Dicarbonylative benzannulation of 3-acetoxy-1,4-enynes with CO and silylboranes by Pd and Cu cooperative catalysis: One-step access to 3-hydroxyarylacylsilanes

Article abstract of DOI:10.1039/c9cc09077k

A new, general Pd/Cu-cocatalysed dicarbonylative benzannulation of 3-acetoxy-1,4-enynes with CO and silylboranes is described. The method utilizes CO as both a one-carbon (C1) unit and an external addition functional reagent to achieve an unprecedented dicarbonylative benzannulation process, and represents a facile, efficient route to 3-hydroxyarylacylsilanes. Mechanistically, the silyl-Cu intermediate formed from CuF₂ and silylboranes, and silyl-Pd intermediate generated by transmetallation are two key factors for successfully targeting the reaction and selectivity.

Full text of DOI:10.1039/c9cc09077k

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DOI: 10.1039/C9CC09077K
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Dicarbonylative Benzannulation of 3-Acetoxy-1,4-enynes with CO
and Silylboranes by Pd and Cu Cooperative Catalysis: One-Step
Access to 3-Hydroxyarylacylsilanes
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Li-Jun Wu,ab‡ Liang-Feng Yang,ab‡ Jin-Heng Li*abc and Qiu-An Wang*a
strategies that offer differently site-selective access to diverse
unprotected functional group-substituted arylacylsilanes.
Transition-metal-catalysed carbonylative benzannulation of
enynes is a powerful tool that utilizes CO as a C1 resource for
the de novo construction of the phenolic frameworks,
particularly meta-functionalized variations.7,8 For example,
A new, general Pd/Cu-cocatalysed dicarbonylative benzannulation
of 3-acetoxy-1,4-enynes with CO and silylboranes is described. The
method utilizes CO as both a one-carbon (C1) unit and an external
addition functional reagent to achieve an unprecedented
dicarbonylative benzannulation process, and represents a facile,
efficient access to 3-hydroxyarylacylsilanes. Mechanistically, silyl-
Cu intermediate formed from CuF2 and silylboranes, and silyl-Pd
intermediate generated by transmetallation are two key factors
for successfully targeting the reaction and selectivity.
resorcinols were prepared by
a Rh-catalysed carbonylative
benzannulation of 3-acyloxy-1,4-enynes with CO (50-80 atm) via
intramolecular 1,2-acyloxy shift [Scheme 1a(i)].8a-b. Tang8c-d have
established an inherent amido addition strategy to assemble 9H-
carbazol-2-ols by Rh-catalysed carbonylative benzannulation of
3-(2-aminophenyl)-3-hydroxy-1,4-enynes with CO (1 atm)
[Scheme 1a(ii)]. However, these events are primarily limited to a
nucleophilic functional group intramolecular incorporation
mode. To enable intermolecular incorporation of functional
groups, we recently developed a mechanistically novel Pd
reductive catalysis for the carbonylative benzannulation of 3-
acetoxy-1,4-enynes with CO (1 atm) and hydrosilanes leading to
phenols, where a hydride source is needed to promote reductive
elimination of the vinyl-Pd(II)-OAc intermediate A (Scheme
1b).8e We reasoned that formation of meta-silyl phenolic
frameworks via the carbonylative benzannulation of 3-acetoxy-
1,4-enynes, CO and silylboranes could be addressed by utilizing
a suitable catalytic system to form the silyl-[M] intermediate B9
followed by transmetallation with the intermediate A to afford
the C-Pd-Si intermediate C that would readily undergo reductive
elimination.
Herein, we report the first example of a single-pot Pd/Cu-
cocatalysed dicarbonylative benzannulation of 3-acetoxy-1,4-
enynes with CO and silylboranes for producing 3-hydroxyarylacyl-
silanes through intermolecular incorporation of silyl-containing
functional groups under Lewis base-free conditions9 (Scheme 1c).
The reaction enables the formation of four new bonds, including
two C-C bonds, a C-Si bond and a O-H bond, to assemble valuable 3-
hydroxyarylacylsilanes, wherein CO serves as both a one-carbon (C1)
unit and an external addition functional reagent.
