Nickel-Copper-Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes

Article abstract of DOI:10.1002/chem.201900822

The hydroacylation of vinylarenes with acyl fluorides and hydrosilanes was enabled by a synergistic bimetallic Ni/Cu-catalytic system, giving access to the corresponding branched ketone products. The reaction takes place under mild conditions at 25–80 °C and tolerates base-sensitive functional groups such as methoxycarbonyl and acetoxy groups.

Full text of DOI:10.1002/chem.201900822

A Journal of
Accepted Article
Title: Nickel-Copper-Catalyzed Hydroacylation of Vinylarenes with Acyl
Fluorides and Hydrosilanes
Authors: Yusuke Ueda, Tomohiro Iwai, and Masaya Sawamura
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Nickel-Copper-Catalyzed Hydroacylation of Vinylarenes with Acyl
Fluorides and Hydrosilanes
Yusuke Ueda, Tomohiro Iwai,* and Masaya Sawamura*
Abstract: The hydroacylation of vinylarenes with acyl fluorides
and hydrosilanes by synergistic Ni/Cu two-metal catalysis was
developed, giving the corresponding branched ketone products.
The reaction occurs under mild conditions at 25–80 °C and
fluorides as acylating reagents for the Cu-catalyzed boraacylation
of allenes with bis(pinacolato)diboron (Scheme 1b).[9]
Our long-standing interest in synergistic two-metal catalysis
prompted us to explore the possibility of enabling the
hydroacylation of vinylarenes with acyl fluorides and hydrosilanes
by synergistic Ni/Cu two-metal catalysis.[10-15] As shown in
Scheme 1c, an acyl fluoride is activated through oxidative addition
to a Ni(0) complex (step a). Concurrently, a vinylarene is
converted to a nucleophilic alkylcopper species via insertion into
a Cu–H species (hydrocupration, step d)[16] that is generated in
situ from a Cu–F species with a hydrosilane (step e).[17] The two
catalytic species meet and transmetalation occurs to give the
corresponding diorganonickel(II) complex with simultaneous
regeneration of the Cu–F species (step b). Finally, reductive
elimination of the diorganonickel(II) complex furnishes the
hydroacylation product (step c) and the Ni(0) species to complete
the two-cycle catalytic reaction pathway.[18]
tolerates
base-sensitive
functional
groups
such
as
methoxycarbonyl and acetoxy groups.
Acyl fluorides, which are easily prepared from carboxylic
acids,[1] are less common as acylating reagents than the
corresponding chlorides and bromides due to their inertness as
acylating reagents under conventional conditions. However, the
use of acyl fluorides as reagents in organic synthesis through
activation of the C–F bond have attracted growing interest in
recent years, offering new types of molecular transformations that
have not been achieved with acyl chlorides or bromides.
Generally, the fluorides show better tolerance toward nucleophilic
or basic functional groups than the chlorides and bromides. A
pioneering work by Rovis described an efficient ketone synthesis
through Ni-catalyzed cross-coupling of acyl fluorides with
organozincs (Scheme 1a).[2] Later, Ogiwara and Sakai reported
similar transformations using organosilicons or organoborons by
Pd catalysis.[3] These reactions were initiated by oxidative
addition of the acyl C(sp2)–F bonds to low-valent metal complexes,
producing acyl metal intermediates.[4,5]
(a) Conventional cross-coupling (Rovis; Ogiwara and Sakai)
oxidative addition
O
