Nickel/copper-cocatalyzed decarbonylative silylation of acyl fluorides

Article abstract of DOI:10.1039/c9cc05325e

Ni/Cu-cocatalyzed decarbonylative silylation of acyl fluorides with silylboranes has been developed to afford various arylsilanes with high efficiency and good functional-group compatibility via carbon-fluorine bond cleavage and carbon-silicon bond formation. Such transformation can not only extend the functionalization type of acyl fluorides but complement the synthetic route for arylsilanes.

Full text of DOI:10.1039/c9cc05325e

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Wang, Z. Wang
and Y. Nishihara, Chem. Commun., 2019, DOI: 10.1039/C9CC05325E.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Page 1 of 5
Please doChneomt Cadomjumst margins
View Article Online
DOI: 10.1039/C9CC05325E
COMMUNICATION
Nickel/copper-cocatalyzed decarbonylative silylation of acyl
fluorides
Xiu Wang,a Zhenhua Wanga and Yasushi Nishihara*b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Ni/Cu-cocatalyzed decarbonylative silylation of acyl fluorides with decarbonylative silylation of acyl chlorides was observed with
silylboranes has been developed to afford various arylsilanes with chlorinated disilanes.11 Rueping12 and Shi13 independently
high efficiency and good functional-group compatibility via carbon- succeeded in nickel/copper-cocatalyzed decarbonylative silylation of
fluorine bond cleavage and carbon-silicon bond formation. Such phenolic esters via C−O bond cleavage. Building up on the previous
transformation can not only extend the functionalization type of work, Reuping expanded the decarbonylation silylation strategy for
acyl fluorides but complement the synthetic route for arylsilanes.
arylamides via C−N bond cleavage (Scheme 1b).14 However, phenolic
esters and arylamides are generally prepared from the
corresponding carboxylic acids via acyl chlorides in two steps, and a
large waste derived from phenols and amines are generated after the
reaction.12,14
Since organosilicon compounds are of a great importance in
organic synthesis,1 drug discovery2 and materials science,3
various synthetic strategies have been established by
constructing the C−Si bond. Traditional synthetic methods of
arylsilanes involves the reactions of Grignard or organolithium
reagent with silyl electrophiles,1a,4 in which ester and ketone
functional groups cannot be incorporated. Alternatively,
transition-metal-catalyzed silylation of aryl halides has been
developed for the preparation of arylsilanes.5 Although
defluorosilylation of fluoroarenes via C−F bond activation has
been reported recently, the synthesis of the starting materials
requires multi-step reactions.6 In addition, a direct C−H
silylation of unreactive aromatic compounds with hydrosilanes
were also investigated to obtain arylsilanes.7 Furthermore,
silylation of nitriles with disilanes via C−CN bond cleavage8 and
of pivalates or anisoles with silylboranes via C−O bond cleavage9
provided a new access to arylsilanes (Scheme 1a).
Utilizing decarboxylation/decarbonylation, transformations of
carboxylic acid and their derivatives into valuable compounds under
transition metal catalysis have drawn much attention owing to their
natural abundance and easy availability.10 Among them, early study
found that palladium-catalyzed silylation of acyl chlorides bearing
strong electron-withdrawing groups with hexamethyldisilanes gave
a mixture of acylsilane and arylsilane, in which the selective
On the other hand, acyl fluorides display many superiorities
than the corresponding carboxylic derivatives, showing great
stability and high reactivity.15 Moreover, acyl fluorides acting as
the acyl fragment without a CO loss in transition-metal-
catalyzed have been witnessed in cross-couplings of Negishi,16
Hiyama,17 Suzuki-Miyaura,18 and other reactions such as
reductive coupling with vinyl triflates,19 reduction,20
boroacylation of allenes,21 and C-H coupling with azoles22 to
give the corresponding ketones or aldehydes. Recently,
reactions of acyl fluorides serving as an arylation moiety via
decarbonylative process for C−C bond formation have been
extensively investigated, including trifluoromethylation,23
reduction,20b Suzuki-Miyaura type-arylation,24 and direct C–H
arylation.25 We have also reported the Ni(cod)2/DPPE catalytic
system for decarbonylative alkylation of acyl fluorides.26 The
outcome suggested that utilization of acyl fluoride is the key to
this transformation and other acyl halides cannot be
participated.
