Nickel-Catalyzed Decarbonylative Borylation and Silylation of Esters

Article abstract of DOI:10.1021/acscatal.6b01956

The nickel-catalyzed direct borylation and silylation of phenolic esters has been established. The key to this highly efficient acyl C-O bond borylative and silylative cleavage depends on the appropriate choice of different ligands and additives in the pr

Full text of DOI:10.1021/acscatal.6b01956

Subscriber access provided by CORNELL UNIVERSITY LIBRARY
Article
Nickel-Catalyzed Decarbonylative Borylation and Silylation of Esters
Xinghui Pu, Jiefeng Hu, Yue Zhao, and Zhuangzhi Shi
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b01956 • Publication Date (Web): 30 Aug 2016
Downloaded from http://pubs.acs.org on August 31, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Catalysis is published by the American Chemical Society. 1155 Sixteenth Street
N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 22
ACS Catalysis
Nickel-Catalyzed Decarbonylative Borylation and Silylation of Esters
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
†
†
Xinghui Pu, Jiefeng Hu, Yue Zhao, and Zhuangzhi Shi*
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China
ABSTRACT: A nickelꢀcatalyzed direct borylation and silylation of phenolic ester has been established. The key to this highly effiꢀ
cient acyl CꢀO bond borylative and silylative cleavage depends on the appropriate choice of different ligands and additives in presꢀ
ence of nickel catalyst. Both transformations exhibit good functional group compatibility and can serve as powerful synthetic tools
for lateꢀstage functionalization of complex compounds. The elucidation of key mechanistic features of this newly developed acyl Cꢀ
O bond activation in esters was confirmed by two wellꢀcharacterized organonickel(II) intermediates.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
KEYWORDS: nickel, borylation, silylation, esters, decarbonylation
INTRODUCTION
The transitionꢀmetalꢀcatalyzed functionalization of unreactive
bonds is one of the most powerful protocols for practitioners
1
in chemical synthesis. Esters are widely found in broad range
of organic molecules, including pharmaceuticals, agrochemiꢀ
cals and organic materials, and their selective functionalization
represents a challenge in the field of organometallic chemistry.
The utilization of esters in the crossꢀcoupling process is meanꢀ
ingful not only because of avoiding formation of toxic wastes
such as halide salts, but also it opens access to a vast number
of nonꢀtoxic and readily available esters and the precursor
carboxylic acids. Among various transitionꢀmetals, nickel
2
catalysis play a dominant role in CꢀO bond activation process
3
in esters. In the early of 1980, Yamamoto et al. demonstrated
the first stoichiometric Ni(0)ꢀmediated decarbonylation of aryl
4
carboxylates via acyl metal species formation. In recent years,
the utilization of acyl CꢀO electrophiles in Niꢀcatalyzed crossꢀ
coupling reactions has received considerable attention. Itami
and Yamaguchi et al. reported important decarbonylative couꢀ
Figure 1. Nickel-Catalyzed Ester C-O Bond Functionaliza-
tion
1
3ꢀ14
15
and silylation of unreactive bonds such as CꢀH,
CꢀN, Cꢀ
16
17
18
5
O , CꢀF and CꢀC bonds has shown promises because it
confers synthetic versatility of such inert functional groups.
For instance, Martin and coꢀworkers developed Niꢀcatalyzed
pling reactions of phenolic esters with 1,3ꢀazoles and arylꢀ
boronic acids via nickelꢀcatalyzed CꢀO bond cleavage (Figure
a & b). Garg and Houk et al. also revealed the first catalytic
6
1
19
20
borylative and silylative cleavage of CꢀOMe bonds in aryl
ethers. Most recently, we have also explored an efficient Niꢀ
catalytic system, which is capable of activating amide C–N
bonds for decarbonylative borylation to produce various orꢀ
ganoboronates. Despite these reported advances, decarbonylꢀ
ative borylation and silylation process of ester CꢀO bonds have
been virtually unexplored.
