl- (1a) and 2-bi-
phenyl tosylate (1b) were zincated as usual (Table 1), and the
reagents exposed to electrophiles (Table 3). Quenching of 1a
with D2O gave (1-D)-naphthalene (entry 1). Halogenation of 1b
with NBS returned ortho-bromobiphenyl near quantitatively
(entry 2). Cross-coupling of organozincs 2a/b was realized with
Buchwald's Pd–S-Phos catalyst system:[26] allylation with allyl
bromide (entry 4), methylation with (13C)-methyl iodide (entry 5),
and Negishi coupling with aryl halides (entries 6 and 7) proceed
at ambient temperature in >90% yield. The incompatibility of
DMF with acid chlorides initially prevented acylations of 1a/b,
CO2Me
[Pd] (2)[d]
IC6H4CO2Me
(1.0) [g]
95
(>99)
6
1a
r.t.,
1 h,
DMF
CN
[Pd] (2)[d]
BrC6H4CN
(1.0) [g]
94
(>99)
7
8
1a
1b
r.t.,
1 h,
DMF
however,
a
Fukuyama-type acylation[27] of
a
thioester
electrophile provided the ketone cleanly (entry 8).
O
PhCH2COSP
[Pd] (5)[d]
Ph
Our work had focussed on catalytic zinc insertion into aryl
tosylates which are among the most readily available derivatives
of phenols. We were also keen to examine the scope of Ni–DAD
catalysts towards other electrophiles. A cursory evaluation of
naphthyl electrophiles bearing various leaving groups is shown
in Table 4.
71
(74)
h
r.t.,
5 h,
(1.0)[g]
DMF
[a] Reaction size: ArOTs (1; 2 mmol), DMF (6 mL). [b] Isolated yields of
chromatographically purified material; numbers in brackets are qNMR yields.
[c] 95% D-incorporation at C-1. [d] Pd(OAc)2–S-Phos 1:2 (mol% loading given
in brackets). [e] ArAll–ArH 95:5. [f] Ar13CH3–ArH 87:13, ArH due to acid traces
Compared with tosylate 1a, the mesylate and 1-/2-naphthyl
triflates were efficiently zincated, as were aminosulfonate
electrophiles. A systematic variation of halides showed that
while 1-fluoronaphthalene is unreactive, both 1-bromo- and 1-
chloronaphthalene were successfully zincated under catalytic
conditions. Combined with the previous experiment involving 1-
chloro-4-tosyloxybenzene (Table 2, entry 19), opportunities for
chemoselective activation arise. Remarkably, the feebly
in 13CH3I. [g] 1.5 equiv. of ArZnOTs (2) used. All = allyl; NBS
= N-
bromosuccinimide.
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species.
A pool of zinc (pseudo)halide (X = Cl, OTs)
Table 4. Propensity of substrates with various leaving groups for nickel-
catalyzed zincation.[a]
accumulates through activation and SET-reduction events, and
transmetalation of aryl from (L)NiIIArX to ZnX2 can be considered
to generate ArZnX. Such a step appears unfavorable with NiII,
however, since the usual course of transmetalation is transfer of
aryl from electropositive (Zn, Mg) to less electropositive metal
centers (NiII, PdII, PtII).[30] By SET-reduction of NiII, a more
nucleophilic (L)NiIAr species is obtained instead, with higher
propensity to transfer aryl to ZnCl(OTs), releasing ArZnOTs and
(L)NiICl in the process.[31] The latter is reduced by another SET
from zinc metal to regenerate (L)nNi0.
1. Zn (4.0 eq.), DBE (0.2 eq.)
solvent, 60 °C, 20 min
I2
2. NiCl2(dme)–L1 (5+10 mol%)
r.t., 30 min
(4.0 eq.)
Nap-X
Nap-ZnX
Nap-I
0 °C,
10 min
3. Substrate addition
solvent, r.t., 20 h
2
3a (1-Nap)
3c (2-Nap)
Reductive coupling of ArOTs (1) to biaryl (5) is a potential
side-reaction,[16] and while the latter is preferred with Ni–
phosphane catalyst systems[16b] and ascribed to a NiI–NiIII cycle
with oxidative addition of ArX to Ni(I)Ar,[16], the DAD-type ligands
of the current catalyst system apparently disallow this route.