Due to the indispensable and versatile main group elements,
namely, boron, silicon, and tin in cross-coupling chemistry,27
carbon-heteroatom bond-forming reactions of acyl fluorides
are highly desired. Encouraged by a unique nature of acyl
fluorides in various decarbonylative C−C bond-forming
reactions and our continuous interest of acyl halides in cross-
coupling reactions,26,28 we have developed nickel-catalyzed
borylation29 and stannylation30 of acyl fluorides with diborons
and silylstannanes, respectively, in a decarbonylation manner.
Herein, we report our new approach to the synthesis of
a.Graduate School of Natural Science and Technology, Okayama University
3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan
b.Research Institute for Interdisciplinary Science, Okayama University
3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan
E-mail: ynishiha@okayama-u.ac.jp
† Electronic Supplementary Information (ESI) available: experimental procedures,
spectroscopic data and copies of 1H, 13C{1H} and 19F{1H} NMR spectra. See DOI:
10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
c
d
e
arylsilanes by nickel/copper-cocatalyzed decarbonylative standard. An isolated yield is given in parentheses. 150 °C. Without Ni(cod)2. 2-
View Article Online
DOI: 10.1039/C9CC05325E
silylation of acyl fluorides with silylboranes (Scheme 1c).
Naphthoyl chloride instead of 1a.
was added because of the reported profound effect of copper salts
in activation of the Si–B bond.31 As expected, 85% of 3a was
obtained, along with 10% of naphthalene as a by-product (entry 2).
Notably, cooperation of the copper salt suppressed the competitive
decarbonylative homocoupling and reduction. Other monodentate
phosphine ligands such as PCy3, PnBu3, and P(OPh)3 showed
moderate to poor activities in this transformation (entries 3-5).
Although acyl fluorides could act as a mild base in some cases,24
exogenous base is still required in the present silylation reaction.
Among the bases used, KF gave the best result (entry 2 and entries
6-9). Various cuprous and cupric salts were also examined (entries
10-13 and Table S5), and CuF2 showed the superior result with the
target product 3a in 89% yield (entry 13). Screening of the reaction
temperatures demonstrated that the higher reaction temperature
greatly increased the conversion of 1a to the decarbonylative
silylation product 3a, suppressing the formation of homocoupled
product (Table S6). Control experiments shown in entries 14-15
confirmed the crucial factors of Ni(cod)2 and PPh3 to succeed in this
transformation; no or trace of 3a was observed. In the absence of
KF, only 46% formation of 3a was detected (entry 16). In a sharp
contrast, employing 2-naphthoyl chloride instead of 1a under the
optimized reaction conditions, 2a remained unreacted and no
silylation product 3a was formed (entry 17). We reasoned that the
oxidative adduct NiAr(Cl)(PPh3)2 cannot undergo ligand exchange
with silylboranes.24 This different reactivity demonstrated the
unique nature of acyl fluorides in the present silylation. It is
noteworthy that no acylsilane in a retentive fashion was detected in
all cases, suggesting that PPh3 with a weak coordinating ability favors
easily dissociation from a nickel center, which is favorable for facile
CO migration and extrusion.
Scheme 1 Synthetic routes for arylsilanes.
Initially, we chose the reaction of 2-naphthoyl fluoride (1a
)
with silylborane 2a under basic conditions as the model reaction.
An inexpensive PPh3 ligand was preferable due to its excellent
performance in nickel-catalyzed decarbonylative borylation.29
However, only 5% of silylated product 3a was detected, along
with a large amount of 2a unconsumed (Table 1, entry 1), where
22% of naphthalene from decarbonylative reduction and 58% of
2,2'-binaphthalene derived from decarbonylative homo-
coupling were observed.