method to synthesize anilide products via activating the meꢀ
thyl ester CꢀO bonds. Interestingly, decarbonylation process
7
does not occur in their reactions (Figure 1c). Although the
events of these Niꢀcatalyzed reactions were supported by DFT
21
6
ꢀ7
calculation, there are still many fundamental issues need to
be clarified. (1) The transient acylnickel species in these transꢀ
formations has never been structurally characterized to conꢀ
firm CꢀO bond cleavage step; (2) The essential difference beꢀ
tween decarbonylative and nonꢀdecarbonylative processes
need to be investigated; (3) More diversified reactions have
not been developed.
Herein, we report the first Nickelꢀcatalyzed
decarbonylative borylation and silylation reaction of ester
by acyl CꢀO bond cleavage. Remarkably, this
transformation is to cleave a stable ester C−O bond while
forming an easily transformable C−B or CꢀSi bond.
Moreover, this new CꢀB or CꢀSi bond crossꢀcoupling can
be accomplished in high yields with a broad scope of
phenolic esters, w the further Suzuki–Miyaura or Hiyama
8
9
Organoꢀboron and silicon compounds are significantly
valuable synthetic intermediates with considerable interest in
modern organic synthesis. They are usually prepared from
Grignard or organolithium reagents, processes that are not
compatible with numerous functional groups according to the
6, 22
coupling
with unconsumed esters. In light of the
10
importance of esters and the advantages offered by nickel
catalysis, we expect that this concept will provide an
efficient strategy for the application of ubiquitous esters
traditional routes. Alternatively, the development of transiꢀ
tionꢀmetalꢀcatalyzed crossꢀcouplings of organohalides with
1
1
12
diborons or disilanes has allowed the synthesis of these
compounds under mild conditions. Remarkably, borylation
ACS Paragon Plus Environment

ACS Catalysis
Page 2 of 22
as unconventional electrophiles in synthesis of organoꢀ
boron and silicon compounds.
Table 2. Ni-catalyzed Decarbonylative Borylation of Phe-
nolic Esters
a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
RESULTS AND DISCUSSION
Nickel-catalyzed decarbonylative borylation of
esters: Initial studies involved the evaluation of the
borylation of phenyl 1ꢀnaphthoate (1a) with B (nep) (2a
)
2
2
(Table 1). In the presence of 5.0 mol% Ni(COD) , 10
2
mol% NHC ligand L1 and 2.0 equiv NaF as additive, at
o
1
60 C under an Ar atmosphere in 1,4ꢀdioxane. We
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
indeed observed the desired product 3a in trace amount
after 12 h in GCꢀMS (entry 1). Under these conditions,
Na PO works better than NaF (entry 2) and 21% yield
3
4
was observed by employing Na CO as the base (entry 3).
2
3
Among other NHC ligands L2-L4, a dramatic effect of
ICyꢁHCl (L3) was observed with 71% yield of 3a (entry
5). We next turned our attention to phosphine ligands, and
found that the former success with ligands for activating
23
t
aryl CꢀO bonds such as PCy3 (L5), P Bu (L6), dcype
3
Table 1. Optimizaion of Decarbonylative Borylation Pro-
a
cess
additives
(equiv)
yield
(%)
a
entry
[Ni]
L
b
Reaction conditions A: 1 (0.20 mmol), 2a (0.80 mmol), 5 mol%
t
of Ni(COD) , 10 mol% of L3, 10 mol% of NaO Bu, 2.0 equiv of
Na
2
o
1
2
3
4
5
6
7
8
9
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
L1
L1
L1
L2
L3
L4
L5
L6
L7
L8
NaF (2.0)
8
15
21
9
2
CO
3
, 2.0 equiv of NaCl in dioxane (2.0 mL), at 160 C, 12 h,
under Ar; Isolated yields.