Besides the preparative opportunities that the catalytic zincation
of aryl sulfonates offers, our results imply that mechanistic
pathways involving transmetalation with temporary release of
organometallics ArMX enable additional options in Ni-catalyzed
reductive coupling reactions, which have previously been
assumed to take place at the Ni-center exclusively.[22]
OTs
OMs
OTf
OTf
DMF (97%)
DMF (95%)
NMP (78%)
DMF (84%)
O
S
O
S
O
O
F
O
NMe2
N
N
O
DMF (98%)
DMF (0%)
DMF (95%)
In summary, we have developed a generally applicable
method to catalytically zincate aryl sulfonates and other
deactivated electrophiles that provides synthetically useful
arylzinc reagents. The DAD ligands used are readily available
and easy to modify synthetically. As such, the Ni–DAD catalyst
systems introduced by tom Dieck[19] may yet find more
widespread application in reductive transformations.
Cl
Br
SMe
SMe
DMF (80%)
NMP (84%)
DMF (90%)
DMF (65%)
[a] Reactions performed at the 1 mmol scale. Solvent and yield of ArZnX (in
brackets) indicated for each substrate. ArZnX was quantified after iodolysis as
1-NapI (3a) or 2-NapI (3c) by qNMR.
Acknowledgements
Based on the experimental observations in hand and with
reference to previous work on catalytic zincations[9] or Ni–bipy
catalyzed reductive carboxylation,[22d] we formulate a likely
catalytic cycle for the nickel-catalyzed reaction as in Scheme 2.
We thank the Luxembourg National Research Fund for an AFR-
individual PhD grant to P. Klein.
Keywords: aryl sulfonates • catalysis • nickel • metalation •
(L)NiIICl2
NiCl2·(dme) + L
organozinc reagents
activation
- dme
Zn
Zn*
[1]
a) The chemistry of organomagnesium compounds, Z. Rappoport, I.
Marek (Eds.), John Wiley & Sons, Ltd. 2008; b) G. S. Silverman, P. E.
Rakita, Handbook of Grignard Reagents, CRC Press, Boca Raton,
1996; c) B. J. Wakefield, Organomagnesium Methods in Organic
Chemistry, Elsevier, 1995.
ZnCl2
[(L)Ni0]
0.5 Zn*
Ar OTs
[2]
a) P. Knochel in Organometallics in Synthesis, Third Manual, M.
Schlosser (Ed.), John Wiley & Sons, 2013, 223; b) P. Knochel, Science
of Synthesis 2004, 3, 5; c) P. Knochel, P. Jones, Organozinc Reagents
- A Practical Approach, Oxford University Press, New York, 1999.
V. Grignard, Ann. Chim. Phys. [Sér. 7] 1901, 24, 433.
0.5 ZnCl2
0.5 Zn(OTs)2
+
[(L)NiI]Cl
[(L)NiII]Ar(OTs)
[3]
[4]
[5]
E. von Frankland, Liebigs Ann. Chem. 1849, 71, 171.
0.5 Zn*
a) D. E. Pearson, D. Cowan, J. D. Beckler, J. Org. Chem. 1959, 24,
504; b) H. E. Ramsden, A. E. Balint, W. R. Whitford, J. J. Walburn, R.
Cserr, J. Org. Chem. 1957, 22, 1202; c) H. Gilman, N. B. St. John, Rec.
Trav. Chim. Pays-Bas 1930, 49, 717; d) H. Normant, Cpts. Rds. Hébd.
Séanc. Acad. Sciences 1954, 239, 1510.
ArZnOTs
[(L)NiI](Ar)
Scheme 2. Proposed catalytic cycle.
dimethoxyethane;
L
=
IPr-MeDAD (L1); dme
=
[6]
[7]
For an indirect route (ArCl®ArLi®ArZnCl): P. Knochel, Z.-L. Shen, K.
Sommer, Synthesis 2015, 47, 2617.
Specific approaches to zincation of ArBr: a) Q. Cao, J. L. Howard, E.
Wheatley, D. L. Browne, Angew. Chem. 2018, 130, 11509; Angew.
Chem. Int. Ed. 2018, 57, 11339; b) N. Boudet, S. Sase, P. Sinha, C.-Y.