O
O
cat. [TM]
R2–M
+
R1
R1
R2
[TM]
F
F
TM = Ni, Pd
R1
M = Zn, Si, B
(b) Boraacylation of allenes with diboron (Gagosz and Riant)
H
R2
R3
R4
O
O
cat. [Cu]
+
R4
R1
R1
F
Bpin
NaOTMS
R
2 R3
pinB–Bpin
(c) Hydroacylation of vinylarenes with hydrosilane (This work)
Catalytic in situ generation of nucleophilic organometallic
species via insertion of unsaturated C–C bonds to M–X bonds
followed by trapping with acyl electrophiles affords attractive
synthetic methods, which can avoid the use of stoichiometric
amounts of pre-formed organometallic reagents.[6] Metal-
catalyzed reductive coupling of C–C unsaturated compounds with
electrophiles is representative.[7,8] For acylation, carboxylic
anhydrides were used as acylating electrophiles in the reaction of
O
cat. [Ni]
cat. [Cu]
Ar
O
Ar
R1
+
R1
F
H–SiR3
H
Working Hypothesis: Synergistic Two-metal Catalysis
O
[Cu]
Ar
H
R1
[Ni(II)]
F
step a
step d
O
R1
Ar
F
vinylarenes in the presence of hydrosilanes or H2 as
H
sources.[6a,7a,b] More recently, Gagosz and Riant used acyl
Cu cycle
[Cu]–H
[Ni(0)]
Ni cycle step b
O
H
Ar
step c
O
R1
Ar
F–SiR3
step e
H–SiR3
R1
[Ni(II)]
[Cu]–F
[*]
Prof. Dr. M. Sawamura
H
Institute for Chemical Reaction Design and Discovery (WPI-
ICReDD), Hokkaido University
Kita 21, Nishi 10, Kita-ku, Sapporo 001-0021 (Japan)
E-mail: sawamura@sci.hokudai.ac.jp
Related work: Reductive coupling with carboxylic anhydrides as an acyl source
(Miura; Krische; Buchwald)
O
Ar
O
O
cat. [M]
Ar
R1
+
R1
R1
O
H–X
(X = H, SiR3)
H
Y. Ueda, Dr. T. Iwai, Prof. Dr. M. Sawamura
Department of Chemistry, Faculty of Science, Hokkaido University
Sapporo 060-0810 (Japan)
Scheme 1. Transition metal catalysis using acyl fluorides as acyl
E-mail: iwai-t@sci.hokudai.ac.jp
sawamura@sci.hokudai.ac.jp
sources.
Homepage: http://wwwchem.sci.hokudai.ac.jp/~orgmet/
Supporting information for this article is given via a link at the end
of the document.
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To this end, the conditions were optimized for the reaction
between benzoyl fluoride (1a) and styrene (2a). The results are
summarized in Table 1, with the optimal conditions given in entry
1. Namely, a THF solution of a Ni catalyst was prepared from
[Ni(cod)2] (5 mol%) and DCYPBz (5 mol%), featuring high
electron-donating and rigid chelating properties, at room
temperature.[19] Meanwhile, a Cu catalyst was prepared from
CuF2 (10 mol%) and DPPBz (10 mol%) in THF at room
temperature. To the Cu catalyst solution, HSiMe(OMe)2 (2 eq)
and styrene (2a, 2.5 eq), benzoyl fluoride (1a, 0.15 mmol), and
the Ni catalyst solution were successively added in this order. The
resulting mixture was stirred at 25 °C for 20 h to give the branched
hydroacylation product 3a as a single constitutional isomer in 71%
yield (1H NMR analysis) along with its carbonyl reduction product
4a (6%).[20] No decarbonylative coupling product (1,1-
diphenylethylene) was observed in the crude product.[5] Silica gel
column chromatography and preparative TLC purification gave
analytically pure 3a in 52% yield. Control experiments using a
single metal component confirmed that both Ni and Cu were
indispensable for the hydroacylation to occur (entries 2 and 3).
With the synergistic Ni/Cu catalysis, the use of benzoyl chloride
instead of the fluoride 1a induced no hydroacylation (entry 4),[21]
indicating the utility of acyl fluorides as acylating reagents.