Na PO (2.0)
3
4
5, 24
(L7)
and dppe (L8) were ineffective for the present decarꢀ
Na CO (2.0)
2
3
bonylative borylation coupling (entries 7ꢀ10). When both
Na CO and NaCl (1:1) were added as the additives, we
Na CO (2.0)
2
3
2
3
Ni(COD)2
Na CO (2.0)
2
3
71
0
achieved better yield improving up to 81% (entry 11). Other
airꢀstable nickel sources such as Ni(PCy Cl and anhydrous
Ni(COD)2
Na CO (2.0)
3
)
2
2
2
3
Ni(OAc) was also proven successful in this coupling reaction
2
Ni(COD)2
Na CO (2.0)
6
2
3
with a high reactivity (entries 12ꢀ13). We also examined the
o
Ni(COD)2
Na CO (2.0)
2
3
4
ttemperature effect and lower temperature (140 C) was found
Ni(COD)2
Na CO (2.0)
32
15
to be not optimal (entry 14). Notably, increasing the Ni(COD)
2
2
3
loading to 10 mol% still resulted in a similar yield (entry 15),
and no product was observed in the absence of Ni catalyst
(entry 16).
1
1
1
0
1
2
Ni(COD)2
Na CO (2.0)
2 3
c
Ni(COD)2 L3 Na CO (2.0) + NaCl (2.0) 81 (78)
2
3
Ni(PCy ) Cl L3 Na CO (2.0) + NaCl (2.0)
66
62
74
82
0
3 2
2
2
3
To evaluate the utility of this decarbonylative
borylation reaction, a series of esters have been carried
out (Table 2). As shown, a wide range of electronically
and sterically diverse arene carboxylic acid esters underꢀ
13
Ni(OAc)2
L3 Na CO (2.0) + NaCl (2.0)
2 3
d
1
4
5
Ni(COD)2
Ni(COD)2
ꢀ
L3 Na CO (2.0) + NaCl (2.0)
2 3
e
1
L3 Na CO (2.0) + NaCl (2.0)
2
3
went crossꢀcoupling with B nep2
(
2a) in moderate to
excellent yields. Polyaromatic substrates, including
naphthalenes (3a 3d) and 9 ꢀfluorene (3e) were also
2
1
6
L3 Na CO (2.0) + NaCl (2.0)
2 3
ꢀ
H
shown to exhibit high levels of reactivity. The
chemoselectivity profile of this method was nicely
illustrated by the fact that ethers (3d
,
3fꢀ3h), amines (3i)
and fluorocontaining compounds (3j
ꢀ3k) could all be
equally accommodated to synthesize the desired products.
The unique selectivity toward phenolic ester was
corroborated by the presence of other types of esters such
as ꢀCOOMe group (3l). Decarbonylative borylation of
phenyl [1,1'ꢀbiphenyl]ꢀ2ꢀcarboxylate (1m) satisfactorily
provided desired product 3m in 61% yield, inspite of the
steric hindrance from the orthoꢀphenyl group. Moreover,
a
Reaction conditions: 1a (0.20 mmol), 2a (0.80 mmol), 5 mol% of
t
catalyst, 10 mol% of ligand,10 mol% of NaO Bu (only in L1ꢀL4),
o
2.0 equiv of base in dioxane (2.0 mL), at 160 C, 12 h, under Ar.
b
c
d
o
e
Determined by GC analysis. Isolated yield. At 140 C. Using
0 mol% Ni(COD) and 20 mol% L3.
1
2
ACS Paragon Plus Environment

Page 3 of 22
ACS Catalysis
2
5
a wide variety of πꢀextended systems, participated in the
reaction to afford borylation products 3n 3s in moderate
to high yields. Among them, the presence of substituted
oxygenꢀcontaining heterocycles (3r 3s) did not interfere
Table 4. Ni-catalyzed Decarbonylative Silylation of Phenolic
Esters
a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
ꢀ
ꢀ
with productive C–B bond formation. These methods
suggested that using a nickel catalyst in combination with
a highly nucleophilic boron reagent is a promising
approach to achieve the desired decarbonylative
borylation of esters.