(L)NiIICl2 (L = L1, IPr-MeDAD) formed in situ is reduced to
(L)Ni0, presumably stabilized as (L)2Ni with additional ligand,[19]
that oxidatively adds aryl tosylate to afford an arylnickel(II)
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Liu, A. Krasovskiy, P. Knochel, J. Am. Chem. Soc. 2007, 129, 12358; c)
A. Krasovskiy, V. Malakhov, A. Gavryushin, P. Knochel, Angew. Chem.
2006, 118, 6186; Angew. Chem. Int. Ed. 2006, 45, 6040; d) A. Guijarro,
D. M. Rosenberg, R. D. Rieke, J. Am. Chem. Soc. 1999, 121, 4155; e)
L. Zhu, R. M. Wehmeyer, R. D. Rieke, J. Org. Chem. 1991, 56, 1445; f)
E. Erdik, Tetrahedron 1987, 43, 2203.
Naturforschung B 1984, 39, 180; for a cobalt-DAD catalyst, see: f) A.
Moncomble, P. Le Floch, C. Gosmini, Chem. Eur. J. 2009, 15, 4770.
[19] a) H. tom Dieck, M. Svoboda, T. Greiser, Z. Naturforsch. B 1981, 36,
823; b) H. tom Dieck, J. Dietrich, Chem. Ber. 1984, 117, 694.
[20] NiCl2(dme)–L1–Zn0 failed to catalyze a halide exchange between 1a
and NaI to give 2a in THF, see the Supporting Information.
[8]
[9]
B. Bogdanović, M. Schwickardi, Angew. Chem. 2000, 112, 4788 ;
Angew. Chem. Int. Ed. 2000, 39, 4610.
[21] a) C. Sämann, V. Dhayalan, P. R. Schreiner, P. Knochel, Org. Lett.
2014, 16, 2418; b) F. M. Piller, A. Metzger, M. A. Schade, B. A. Haag, A.
Gavryushin, P. Knochel, Chem. Eur. J. 2009, 15, 7192; c) A. Metzger, F.
M. Piller, P. Knochel, Chem. Commun. 2008, 5824.
a) H. Fillon, J. Périchon, C. Gosmini, J. Am. Chem. Soc. 2003, 125, a)
H. Fillon, J. Périchon, C. Gosmini, J. Am. Chem. Soc. 2003, 125, 3867;
b) I. Kazmierski, C. Gosmini, J.-M. Paris, J. Périchon, Tetrahedron Lett.
2003, 44, 6417; c) C. Gosmini, Mg. Amatore, S. Claudel, J. Périchon,
Synlett 2005, 2171; d) Y. Bourne-Branchu, A. Moncomble, M. Corpet,
G. Danoun, C. Gosmini, Synthesis 2016, 48, 3352. e) J. Périchon, C.
Gosmini, O. Buriez, Electrochemical Generation and Reaction of Zinc
Reagents in PATAI’S Chemistry of Functional Groups, John Wiley &
Sons, 2009. For an application, see: e) C. S. Yeung, V. M. Dong, J. Am.
Chem. Soc. 2008, 130, 7826.
[22] Ni–phenanthrolin type catalysts are widely applied in reductive coupling
or carboxylation reactions involving RX (X typically halogen) and
electrophiles (including RX’, carbonyls, CO2, alkene
+ RX’); for
examples, see: a) Y. Sumida, T. Hosoya, T. Sumida, Synthesis 2017,
49, 3590; b) A. García-Domínguez, Z. Li, C. Nevado, J. Am. Chem. Soc.
2017, 139, 6835; c) M. Börjesson, T. Moragas, R. Martin, J. Am. Chem.
Soc. 2016, 138, 7504; d) F. Rebih, M. Andreini, A. Moncomble, A.