Table 1. Conditions for the reaction of benzoyl fluoride (1a) and styrene (2a) with hydrosilane[a]
[Ni] (5 mol%, Ni/L 1:1)
O
O
OH
Ph
[Cu] (10 mol%, Cu/L 1:1)
Ph
Ph
+
+
Ph
Ph
F
Ph
hydrosilane (2.0 eq)
1a (0.15 mmol) 2a (2.5 eq)
3a
4a
THF (0.5 M), 25 °C, 20 h
H
H
tBu
(PS)
(PS)
tBu
tBu
tBu
Ligands used in this work
tBu
tBu
tBu
(PS)
(PS)
(PS)
(PS)
N
N
P
P
P
P
P
P
PPh2
DPPBz
P
Ph2P
P
tBu
IPr
DCYPBz
DCYPE
(PS)
(PS)
tBu
tBu
tBu
tBu
SciOPP
PS-DPPBz
Ni catalyst
Ligand
Cu catalyst
Ligand
NMR Yield [%]
Entry
Hydrosilane
Metal
Metal
3a
4a
1
[Ni(cod)2]
none
DCYPBz
none
CuF2
CuF2
none
CuF2
CuF2
CuF2
CuF2
CuF2
DPPBz
DPPBz
none
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
HSiMe(OMe)2
PMHS
71 (52)[b]
6
0
0
0
7
9
0
0
0
0
8
0
8
4
0
0
0
0
9
20
12
0
2
0
3
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
Ni(OAc)2
NiCl2
DCYPBz
DCYPBz
DPPBz
DCYPBz
DPPBz
DCYPE
0
4[c]
DPPBz
DCYPBz
DCYPBz
DPPBz
DPPBz
DPPBz
DPPBz
DPPBz
DPPBz
DPPBz
SciOPP
0
5
65
66
0
6
7
8
29
0
9
PCy3 (10 mol%) CuF2
10
11
12
13
14
15
16
17
18
19
20
21
22
IPr (10 mol%)
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
DCYPBz
CuF2
CuF2
CuF2
CuF2
CuF2
CuF2
CuF2
CuF2
0
55
8
[Pd(dba)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
[Ni(cod)2]
40
65
5
PS-DPPBz
PCy3 (20 mol%)
IPr (20 mol%)
DPPBz
20
0
CuCl/NaOtBu
Cu(OAc)2
CuF2
0
DPPBz
20
70
59
0
DPPBz
CuF2
DPPBz
HSi(OEt)3
CuF2
DPPBz
H3SiPh
[a] 1a (0.15 mmol), 2a (0.375 mmol), [Ni] (5 mol%, M/L 1:1), [Cu] (10 mol%, M/L 1:1), hydrosilane (0.30 mmol), THF (0.3 mL), 25 °C, 20 h. [b]
Isolated yield. [c] Using benzoyl chloride instead of 1a.
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Table 2. Scope of acyl fluorides (1) and vinylarenes (2)
When the metal-ligand combinations were interchanged (Ni-
DPPBz and Cu-DCYPBz) or DCYPBz was employed for both the
Ni and Cu systems, the yield of the hydroacylation product (3a)
was only marginally decreased (65 and 66% yields, respectively,
Table 1, entries 5 and 6). In sharp contrast, the use of DPPBz for
both the Ni and Cu systems resulted in no hydroacylation, while
reduction of 1a occurred to give benzyl alcohol (entry 7). These
results suggest the critical importance of the existence of the Ni-
DCYPBz species and the occurrence of partial ligand exchange
between the Ni and Cu systems to form the active Ni-DCYPBz
species when the metals and the ligands were premixed in the
wrong order as in entry 5.[22]
[Ni(cod)2]/DCYPBz (5 mol%)
CuF2/DPPBz (10 mol%)
O
O
Ar
+
Ar
Me
R1
R1
F
HSiMe(OMe)2 (2.0 eq)
THF (0.5 M), 25 °C, 20 h
1
2 (2.5 eq)
3
Yield
[%]
Entry Acyl Fluorides Vinylarenes
Product (3)
tBu
tBu
O
1
2
3
4
1a
1a
1a
1a
44
47
68
30
Ph
2b
Me
3b
F
F
O
Ph
2c
Me
3c
The effects of other ligands premixed with [Ni(cod)2] are
shown in Table 1, entries 8–10. DCYPE, having a flexible
ethylene linker between the two Cy2P groups, decreased the yield
(29%, entry 8). Monodentate ligands such as PCy3 and IPr were
ineffective (entries 9 and 10). An air-stable Ni(II) complex
Ni(OAc)2 was applicable, but less effective than [Ni(cod)2] (55%,
entry 11). NiCl2 was not suitable (8%, entry 12). A Pd catalyst
prepared from [Pd(dba)2] and DCYPBz also induced the
hydroacylation, but did not improve the yield over that obtained
with the Ni catalyst (40%, entry 13).
CN
CN
O
3d
Ph
2d
Me
CO2Me
CO2Me
O
3e
Ph
2e
Me
OAc
OAc
O
5
6
7
1a
1a
1a
63
70
40
2f
3f
Ph
Me
O
N
Table 1 also includes effects of other parameters with respect
to the Cu catalyst system (entries 14–22). The sterically
demanding DPPBz-type ligand SciOPP showed a ligand effect
similar to DPPBz (65%, entry 14). The polystyrene-cross-linking
DPPBz-type ligand, PS-DPPBz, the utility of which was previously
demonstrated in our studies on Cu catalysis,[23] was much less
effective than the parent soluble ligand DPPBz (5%, entry 15).