Nickel-catalyzed decarbonylative silylation of esters.
After successful synthesis of arylboronates, we enviꢀ
sioned that aryl silanes could also be derived by a CꢀSi
bondꢀforming event via the decarbonylative process under
certain reaction conditions. Our investigation commenced
with the cross coupling of phenyl 1ꢀnaphthoate (1a) and
silylborane 2a to give triethyl(naphthalenꢀ1ꢀyl)silane (4a).
During experimentation to optimize the reaction condition,
the best results were obtained with a catalytic amount of
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
17c, 20, 26
Ni(COD) and CuF as a multimetallic system,
2
2
a
Reaction conditions B: 1 (0.20 mmol), 2b (0.50 mmol), 10 mol%
dcpye (L7) as the ligand and NaOAc as the additive in
of Ni(COD) , 20 mol% of L7,40 mol% of CuF , 3.0 equiv of
NaOAc, in toluene (1.0 mL), at 160 C, 48 h, under Ar; Isolated
yields.
2
2
toluene (Table 3, entry 1). Under these conditions, conꢀ
o
o
version was completed within 48 h at 160 C with 72%
isolated yield. Control experiments revealed that all reacꢀ
tion parameters were critical for the success (entries 2ꢀ5),
suggesting that a nucleophilic aromatic substitution pathꢀ
coupling of naphthoic acid derivatives was performed
very well to afford the desired products in good
efficiency, irrespective of the ester group location either
way may not be in effect. Lowering the Ni(COD) loading
2
to 5 mol% and L7 to 10 mol% resulted in a decreased
yields (entries 6ꢀ7). As expected, the nature of the ligand
played a critical role on the reactivity, the best ligand in
the borylation reaction (L3) provided 4a only in 18%
yield (entry 8). Moreover, a significant erosion in yield
at 1ꢀ or at 2ꢀpositions (4aꢀ4d). This Ni/Cuꢀcocatalyzed
silylation event could be even extended to the use of
simpler, yet challenging phenyl esters. For instance, the
ester (4l) and phenyl groups (4n) did not affect in desired
outcome of the process. In addition, the reaction of exꢀ
tended π systems can also afforded desired products 4oꢀ4s
in 56ꢀ66% yields.
Since most heteroarylboronates are inherently unstable,
which can’t be synthesized by this present Niꢀcatalyzed
method. However, a great variety of heteroaryl esters
can be transformed into the corresponding silanes under
the optimized reaction conditions (Table 5). Heteroaryl
esters bearing a benzofuran (4t), furan (4u), benꢀ
was observed when using anhydrous Ni(OAc) in this
2
reaction (entry 9). Interestingly, a slight decrease in temꢀ
perature gave a dramatic change in reactivity, providing
4
a
in 55% yield (entry 10).
2
7
a
Table 3. Optimization of Reaction Conditions
zo[b]thiophen (4v), thiophen (4w), quinolone (4x) and
pyridine (4y) which are often found in bioactive comꢀ
pounds, participated in the reaction, affording the correꢀ
sponding products in acceptable yields.
Table 5. Ni-Catalyzed Decarbonylative Silylation of Het-
eroaryl Esters
Yield of 4a
entry Variation from the “standard conditions”
b
(%)
c
1
2
3
4
5
6
7
8
9
none
without Ni(COD)2
without L7
78 (72)
a
0
0
without CuF2
0
without NaOAc
Using 5 mol% Ni(COD)2
10 mol% L7
trace
32
26
18
25
55
L3 instead of L7
Ni(OAc) instead of Ni(COD)
2
2
o
1
0
At 140 C
a
Reaction conditions: 1a (0.20 mmol), 2b (0.50 mmol), Ni(COD)2
a
(
10 mol%), L7 (20 mol%), CuF (40 mol%), NaOAc (0.6 mmol),
Reaction conditions B: 1 (0.20 mmol), 2b (0.50 mmol), 10 mol%
2
o
b
toluene (1.0 mL), 160 C, 48 h, under Ar. Determined by GC
analysis. Values in parentheses indicate isolated yield.