nickel/PPh3 catalytic system cannot efficiently activate 2a to
promote transmetalation of the oxidative adduct. Thus, CuOAc
This outcome revealed that
Table 1 Optimization of the reaction conditionsa
With the optimized reaction conditions in hand, a wide range of
acyl fluorides were investigated as shown in Table 2. The π-extended
aromatic acyl fluorides could be accommodated, providing
naphthylsilanes 3a and 3b in 85% and 82% yields, respectively. The
benzoyl fluoride substituted by a methyl group in the para-position
was well tolerated in this reaction, affording the target product 3c in
85% yield. A steric effect was illustrated by the phenyl-substituted
substrates in the ortho-, meta-, and para-positions; p-phenylbenzoyl
fluoride (1d) gained superiority than m-phenyl- (1e) and o-phenyl (1f)
counterparts. Other electron-rich alkoxy groups such as p-methoxy
(3g), 3,4,5-trimethoxy (3h) and p-butoxy (3i) were also well tolerated
during the reaction, although the Ni-catalyzed silylation via C−O bond
cleavage has been reported at lower temperature.9 This protocol
was also featured by acyl fluorides bearing functional groups at the
para-position, including amine, fluoride, ketone, and methyl ester,
resulting in the formation of the desired products 3j-3m in 50-66%
yields. In particular, phenolic ester skeleton (3n) was reported as a
reactive electrophile under the nickel/copper cocatalysis in a
decarbonylative silylation.12,13 Therefore, our method could be a
useful complement to other silylation processes that are inaccessible
for compatibility of alkoxy and phenolic ester groups. Furthermore,
the reaction could be extended to heteroatom-containing acyl
fluorides, affording arylsilanes 3o and 3p in 71% and 65% yields,
respectively. Unfortunately, other surrogate alkenyl and aliphatic
acyl fluorides failed to participate in this transformation. For
Entry
1
[Cu]
Ligand
PPh3
PPh3
PCy3
PnBu3
P(OPh)3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
-
Base
KF
3a (%)b
5
-
2
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
Cu(OAc)2
CuCl2
CuF2
KF
85
50
32
11
18
49
45
71
31
0
3
KF
4
KF
5
KF
6
CsF
NaF
LiF
KOAc
KF
7
8
9
10
11
12
13c
14d
15
16
17e
KF
KF
77
89 (85)
0
CuF2
KF
CuF2
KF
CuF2
KF
<1
CuF2
PPh3
-
46
CuF2
PPh3
KF
0
a 1a (0.2 mmol), 2a (0.4 mmol), Ni(cod)2 (0.02 mmol) in toluene (1.0 mL) at 140 °C for 24
b
h. Determined by GC analysis of the crude mixture, using n-dodecane as an internal
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
example, only a trace amount of the decarbonylative silylation late-stage decarbonylative silylation of estrone dVeireiwvaArttiivclee Ownlianes
DOI: 10.1039/C9CC05325E
product was detected when dodecanoyl fluoride was employed as conducted as shown in Scheme 3b, the etherification of estrone with
the coupling partner (Scheme S1).
methyl 4-(bromomethyl)benzoate (4), followed by hydrolysis
afforded carboxylic acid 6. Finally, compound 6 was subjected to the
two-step deoxyfluorination/decarbonylative silylation to provide 3v
in 75% yield.
Table 2 Decarbonylative silylation of acyl fluoridesa,b
a Reaction conditions:
1
(0.2 mmol), 2a (0.4 mmol), Ni(cod)2 (0.02 mmol), CuF2
b
(0.06 mmol), PPh3 (0.08 mmol), KF (0.6 mmol), toluene (1 mL), 150 °C, 24 h.
Isolated yields.
a Reaction conditions for deoxyfluorination of carboxylic acid: carboxylic acid (3
mmol), Deoxo-Fluor® reagent (3.3 mmol), CH2Cl2 (15 mL), 0 °C, 30 min. b Reaction
conditions for decarbonylative silylation:
1 (0.2 mmol), 2a (0.4 mmol), Ni(cod)2
(0.02 mmol), CuF2 (0.06 mmol), PPh3 (0.08 mmol), KF (0.6 mmol), toluene (1 mL),
150 °C, 24 h.
Scheme 3 Synthetic applications.
Considering related references and our previous work, a plausible
mechanism is shown in Scheme 4. Oxidative addition of acyl
fluorides 1 to the nickel(0) catalyst A yields acylnickel(II) complex B.
Subsequently, decarbonylation of complex B gave the arylnickel
species C.24,29 In the copper catalytic cycle, the formation of active
Cu-Si species from silylboranes 2 can be accounted for a larger
electronegativity of B (2.051) than Si (1.916),36 as well as bond
dissociation energy of diatomic B–F (732 kJ mol–1) and Si–F (576 kJ
mol–1).37 Therefore, a fluoride ion activates silylborane by a
construction of the more stronger B–F bond to generate silylcopper
species D.31 Transmetalation between aryl(fluoro)nickel(II) complex
C and silylcopper species D afforded complex E, the subsequent
reductive elimination of E yields the desired arylsilanes 3,
regenerating nickel(0) species A.