Organosilanes,1 including acylsilanes,2 are a class of unique
compounds that existed in bioactive molecules, materials and
endowed with versatile reactivity profiles in synthesis due to
their favorable bioactivity, reactivity and unusual spectroscopic
properties. For these reasons, methods for the preparation of
the acylsilane motif have been extensively exploited2-6 and the
elegantly robust procedures involve the silylation of carboxylic
acid derivatives (e.g., acids, acyl chlorides, esters, amides),3
hydroboration/oxidation of alkynylsilanes,4 transformations of
dithianes or benzotriazoles.5 However, these processes suffer
from modest functional group compatibility, limited substrate
scope and/or stoichiometric amounts of wastes (e.g., halogens,
Li+). To address these issues, transition-metal-catalysed C-H
functionalization of the pre-existing acylsilane motif has been
developed.6 However, such events most are restricted to the
introduction of functional groups into ortho position to
arylacylsilanes, and remain a highly challenging task for meta-
selectivity beyond the strategies that enable silylation of the
meta-prefunctionalized and protected phenols because the
hydroxy group is an ortho/para-orientating group. Thus, there is
an urgently fundamental need for developing general synthetic
a State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University,
Changsha 410082, China
b Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources
Recycle, Nanchang Hangkong University, Nanchang 330063, China
c State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou
730000, China
Initially, 1,5-diphenylpent-1-en-4-yn-3-yl acetate 1a, CO and
silylborane 2a were chosen to optimize conditions for the
dicarbonylative benzannulation reaction (Table 1). The reaction
of enyne 1a with CO, silylborane 2a, 10 mol% of Pd(PPh3)2Cl2
E-mail: jhli@hnu.edu.cn, wangqa@hnu.edu.cn
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
‡ These authors contributed equally to this work.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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a) Previous work via Rh catalysis:
(i) intramolecular 1,2-acyloxy shift
14
CuOAc instead of CuF2
toluene instead of PhCF3
MeCN instead of PhCF3
at 55 oC
43
(ii) dehydroxylation/intramolecular nucleophilic N-addition
View Article Online
R2
15
16
62
DOI: 10.1039/C9CC09077K
R2
R1
OR
H
R4
CO
RO
R1
CO
[Rh]
38
52
70
70
R2
R1
[Rh]
R2
R1
R2
R1
NBoc
R3
NBoc
R3
,
Rh
17
R3
OR
18
at 65 oC
1
OH
H
Rh
CO
[Pd]
R = Ac, Piv, Bz R3 = R4 = H
b) Our Previous Pd reductive catalysis:
19d
none
OH
R = H R4 = 2-NHBocC6H4
[Rh] = [{RhCl(CO)2
}
]
2
a
Reaction conditions: 1a (0.2 mmol), CO (1 atm), 2a (2 equiv),
H
R2
R1
Pd
R3
R2
OR
HSiR'3
Hydride-prompted reductive elimination/
intermolecular electrophilic H-addition
Pd(PPh3)2Cl2 (10 mol%), CuF2 (20 mol%), PhCF3 (2 mL), 60 oC and
12 h. b Isolated yield. c PPh3 (20 mol %). d 1a (1 mmol) and PhCF3
(4 mL) for 24 h.
R3
R1
R = H, Ac, Piv, Bz
R4 = H
O
OH
A
c) This work: Pd/Cu cooperative catalysis
R4
Si CuX
CuX2
R4
R4 Si
R5
O
O
?
R4
transmetallation/reductive elimination/
intermolecular nucleophilic Si-addition
B
O
O
R5
B
2
XB
Having establishing the optimal conditions, we set out to
investigate the generality of this dicarbonylative benzannulation
reaction with regard to 3-acetoxy-1,4-enynes 1 and silylboranes
2 (Table 2). For 3-acetoxy-1,4-enynes 1, the substitution effect
at the terminal alkyne was initially examined. A wide range of
aryl substituents at the terminal alkyne could be either electron-
donating (e.g., 4-MeC6H4, 4-MeOC6H4, 4-FC6H4, 4-ClC6H4, 4-
BrC6H4, 3-ClC6H4 and 2-ClC6H4) or electron-withdrawing (e.g., 4-
CF3C6H4), providing 3ba-ia in moderate to good yields. Notably,
the reactivity was influenced by the steric hindrance of the aryl
ring: While 4-ClC6H4- or 3-ClC6H4-possessing enynes led to 3ea
and 3ha, respectively, in 71% and 63% yields, 2-ClC6H4-
substituted enyne tendered 3ia in diminishing yield. Importantly,
the biologically relevant molecule estrone-containing enyne was
X = F, OAc
CuX(OR)
R2
SiR42R5
O
CO
Pd
R2
R1
R2
R1
R4
R4
Pd
Si
O
Si
R4
R4
Pd0
R1
R3
R5
R3
R2
R5
O
O
OH
C
D
3
Lewis base-free
cascade of dehydroxylation/dicarbonylation/silylation
Pd/Cu-cocatalysed access to meta-silane-based group-substituted phenols
Scheme 1. Carbonylative benzannulation of 3-acetoxy-1,4-enynes
with CO.