Monodentate ligands such as PCy3 and IPr did not give an
efficient catalyst (entries 16 and 17). The use of other copper
sources such as CuCl/NaOtBu and Cu(OAc)2, instead of CuF2,
caused a decrease in the yields (0% and 20%, entries 18 and 19),
indicating that the fluoride ligand on Cu was important for the
reaction with the hydrosilane to produce the Cu–H species
(Scheme 1c, step e). Changing HSiMe(OMe)2 to other alkoxy-
substituted hydrosilanes such as PMHS and HSi(OEt)3 was
possible while maintaining similar reaction efficacies (70% and
59%, entries 20 and 21), but a monoorgano-substituted silane,
H3SiPh, was not effective (entry 22).
N
Ph
3g
2g
Me
O
N
N
Ph
3h
2h
Me
O
O
8[b,c]
2a
35
69
49
48
43
50
F
3i
Me
1b
Me
MeO
Cl
Me
O
N
9[b]
1b
1c
2g
2a
2g
2g
3j
Me
Me
MeO
MeO
Cl
O
O
10[c]
11
F
3k
Me
1c
O
N
3l
Me
With the combination of the [Ni(cod)2]/DCYPBz and
CuF2/DPPBz system in the presence of HSiMe(OMe)2, various
branched hydroacylation products 3 were obtained from 1 and 2
(Table 2). The 4-substituted styrenes 2b–2f underwent
hydroacylation with 1a, giving 3b–3f in 30–68% yields (entries 1–
5). Notably, base-sensitive functional groups such as
methoxycarbonyl (3e) and acetoxy (3f) groups on the benzene
ring were tolerated. The reaction of 4-vinylpyridine (2g) with 1a
proceeded cleanly to give 3g in 70% yield (entry 6). When benzoyl
chloride was used instead of 1a in this reaction, no hydroacylation
product was obtained due to immediate occurrence of N-acylation
of 2g to give the corresponding pyridinium salt. 2-Vinylpyridine
(2h) was also a suitable substrate for the protocol with acyl
fluoride 1a (3h, entry 7).
O
O
N
12[c]
F
3m
Me
1d
O
O
N
13[b,c]
2g
F
3n
Me
1e
MeO2C
MeO2C
O
O
N
14[b,d]
2g
47
F
N
N
Me
3o
1f
Me
Me
[a] 1 (0.15 mmol), 2 (0.375 mmol), [Ni(cod)2]/DCYPBz (5 mol%),
CuF2/DPPBz (10 mol%), HSiMe(OMe)2 (0.30 mmol), THF (0.3 mL),
25 °C, 20 h. Isolated yields. [b] SciOPP was used as a ligand on Cu
instead of DPPBz. [c] 60 °C. [d] 80 °C.
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COMMUNICATION
2018, 20, 4204–4208; b) S. T. Keaveney, F. Schoenebeck, Angew.
Chem. 2018, 130, 4137–4141; Angew. Chem. Int. Ed. 2018, 57, 4073–
4077; c) Okuda, J. Xu, T. Ishida, C. Wang, Y. Nishihara, ACS Omega
2018, 3, 13129–13140; d) Z. Wang, X. Wang, Y. Nishihara, Chem.
Commun. 2018, 54, 13969–13972; e) S. Sakurai, T. Yoshida, M. Tobisu,
Chem. Lett. 2019, 48, 94–97. See also ref 4b.
In addition to an electronically non-biased acid fluoride (1b),
electron-rich and -poor acid fluorides 1c–1e participated in the
hydroacylation of vinylarenes 2a or 2g at 25–60 °C (Table 2,
entries 8–13).[24] In some cases, the use of SciOPP instead of
DPPBz on Cu increased the yields. Notably, the C(sp2)–Cl bond
on the benzene ring, which can undergo oxidative addition to Ni(0)
species, was tolerated.[25] N-Methyl-2-indolyl carbonyl fluoride
reacted with 2g at 80 °C, giving 3o in 47% yield (entry 14). Neither
aliphatic acid fluorides nor aliphatic alkenes provided the
hydroacylation products 3.
[6]
For selected examples using Cu catalysts, see: a) J. S. Bandar, E. Ascic,
S. L. Buchwald, J. Am. Chem. Soc. 2016, 138, 5821–5824; b) Y. Zhou,
J. S. Bandar, S. L. Buchwald, J. Am. Chem. Soc. 2017, 139, 8126–8129;
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13503; Angew. Chem. Int. Ed. 2017, 56, 13314–13318; d) T. Fujihara, A.