Harrison-Marchand, J. Maddaluno, M. Durandetti, Chem. Eur. J. 2016,
22, 3758; e) Y. Zhou, C. Uyeda, Angew. Chem. 2016, 128, 3223;
Angew. Chem. Int. Ed. 2016, 55, 3171; f) G. A. Molander, K. M. Traister,
B. T. O’Neill, J. Org. Chem. 2015, 80, 2907; g) L. K. G. Ackerman, M. M.
Lovell, D. J. Weix, Nature 2015, 524, 454; h) X. Wang, Y. Liu, R. Martin,
J. Am. Chem. Soc. 2015, 137, 6476; i) K. M. Arendt, A. G. Doyle,
Angew. Chem. 2015, 127, 10014; Angew. Chem. Int. Ed. 2015, 54,
9876; k) Y. Liu; J. Cornella; R. Martin, J. Am. Chem. Soc. 2014, 136,
11212; l) S. Biswas, D. J. Weix, J. Am. Chem. Soc. 2013, 135, 16192;
m) T. Fujihara, K. Nogi, T. Xu, J. Terao, Y. Tsuji, J. Am. Chem. Soc.
2012, 134, 9106; n) D. A. Everson, B. A. Jones, D. J. Weix, J. Am.
Chem. Soc. 2012, 134, 6146; o) D. A. Everson, R. Shrestha, D. J. Weix,
[10] M.-Y. Jin, N. Yoshikai, J. Org. Chem. 2011, 76, 1972.
[11] a) H. Normant, P. Perrin, Bull. Soc. Chim. Fr. 1957, 801; b) C. Jubert, P.
Knochel, J. Org. Chem. 1992, 57, 5425; c) D. Guijarro, G. Guillena, B.
Mancheño, M. Yus, Tetrahedron 1994, 50, 3427; d) T. Harada, T.
Kaneko, T. Fujiwara, A. Oku, J. Org. Chem. 1997, 62, 8966; e) S.-H.
Kim, R. D. Rieke, J. Org. Chem. 2000, 65, 2322.
[12] a) T. Sheppard, Org. Biomol. Chem. 2009, 7, 1043; b) T. P. Burns, R. D.
Rieke, J. Org. Chem. 1987, 52, 3674.
[13] For mostly analytical precedent of zincation of ArOMs with a CoBr2–
bipy-catalyst (0–36% yield), or more efficient reactions with ArOTf (61–
87%): I. Kazmierski, C. Gosmini, J.-M. Paris, J. Périchon, Synlett 2006,
881.
J. Am. Chem. Soc. 2010, 132, 3636; p) D. A. Everson, R. Shrestha, D.
J. Weix, J. Am. Chem. Soc. 2010, 132, 920.
[14] For
a cobalt-catalyzed sulfonate–copper exchange of specifically
[23] Iodide-effects in Ni-catalyzed reductive coupling were also seen in ref.
[Fehler! Textmarke nicht definiert.b].
functionalized ArOSO2R': C. J. Rohbogner, C. R. Diène, T. J. Korn, P.
Knochel, Angew. Chem. 2010, 122, 1918; Angew. Chem. Int. Ed. 2010,
49, 1874.
[24] Remaining activator 1,2-dichloroethane was also detected, indicating
low reactivity of alkyl chlorides in this catalysis.
[15] Besides direct metal insertion, ArOSO2R can be catalytically borylated
with HB(OR)2–base or diboryl reagents: a) W. K. Chow, O. Y. Yuen, P.
Y. Choy, C. M. So, C. P. Lau, W. T. Wong, F. Y. Kwong, RSC
Advances 2013, 3, 12518; b) M. Murata, Heterocycles 2012, 85, 1795;
c) G. A. Molander, S. L. J. Trice, S. M. Kennedy, S. D. Dreher, M. T.
Tudge, J. Am. Chem. Soc. 2012, 134, 11667; d) B. M. Rosen, K. W.
Quasdorf, D. A. Wilson, N. Zhang, A.-M. Resmerita, N. K. Garg, V.
Percec, Chem. Rev. 2011, 111, 1346; e) D. A. Wilson, C. J. Wilson, C.
Moldoveanu, A.-M. Resmerita, P. Corcoran, L. M. Hoang, B. M. Rosen,
V. Percec, J. Am. Chem. Soc. 2010, 132, 1800; f) J. Huffman, A.
Thompson, G. Kabalka, M. Akula, Synthesis 2005, 547. g) M. Murata, T.
Oyama, S. Watanabe, Y. Masuda, J. Org. Chem. 2000, 65, 164; h) T.
Ishiyama, Y. Itoh, T. Kitano, N. Miyaura, Tetrahedron Lett. 1997, 38,
3447.
[25] a) L. C. McCann, M. G. Organ, Angew. Chem. 2014, 126, 4475; Angew.