and 20 mol% of CuF2 in PhCF3 at 60 oC for 12 h proved to be optimal,
affording the desired 3-hydroxyarylacylsilane 3aa in a 73% yield
(entry 1). The reason might be because the strong electron-
withdrawing nature of CF3 group would coordinate the radical
intermediate to adjust its electronic property and activate it. Both
Pd(PPh3)2Cl2 and CuF2 played a critical role in the reaction, as lack of converted successfully into complex phenol 3ja.10 Thiophen-2-yl
alkyne also performed well (3ka). Aliphatic alkyne was a suitable
substrate for accessing 3la. However, terminal alkyne 1m was
any one resulted in no formation of 3aa (entry 2). Moreover, brief
screening of the Pd(PPh3)2Cl2 and CuF2 loadings revealed a catalytic
system consist of 10 mol% of Pd(PPh3)2Cl2 and 20 mol% of CuF2 as
the best choice (entries 3, 4, 10, and 11). Replacement of
Pd(PPh3)2Cl2 with PdCl2, Pd(OAc)2, Pd(dba)2 or Pd(PPh3)4 led to
diminishing yields (entries 5-9). Other Cu catalysts, such as Cu(OAc)2,
CuCl2 and CuOAc, also exhibited high catalytic activity, albeit
stunting the formation of 3aa slightly (entries 12-14). While toluene
is also effective for the reaction (entry 15), MeCN showed lower
reactivity (entry 16). Lowering or raising temperature decreased the
yield of 3aa slightly (entries 17 and 18). Gratifyingly, the standard
conditions were applicable to a scale up to 1 mmol of 1a, giving 3aa
in high yield (entry 19).
Table 2. Synthesis of 3-Hydroxyarylacylsilanes (3)a
O
R5
OR
R2
R1
R4
R4
Pd (PPh3)2Cl2 (10 mol%)
CuF2 (20 mol%)
PhCF3, 60 oC, 12 h
R4
R4 Si
R5
R2
R1
O
O
Si
CO
+
B
+
R3
O
R3
1
2
O
H
3
O
O
Ph
Si
Ph
Ph
Si
R' = Me, 3ba, 66%
R' = MeO, 3ca, 73%
R' = F, 3da, 69%
R' = Cl, 3ea, 71%
R' = Br, 3fa, 70%
R' = CF3, 3ga, 63%
Si
Cl
Ph
Ph
Ph
O
O
O
H
Cl
H
H
R'
3ia, 45%
R' = Cl, 3ha, 63%
Ph
O
O
O
Ph
Si
Ph
Si
H
Si
H
O
H
Table 1 Screening of optimal reaction conditionsa
Ph
Ph
O
Ph
Ph
O
O
S
O
H
H
H
3ja, 68% (estrone derivative)
3la, 51%
3ka, 46%
O
O
O
OAc
Ph
Si
Ph
O
Ph
Si
Ph
Si
Pd (PPh3)2Cl2 (10 mol%)
CuF2 (20 mol%)
PhCF3, 60 oC, 12 h
O
O
Si
H
OMe
+
CO
+
Si
B
R'' = Me, 3na, 66%
R'' = MeO, 3oa, 71%
R'' = Cl, 3pa, 68%
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2a
O
1a
O
O
H
O
H
H
3aa
R''
H
3qa, 63%/61%b
3ma, trace
O
O
O
Ph
Si
O
Ph
Si
Ph
Si
Ph
Si
Entry
Variation from the standard conditions
Yield (%)b
1
2
none
73
0
Ph
H
Ph
Ph
Ph
Ph
Ph
O
without Pd(PPh3)2Cl2 or CuF2
Pd(PPh3)2Cl2 (5 mol %)