In summary, we have developed the nickel/copper co-catalyst
system for decarbonylative silylation reaction of acyl fluorides
to synthesize a wide range of aryl and heteroarylsilanes, in
which an inexpensive and stable PPh3 is indispensable. This
study can expand the chemistry of acyl fluorides in terms of
carbon-heteroatom bond formations, as well as a useful
complement to other silylation processes.
Scheme 2 Evaluation of different silylboranes.ab
Different silyl groups in organosilicon compounds can control the
reactivity in Hiyama reaction to construct the new C−C bonds,32 and
in halogenation to provide new building blocks for further
transformations.6a,9b,33 Thus, electronic and steric effects of the
silicon moiety on the present decarbonylative silylation were tested
by using four types of silylboranes under the standard reaction
conditions (Scheme 2). All of silylboranes are proved to be good
coupling partners using 2-naphthoyl fluoride (1a), yielding the
corresponding arylsilanes 3q-3t in 63-96% yields. It is noteworthy
that nPr3Si-Bpin could be converted into the desired product 3q in 64%
with our method, whereas phenyl 2-naphthoate gave only 31% of 3q
with Rueping’s protocol,12 which further demonstrated the efficiency
of our method.
Carboxylic acid-containing drug-probenecid, primarily used to
treat gout and hyperuricemia34 was also viable in nickel/copper-
catalyzed decarbonylative silylation reaction. Deoxyfluorination of
probenecid by conventional method,35 followed decarbonylative
silylation process furnished the target product 3u in 72% yield
(Scheme 3a), whereas the attempt of one-pot synthesis of 3u
without isolation of acyl fluoride (1u) provided an unsatisfactory
result with the formation of 3u in 28% yield (Scheme S2). Besides,
This study was partly supported by Marubun Research Promotion
Foundation. We gratefully thank the SC-NMR Laboratory (Okayama
University) for the NMR spectral measurements.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
14 S.-C. Lee, L. Guo, H. Yue, H.-H. Liao, M. Rueping, VSiyewnlAerttitc,le2O0n1lin7e,
28, 2594.
15 Recent reviews for transformations of aDcyOlI:fl1u0o.1r0id39e/sC,9sCeCe:0(5a3)2N5E.
Blanchard, V. Bizet, Angew. Chem., Int. Ed., 2019, 58, 6814; (b)
Y. Ogiwara, N. Sakai, Angew. Chem., Int. Ed.,
10.1002/anie.201902805.
16 Y. Zhang, T. Rovis, J. Am. Chem. Soc., 2004, 126, 15964.
17 Y. Ogiwara, Y. Maegawa, D. Sakino, N. Sakai, Chem. Lett., 2016,
45, 790.
18 Y. Ogiwara, D. Sakino, Y. Sakurai, N. Sakai, Eur. J. Org. Chem.,
2017, 4324.
19 F.-F. Pan, P. Guo, C.-L. Li, P. Su, X.-Z. Shu, Org. Lett., 2019, 21
3701.
20 (a) R. Braden, T. Himmler, J. Organomet. Chem., 1989, 367
,
,
Scheme 4 Proposed mechanism.
C12; (b) Y. Ogiwara, Y. Sakurai, H. Hattori, N. Sakai, Org. Lett.,
2018, 20, 4204.
21 (a) A. Boreux, K. Indukuri, F. Gagosz, O. Riant, ACS Catal., 2017,
Conflicts of interest
There are no conflicts to declare.
7, 8200; (b) J. Han, W. Zhou, P.-C. Zhang, H. Wang, R. Zhang,
H.-H. Wu, J. Zhang, ACS Catal., 2019, 9, 6890.
22 Y. Ogiwara, Y. Iino, N. Sakai, Chem. Eur. J., 2019, 25, 6513.
23 S. T. Keaveney, F. Schoenebeck, Angew. Chem., Int. Ed., 2018,
57, 4073.