of Ni(COD) , 20 mol% of L7,40 mol% of CuF , 3.0 equiv of
NaOAc, in toluene (1.0 mL), at 160 C, 48 h, under Ar; Isolated
yields.
2
2
c
o
As outlined in Table 4, we have found that a broad
range of aryl rings can be selectively coupled with
silylborane 2a using this multimetallic system. The
ACS Paragon Plus Environment

ACS Catalysis
Late-stage decarbonylative borylation and silylation
Page 4 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
of Adapalene. Lateꢀstage modification of naturally sigꢀ
nificant molecules to access new bioactive compounds
2
8
has been an promising concept in organic chemistry.
Encouraged by this successful decarbonylative borylation
and silylation process, we also turned our attention to utiꢀ
lize the method as a key step for selective functionalizaꢀ
tion of a complex molecule, Adapalene
5, a secondꢀ
generation topical retinoid primarily used in the treatment
2
9
of mildꢀmoderate acne. This compound could be conꢀ
verted to the corresponding ester by the treatment of
PhOH in excellent yield. Under the standard condition A,
the formed ester could be subjected to decarbonylative
borylation with B (nep) (2a) to produce the arylboronate
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
2
2
Figure 2. Molecular Structure of 1a-I Shown with 30%
Probability Ellipsoids
7
in 61% isolated yield. Alternatively, this substrate can
also be subjected to standard condition B to take place the
decarbonylative silylation with silylborane 2a generating
arylsilane
8 in 84% yield (Scheme 1).
Figure 3. Molecular Structure of 1a-II Shown with 30%
Probability Ellipsoids
We prepared (1ꢀnaphthoyl)NiCl(ICy) (1aꢀI) by treatꢀ
2
ment of ester 1a with Ni(COD) , NHC ligand L3 andꢀ
NaO Bu in toluene at room temperature (Scheme 2). The
molecular structures of complexes 1a-I in the solid state
2
t
Scheme 1. Late-stage Decarbonylative Borylation and
Silylation of Adapalene.
Synthesis, isolation and identification of nickel in-
was shown in Figure 2, and the structure refinement data
are given in supporting information. In 1aꢀI, two carbene
termediates. Previously, we reported the synthesis of
II
0
acylnickel complexes from oxidative addition of Ni to
ligands are coordinated to nickel mutually in trans posiꢀ
tion to each other with one 1ꢀnaphthoyl group and a chloꢀ
rine atom, building up the formal coordination number to
4 and displaying a square planar geometry. Under these
conditions, the acyl CꢀO bonds of methyl ester 1a' seems
2
1
amide CꢀN bond. However, as a key intermediate, the
transient acylnickel species has never been structurally
II
characterized in acyl C–O bond cleavage. According the
above investigation, NHC ligand L3 is beneficial for the
Niꢀcatalyzed borylation of esters, but fundamental underꢀ
standing of the ligand effect on acyl C−O bond cleavage
has been limited by the challenges associated with the
infective to generate 1aꢀI through an oxidative addition
process. According to the DFT calculation from Garg,
Houk and coworkers, the addition of Lewis acid
II
t
isolation of acylnickel intermediates.