Pd(PPh3)2Cl2 (15 mol %)
O
O
H
O
H
H
H
3ra, 57%
3sa, 42%
3ta, 46%
3
29
63
64
15
34
42
53
63
35
69
60
3ua, trace
O
Ph
Si
4
O
O
O
Et
5
PdCl2/PPh3 (20 mol %) instead of Pd(PPh3)2Cl2
PdCl2 instead of Pd(PPh3)2Cl2
Pd(OAc)2 instead of Pd(PPh3)2Cl2
Pd(dba)2 instead of Pd(PPh3)2Cl2
Pd(PPh3)4 instead of Pd(PPh3)2Cl2
CuF2 (10 mol %)
Si
SiEt3
Si
Ph
Ph
6
Ph
Ph
Ph
Ph
O
Ph
Ph
7c
8c
9
H
O
O
O
R = H, 3aa, 19%
R = Piv, 3aa, 45%
H
H
H
3ab, 66%
3ac, 71%
3ad, 35%
a
Reaction conditions: 1 (0.2 mmol), CO (1 atm), 2 (2 equiv),
Pd(PPh3)2Cl2 (10 mol%), CuF2 (20 mol%), PhCF3 (2 mL), 60 oC and
12 h. (E)-isomer gave 63% yield and (Z)-isomer afforded 61%
10
11
12
13
CuF2 (100 mol %)
b
Cu(OAc)2 instead of CuF2
yield.
CuCl2 instead of CuF2
2 | J. Name., 2012, 00, 1-3
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inert, and >95% of which was recovered (3ma). We next evaluated
3-acetoxy-1,4-enynes 1 with the substitution effect at the terminal
alkenes. Several aryl groups (e.g., 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4,
2-MeOC6H4) at the terminal alkene were perfectly tolerated (3na-
qa). It was noted that either (Z)- or (E)-enynes proceeded well to
give same results (3qa), supporting this reaction as a kinetic control
approach. Both aliphatic and terminal alkenes were accommodate
(3ra-sa). Using 2-methyl-substituted enyne also succeeded in
accessing 3ta. However, 3-methyl-substituted enyne was inert (3ua).
Replacement of the OAc with either OH or OPiv decreased the
reactivity (3aa). Pleasingly, the reaction was applicable to
substrate scope. Mechanistically, by utilizing CuF2 and a silylborane
DOI: 10.1039/C9CC09077K
to afford the active Cu-Si intermediate and transmetallation, the
View Article Online
putative new-formed C-Pd-Si complex intermediate might be
generated and exhibits high reactivity to allow the second CO
insertion. Notably, a facile, successful combination of the phenolic
moieties and the bioactive structural systems illustrates the
potential synthetic application of this methodology.
We thank the National Natural Science Foundation of China
(Nos. 21625203 and 21871126) for financial support. L.-J. Wu also
thanks the Presidential Scholarship for Doctoral Students and the
Hunan Provincial Innovation Foundation for Postgraduate
(CX2018B183).
(ethyldimethylsilyl)borane,
(triethylsilyl)borane
and
(tri-n-
butylsilyl)borane, affording 3ab-ad in good yields.