Chem. Int. Ed. 2014, 53, 4386; b) A. Hernán-Gómez, E. Herd, E. Hevia,
A. R. Kennedy, P. Knochel, K. Koszinowski, S. M. Manolikakes, R. E.
Mulvey, C. Schnegelsberg, Angew. Chem. 2014, 126, 2744; Angew.
Chem. Int. Ed. 2014, 53, 2706; c) L. Jin, C. Liu, J. Liu, F. Hu, Y. Lan, A.
S. Batsanov, J. A. K. Howard, T. B. Marder, A. Lei, J. Am. Chem. Soc.
2009, 131, 16656.
[26] a) R. A. Altman, S. L. Buchwald, Nature Protocols 2007, 2, 3115; b) G.
Manolikakes, C. Muñoz Hernandez, M. A. Schade, A. Metzger, P.
Knochel, J. Org. Chem. 2008, 73, 8422.
[27] a) H. Tokuyama, S. Yokoshima, T. Yamashita, T. Fukuyama,
Tetrahedron Lett. 1998, 39, 3189; b) L. Melzig, A. Metzger, P. Knochel,
Chem. Eur. J. 2011, 17, 2948; c) P. H. Gehrtz, P. Kathe, I. Fleischer,
Chem. Eur. J. 2018, 24, 8774; d) K. Murakami, J. Imoto, H. Matsubara,
S. Yoshida, H. Yorimitsu, K. Oshima, Chem. Eur. J. 2013, 19, 5625.
[28] Precedent of cobalt-catalyzed zincation of heteroaryl methylthioethers:
J.-M. Begouin, M. Rivard, C. Gosmini, Chem. Commun. 2010, 46, 5972.
[29] Cursory experiments showed the inactivity of 1-naphtyhl methyl ether, -
trifluoroacetate and pivalate.
[16] For reductive homocoupling of ArOSO2R to Ar–Ar under simlar
conditions, see: a) M. Durandetti, J. Maddaluno, Synlett 2015, 26,
2385; b) A. Jutand, A. Mosleh, J. Org. Chem. 1997, 62, 261; c) A.
Jutand, A. Mosleh, Synlett 1993, 568.
[17] T. Schimmel, Übergangsmetall-katalysierte Metallierungsreaktionen,
Thesis for the First State Examination for Secondary School Teachers,
RWTH Aachen, 2004. Key results from the screening are presented in
the Supporting Information.
[30] Transmetalation MX
+ RM’ = MR + M’X is thermodynamically
favourable if aryl/alkyl group R is moving from electropositive M’ to less
electropositive (more electron-rich) M: a) J. Chatt, B. L. Shaw, J. Chem.
Soc. (Resumed) 1960, 1718; b) O. Wendt, Curr. Org. Chem. 2007, 11,
1417.
[18] Ni-DAD combinations in catalysis: a) Y. Kuang, D. Anthony, J. Katigbak,
F. Marrucci, S. Humagain, T. Diao, Chem 2017, 3, 268; b) A. Y.
Lebedev, A. F. Asachenko, A. Z. Voskoboynikov, A. Razavi,
WO2007111537 (A2); c) J. C. M. Sinnema, G. H. B. Fendesak, H. tom
Dieck, J. Organomet. Chem. 1990, 390, 237; d) R. Diercks, H. Dieck
tom, Chem. Ber. 1985, 118, 428; e) R. Diercks and H. tom Dieck, Z.
[31] Species of type Ni0(L)2 (ref.[19]) and [(NiIBr(L))2] (ref.[18a]) have been
characterized with either L1 or similar DAD ligands.
This article is protected by copyright. All rights reserved.

10.1002/chem.201904545
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
Unlike aryl halides, common aryl
sulfonates do not undergo metal
insertion to give organometallic
reagents. A nickel-diazadiene
complex has been found to catalyze
zincation of aryl sulfonates and
provide synthetically valuable arylzinc
sulfonates.
Philippe Klein, Vivien Denise Lechner,
Tanja Schimmel, Lukas Hintermann*
Page No. – Page No.
Generation of Organozinc Reagents
by Nickel-Diazadiene-Complex
Catalyzed Zinc Insertion into Aryl
Sulfonates
This article is protected by copyright. All rights reserved.