Al(O Bu)
3
can lower the kinetic barrier for activating the
7
acyl CꢀO bonds of methyl esters. To prove the theoretical
t
study, 1.25 equiv Al(O Bu) was added to the system and
the desired acylnickel species 1a
3
II
ꢀ
1
was indeed formed in
1
2% isolated yield. Furthermore, the decarbonylative proꢀ
cess was also observed. Complex 1a undergoes decarꢀ
bonylation to produce an arylnickel intermediate 1a II
ꢀ
1
ꢀ
o
with 85% isolated yield at 60 C. This complex was obꢀ
tained in pure form after column chromatography, which
was also confirmed by NMR and Xꢀray analysis (Figure
3). We next investigated the reactivity of this isolated
arylnickel complex towards the reversible path. Upon
heating at 60°C for 12 hours under 1 atm CO atmosphere,
complex 1a
acylnickel intermediate 1a
the stoichiometric reactions of complex 1a
ꢀ
II underwent carbonylation to produce
in high yield. Treatment of
II with B nep
Scheme 2. Stoichiometric Reactions of Ester 1a with
Ni(COD)2
ꢀI
ꢀ
2
2
ACS Paragon Plus Environment

Page 5 of 22
ACS Catalysis
o
in presence of Na CO and NaCl at 80 C in dioxane gave
that these two reactions have a lot of similarities (Figure
5). In this silylation process, the formed aryl nickel speꢀ
2
3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
the corresponding arylboronate 3a in 68% yield (Scheme
3a). Nickel complexes 1a and 1a II were also capable
of effecting the catalytic borylation approximately in
identical efficiency (Scheme 3bꢀ3d), suggesting the inꢀ
termediacy of these complexes in the catalytic cycle.
ꢀI
ꢀ
cies
C
undergoes transmetalation with in situ generated
, followed by a reductive
copper silane intermediate
D
elimination that delivers the final product and regenerates
0
the active Ni catalytic species.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 5. Proposed Catalytic Cycle Decarbonylative
Silylation of Esters
CONCLUSION
In summary, we have developed two efficient Niꢀ
catalyzed systems capable of activating ester C–O bonds
for decarbonylative borylation and silylation to produce
various aryl boronates and silanes. In view of the wideꢀ
spread ester group and its precursors in chemicals, this
method offers a meaningful tool to enable them as valuaꢀ
ble building blocks. The elucidation of key mechanistic
features of this newly developed reaction was confirmed
by two wellꢀcharacterized Ni intermediates. Further
mechanistic details of this borylation and silylation proꢀ
cess as well as expansion of the scope of the transforꢀ
mation are in progress in our laboratory.
Scheme 3. Studies Designed to Support the Mecha-
nism
On the basis of these investigations, we have hypotheꢀ
sized that the mechanism outlined in Figure 4 is operative
when ester
1 is employed as electrophile. This reaction
0
triggered by oxidative addition of the nickel catalyst into
II
ester C−O bond generates an cis acylnickel intermediate
30
A
.
This complex can easily undergo ligand exchange
ꢀ
with Cl (or other anionic reagents in the system such as
ꢀ
t
ꢀ
ASSOCIATED CONTENT
AcO , BuO ) generating trans acyl nickel species
lowed by decarbonylation to provide aryl nickel species
Decarbonylation of to trans aryl nickel species , folꢀ
B, folꢀ
C
.
Experimental procedures and full spectroscopic data for all new
compounds. This material is available free of charge via the Interꢀ
net at http://pubs.acs.org.
B
C
lowed by boryl transfer assisted by the base and subseꢀ
quent cis reductive elimination delivers the target product
AUTHOR INFORMATION
3
and regenerates the Ni(ICy) species.
2
Corresponding Authors
shiz@nju.edu.cn
Author Contributions
†
X.P and J.H contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank the “1000ꢀYouth Talents Plan”, the “Jiangsu Speciallyꢀ
Appointed Professor Plan”, NSF of China (Grant 21402086,
2
1401099), and NSF of Jiangsu Province (Grant BK20140594)
Figure 4. Proposed Catalytic Cycle for Decarbonyla-
tive Borylation of Esters
for financial support. This work was also supported by a Project
Funded by the Priority Academic Program Development of Jiangꢀ
su Higher Education Institutions.