The control experiments showed that both the reported 2'-
hydroxy-[1,1':3',1''-terphenyl]-4'-yl acetate8e (Eq. 1; Scheme 3) and
product 4aa (Eq. 2) were not the intermediates for this this Pd/Cu-
cocatalysed dicarbonylative benzannulation protocol. Consequently,
the possible mechanisms for this Pd/Cu-cocatalysed dicarbonylative
benzannulation protocol were proposed in Scheme 3.7-9 Oxidative
addition of the active Pd(0) species with the allyl acetate 1a forms
the allyl-Pd(II) intermediate A’ 7,8 that is supported by the formation
of allene 4aa without CO.9b Insertion of CO into the intermediate A’
at the benzylic position affords the acyl Pd(II) intermediate A’’,
followed by annulation to produce the stable vinyl-Pd(II)-OAc
intermediate A. Transmetallation between the intermediate A and
the Cu-Si intermediate B9 delivers the C-Pd-Si intermediate C. The
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
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(e) M. Birot, J.-P. Pillot and J. Dunogues, Chem. Rev., 1995, 95,
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W. Bains and R. Tacke, Curr. Opin. Drug Discov. Dev., 2003, 6,
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R. Ramesh and D. S. Reddy, J. Med. Chem., 2018, 61, 3779; (n)
J. Pesti and G. L. Larson, Org. Process Res. Dev., 2016, 20,
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For reviews and selected recent papers, see: (a) P. C. B. Page,
S. S. Klair and S. Rosenthal, Chem. Soc. Rev., 1990, 19, 147; (b)
A. F. Patrocinio and P. J. S. Moran, J. Braz. Chem. Soc., 2001,
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25: Acylsilanes, in: Science of Synthesis, (Ed.: I. Fleming),
Georg Thieme Verlag, Stuttgart, 2001, Vol. 4, pp 513–568; (d)
H.-J. Zhang, D. L. Priebbenow and C. Bolm, Chem. Soc. Rev.,
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and C. Bolm, Angew. Chem., Int. Ed., 2014, 53, 269; (f) J.
Rong, R. Oost, A. Desmarchelier, A. J. Minnaard and S. R.
Harutyunyan, Angew. Chem., Int. Ed., 2015, 54, 3038; (g) J.
González, J. Santamaría and A. Ballesteros, Angew. Chem.,
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Lee and C.-H. Tan, J. Am. Chem. Soc., 2018, 140, 1952.
intermediate
C undergoes the second CO insertion, which
sequentially undergoes reductive elimination and isomerization
cascades to afford 3aa and regenerate the active Pd(0) species.
O
CO
Ph
Si
OAc
Ph
Pd (PPh3)2Cl2 (10 mol%)
CuF2 (20 mol%)
O
O
+
5
Si
B
+
(1)
(2)
PhCF3, 60 oC, 12 h
Ph
Ph
>95%
Ph
Ph
Ph
OH
5
2a
OH
3aa, 0%
O
CO
Ph
Pd (PPh3)2Cl2 (10 mol%)
CuF2 (20 mol%)
PhCF3, 60 oC, 12 h
O
O
Si
Si
B
+
4aa
>92%
+
Ph
SiPhMe2
Ph
Ph
Ph
2a
4aa
O
H
3aa, 0%
O
O
OAc
Ph
Si
Ph
Si
Isomerization
Ph
Pd0Ln
Ph
2
Ph
Ph
Ph
Ph
1a
O
O
O
E
H
Si
3aa
2a
Pd
Ph
Pd
Ph
Ph
OAc
Ph
Ph
A'
Without
CO
Ph
O
Ph
SiPhMe2
D
CO
CO
4aa, 46%
Pd
Ph
Si
Ph
Ph
Ph
Pd
Ph
O
O
OAc
O
O
C
AcO
B
Pd
A''
+
[CuII]
O
OAc
O
O
Ph
Ph
Si CuII
Si
B
+ [CuII]
+
B
Ph
O
Ph
O
B
A
2a
Scheme 3. Control experiments and possible mechanisms
.
3
For representative papers, see: (a) J. Yoshida, S. Matsunaga,
Y. Ishichi, T. Maekawa and S. Isoe, J. Org. Chem., 1991, 56,
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Torvisco, H. Stueger and C. Grogger, Phosphorus, Sulfur
Silicon Relat. Elem., 2016, 191, 638.
In summary, we have developed the first Pd/Cu-cocatalysed
three-component dicarbonylative benzannulation reaction of 3-
acetoxy-1,4-enynes with CO by using silylboranes as external Si-
nucleophile resources. This reaction enables the preparation of 3-
hydroxyarylacylsilanes with excellent regio- and chemo-selectivity,
and features excellent functional group tolerance and a broad
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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4
For representative papers, see: (a) J. A. Miller and G. Zweifel,
View Article Online
DOI: 10.1039/C9CC09077K
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K. Oshima, Org. Lett., 2006, 8, 1185; (d) A. Nikolaev and A.
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5
For representative papers, see: (a) A. G. Brook, J. M. Duff, P.
F. Jones and N. R. Davis, J. Am. Chem. Soc., 1967, 89, 431; (b)
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