24 C. A. Malapit, J. R. Bour, C. E. Brigham, M. S. Sanford, Nature,
2018, 563, 100.
Notes and references
1
(a) T. Hiyama, In Metal-Catalyzed Cross-Coupling Reactions;
F. Diederich, P. J. Stang, Eds.; Wiley-VCH: Weinheim, 1998; p
421. (b) For synthesis of arylsilane, see: The Chemistry of
Organic Silicon Compounds; S. Patai, Z. Rappoport, Eds.;
Wiley: New York, 2000.
25 S. Sakurai, T. Yoshida, M. Tobisu, Chem. Lett., 2019, 48, 94.
26 Y. Okuda, J. Xu, T. Ishida, C. A. Wang, Y. Nishihara, ACS Omega,
2018, 3, 13129.
27 M. Oestreich, E. Hartmann, M. Mewald, Chem. Rev., 2013, 113
402.
,
2
3
G. A. Showell, J. S. Mills, Drug Discovery Today, 2003,
8, 551.
28 (a) Y. Nishihara, Y. Inoue, M. Fujisawa, K. Takagi, Synlett, 2005,
15, 2309; (b) Y. Nishihara, D. Saito, E. Inoue, Y. Okada, M.
Miyazaki, Y. Inoue, K. Takagi, Tetrahedron Lett., 2010, 51, 306;
(c) D. Ogawa, K. Hyodo, M. Suetsugu, J. Li, Y. Inoue, M.
Fujisawa, M. Iwasaki, K. Takagi, Y. Nishihara, Tetrahedron,
(a) X.-M. Liu, C. He, J. Haung, J. Xu, Chem. Mater., 2005, 17
,
434; (b) Y. You, C.-G. An, J.-J. Kim, S. Y. Park, J. Org. Chem., 2007,
72, 6241.
A. S. Manoso, C. Ahn, A. Soheili, C. J. Handy, R. Correia, W. M.
Seganish, P. DeShong, J. Org. Chem., 2004, 69, 8305.
(a) S. E. Denmark, J. M. Kallemeyn, Org. Lett., 2003,
(b) Y. Yamanoi, J. Org. Chem., 2005, 70, 9607; (c) A. Hamze, O.
Provot, M. Alami, J.-D. Brion, Org. Lett., 2006, , 931; (d) E.
McNeill, T. E. Barder, S. L. Buchwald, Org. Lett., 2007, , 3785;
4
5
2013, 69, 2565; (d) X. Wang, Z. Wang, Y. Asanuma, Y. Nishihara,
Org. Lett., 2019, 21, 3640.
5, 3483;
29 Z. Wang, X. Wang, Y. Nishihara, Chem. Commun., 2018, 54
,
8
13969.
9
30 X. Wang, Z. Wang, L. Liu, Y. Asanuma, Y. Nishihara, Molecules,
2019, 24, 1671.
(e) Y. Yamanoi, H. Nishihara, J. Org. Chem., 2008, 73, 6671.
(a) B. Cui, S. Jia, E. Tokunaga, N. Shibata, Nat. Commun., 2018,
6
7
31 For Si−B bond activation by Cu, see: (a) D. J. Vyas, M. Oestreich,
Angew. Chem., Int. Ed., 2010, 49, 8513; (b) D. J. Vyas, R.
Frçhlich, M. Oestreich, Org. Lett., 2011, 13, 2094; (c) C.
Kleeberg, E. Feldmann, E. Hartmann, D. J. Vyas, M. Oestreich,
Chem. Eur. J., 2011, 17, 13538; (d) P. Wang, X.-L. Yeo, T.-P. Loh,
J. Am. Chem. Soc., 2011, 133, 1254; (e) E. Hartmann, D. J. Vyas,
M. Oestreich, Chem. Commun., 2011, 47, 7917; (f) V. Cirriez, C.
Rasson, O. Riant, Adv. Synth. Catal., 2013, 355, 3137; (g) V.
Cirriez, C. Rasson, T. Hermant, J. Petrignet, J. D. Alvarez, K.
Robeyns, O. Riant, Angew. Chem., Int. Ed., 2013, 52, 1785; (h)
H. Yoshida, Y. Hayashi, Y. Ito, K. Takaki, Chem. Commun., 2015,
51, 9440.