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129, 1561–1565; Angew. Chem. Int. Ed. 2017, 56, 1539–1543.
For selected papers on metal-catalyzed reductive coupling, see: a) K.
Kokubo, M. Miura, M. Nomura, Organometallics 1995, 14, 4521–4524;
b) Y.-T. Hong, A. Barchuk, M. J. Krische, Angew. Chem. 2006, 118,
7039–7042; Angew. Chem. Int. Ed. 2006, 45, 6885–6888; c) H. Xiao, G.
Wang, M. J. Krische, Angew. Chem. 2016, 128, 16353–16356; Angew.
Chem. Int. Ed. 2016, 55, 16119–16122. See also ref 6a.
Finally, the synergistic Ni/Cu two-metal catalyst was applied
to the derivatization of a complex molecule. Vinylestrone 2i
underwent hydroacylation with 1a and HSiMe(OMe)2 at 25 °C,
affording 3p as a 1:1 diastereomeric mixture in 48% yield without
reduction of the cyclopentanone moiety.[26]
[7]
[8]
[9]
For selected reviews on metal-catalyzed reductive coupling, see: a) K. D.
Nguyen, B. Y. Park, T. Luong, H. Sato, V. J. Garza, M. J. Krische,
Science 2016, 354, aah5133; b) M. Holmes, L. A. Schwartz, M. J. Krische,
Chem. Rev. 2018, 118, 6026–6052.
Scheme 2. Reaction of 1a and 2i
O
O
Me
Me
H
[Ni(cod)2]/DCYPBz (5 mol%)
CuF2/DPPBz (10 mol%)
H
H
+
1a
O
H
H
H
A. Boreux, K. Indukuri, F. Gagosz, O. Riant, ACS Catal. 2017, 7, 8200–
8204.
HSiMe(OMe)2 (2 eq)
THF (0.5 M), 25 °C, 20 h
Ph
2i (2.5 eq)
3p 48%
Me
[10] For our work on synergistic cooperative enantioselective Rh/Pd two-
metal catalysis, see: M. Sawamura, M. Sudoh, Y. Ito, J. Am. Chem. Soc.
1996, 118, 3309–3310.
In summary, the hydroacylation of vinylarenes with acyl
fluorides and hydrosilanes by synergistic Ni/Cu two-metal
catalysis was developed. The use of DCYPBz as a ligand with its
electron-donating, sterically demanding, and rigid properties was
effective for producing the catalytically active Ni species. The
stability of the acyl fluorides and the mildness of the reaction
conditions are attractive features of this alkene hydroacylation
protocol. Further studies on synergistic two-metal catalysis for
efficient C–F transformations are ongoing in our laboratory.
[11] For a review on synergistic catalysis, see: A. E. Allen, D. W. C. MacMillan,
Chem. Sci. 2012, 3, 633–658.
[12] For selected reviews on cooperative two-metal catalysis, see: a) J. M.
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D. R. Pye, N. P. Mankad, Chem. Sci. 2017, 8, 1705–1718; c) K. Semba,
Y. Nakao, Tetrahedron 2019, 75, 709–719.
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see: for Pd/Cu catalysis, a) K. Sonogashira, Y. Tohda, N. Hagihara,
Tetrahedron Lett. 1975, 16, 4467–4470; b) F. Nahra, Y. Macé, D. Lambin,
O. Riant, Angew. Chem. 2013, 125, 3290–3294; Angew. Chem. Int. Ed.
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Acknowledgements
This work was supported by JSPS KAKENHI Grant Number JP
17H04877 in Young Scientists (A) to T.I., and by JSPS KAKENHI
Grant Number JP15H05801 in Precisely Designed Catalysts with
Customized Scaffolding to M.S.
Keywords: nickel • copper • cooperative catalysis • acyl fluorides
• hydroacylation
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Yusuke Ueda, Tomohiro Iwai,* and
Masaya Sawamura*
Page No. – Page No.
Nickel-Copper-Catalyzed
Hydroacylation of Vinylarenes with
Acyl Fluorides and Hydrosilanes
The hydroacylation of vinylarenes with acyl fluorides and hydrosilanes by synergistic
Ni/Cu two-metal catalysis was developed, giving the corresponding branched ketone
products. The reaction occurs under mild conditions at 25–80 °C and tolerates base-
sensitive functional groups such as methoxycarbonyl and acetoxy groups.
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