9
, 4393; (b) X.-W. Liu, C. Zarate, R. Martin, Angew. Chem., Int.
Ed., 2019, 58, 2064; (c) S. Mallick, P. Xu, E.-U. Wgrthwein, A.
Studer, Angew. Chem., Int. Ed., 2019, 58, 283.
For selected references of C−H silylation reactions, see: (a) E.
M. Simmons, J. F. Hartwig, J. Am. Chem. Soc., 2010, 132
,
17092; (b) C. Cheng, J. F. Hartwig, Science, 2014, 343, 853; (c)
N. Gandhamsetty, S. Park, S. Chang, J. Am. Chem. Soc., 2015,
137, 15176; (d) Q. Yin, H. F. T. Klare, M. Oestreich, Angew.
Chem., Int. Ed., 2016, 55, 3204.
For selected references of C−CN silylation reactions, see: (a) M.
Tobisu, Y. Kita, N. Chatani, J. Am. Chem. Soc., 2006, 128, 8152;
(b) M. Tobisu, Y. Kita, Y. Ano, N. Chatani, J. Am. Chem. Soc.,
2008, 130, 15982.
For selected references of C−O silylation reactions, see: (a) C.
Zarate, R. A. Martin, J. Am. Chem. Soc., 2014, 136, 2236; (b) C.
Zarate, M. Nakajima, R. A. Martin, J. Am. Chem. Soc., 2017, 139
1191.
8
9
32 (a) T. Komiyama, Y. Minami, T. Hiyama, Angew. Chem., Int. Ed.,
2016, 55, 15787; (b) M. Shibata, H. Ito, K. Itami, Chem. Lett.,
2017, 46, 1701.
33 (a) P. D. Raddo, M. Diksic, D. J. Jolly, Chem. Soc., Chem.
,
Commun., 1984, 3, 159; (b) R. B. Miller, M. I. Al-Hassan, J. Org.
Chem., 1985, 50, 2121.
10 (a) L. J. Goossen, N. Rodríguez, K. Gooßen, Angew. Chem., Int.
Ed., 2008, 47, 3100; (b) W. I. Dzik, P. P. Langea, L. J. Gooßen,
34 V. Morra, P. Davit, P. Capra, M. Vincenti, A. D. Stilo, F. Botrè, J.
Chromatogr. A, 2006, 1135, 219.
Chem. Sci., 2012, 3, 2671; (c) R. Takise, K. Muto, J. Yamaguchi,
Chem. Soc. Rev., 2017, 46, 5864; (d) T. Patra, D. Maiti, Chem.
Eur. J., 2017, 23, 7382; (e) L. Guo, M. Rueping, Acc. Chem. Res.,
35 G. S. Lal, G. P. Pez, R. J. Pesaresi, F. M. Prozonic, H. Cheng, J.
Org. Chem., 1999, 64, 7048.
36 L. C. Allen, J. Am. Chem. Soc., 1989, 111, 9003.
37 Y.-R. Luo, Comprehensive Handbook of Chemical Bond
Energies, CRC Press, Boca Raton, FL, 2007.
2018, 51, 1185; (f) L. Guo, M. Rueping, Chem. Eur. J., 2018, 24
7794.
,
11 J. D. Rich, J. Am. Chem. Soc., 1989, 111, 5886.
12 L. Guo, A. Chatupheeraphat, M. Rueping, Angew. Chem., Int.
Ed., 2016, 55, 11810.
13 X. Pu, J. Hu, Y. Zhao, Z. Shi, ACS Catal., 2016,
6, 6692.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
RSC Author Templates - ChemDraw (CDX) - Graphical Abstracts
All text and images must be placed within the frame.
Ni(cod)2 (10 mol %)
CuF2 (30 mol %)
PPh3 (40 mol %)
KF (3 equiv)
O
SiR3
R3Si Bpin
+
F
R
toluene
R
150 oC, 24 h
22 examples
(SiR3 = SiEt3, SinPr3, SiMeEt2, SiMe2tBu, SiMe2Ph)
50-96% yields
A transformation of aroyl fluorides with silylboron via nickel/copper-
cocatalysed carbon-fluorine bond cleavage and sequential
a
decarbonylation, which provides an efficient protocol to functionalize
arylsilanes, has been disclosed.
View Article Online
DOI: 10.1039/C9CC05325E