Probably due to unstability of nickel intermediates usꢀ
ing dcype as the ligand in decarbonylative silylation of
esters, we could not isolate the desired acylnickel and
arylnickel intermediates at the current stage. Although
detailed mechanism requires further studies, we believe
REFERENCES
(
2
1) For recent reviews, see: (a) Pan, F.; Shi, Z.ꢀJ. ACS Catal. 2014, 4,
80ꢀ288. (b) Yu, D.ꢀG.; Li, B.ꢀJ.; Shi, Z.ꢀJ. Acc. Chem. Res. 2010, 43,
ACS Paragon Plus Environment

ACS Catalysis
Page 6 of 22
1
486ꢀ1495. (c) Nájera, C.; Sansano, J. M. Angew. Chem. Int. Ed. 2009,
wald, S. L. Org. Lett
Kallemeyn, J. M. Org. Lett
(13) For selected recent examples on CꢀH borylation reactions,
see: (a) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J.
.
2007
,
9
, 3785ꢀ3788. (e) Denmark, S. E.;
, 3483ꢀ3486.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
48, 2452ꢀ2456. (d) Murakami, M.; Ito, Y. in Activation of Unreactive
Bonds and Organic Synthesis (Ed.: S. Murai), Springer, Berlin, 1999,
p.97ꢀ129. (e) Rybtchinski, B.; Milstein, D. Angew. Chem. Int. Ed.
.
2003, 5
1
999, 38, 870ꢀ883. For selected recent examples on transitionꢀmetalꢀ
M.; Hartwig, J. F. Chem. Rev
F. Acc. Chem. Res 2012 45, 864ꢀ873. (c) Légaré, M.; Courꢀ
temanche, M.; Rochette, É.; Fontaine, F. Science 2015 349, 513ꢀ
16. (d) Larsen, M. A.; Wilson, C. V.; Hartwig, J. F. J. Am. Chem.
Soc 2015 137, 8633ꢀ8643. (e) Saito, Y.; Segawa, Y.; Itami, K. J.
Am. Chem. Soc 2015 137, 5193ꢀ5198. (f) Dombray, T.; Werncke,
C. G.; Jiang, S.; Grellier, M.; Vendier, L.; Bontemps, S.; Sortais, J.;
SaboꢀEtienne, S.; Darcel, C. J. Am. Chem. Soc 2015 137, 4062ꢀ
065. (g) Obligacion, J. V.; Semproni, S. P.; Chirik, P. J. J. Am.
Chem. Soc 2014 136, 4133ꢀ4136. (h) Zhang, L.ꢀS.; Chen, G.;
Wang, X.; Guo, Q.ꢀY.; Zhang, X.ꢀS.; Pan, F.; Chen, K.; Shi, Z.ꢀJ.
Angew. Chem. Int. Ed 2014 53, 3899ꢀ3903. (i) Kuninobu, Y.;
Iwanaga, T.; Omura, T.; Takai, K. Angew. Chem. Int. Ed. 2013
. 2010, 110, 890ꢀ931. (b) Hartwig, J.
catalyzed functionalization of unreactive bonds, see: (f) Meng, G.;
Szostak, M. Angew. Chem. Int. Ed. 2015, 54, 14518ꢀ14522. (g) Zeng,
R.; Dong, G. J. Am. Chem. Soc. 2015, 137, 1408ꢀ1411. (h) Mo, F.;
Dong, G. Science 2014, 345, 68ꢀ72. (i) Ko, H. M.; G. Dong, Nat.
Chem. 2014, 6, 739ꢀ744. (j) Correa, A.; Martin, R. J. Am. Chem. Soc.
.
,
,
5
.
,
.
,
2
014, 136, 7253ꢀ7256. (k) Cornella, J.; GómezꢀBengoa, E.; Martin, R.
J. Am. Chem. Soc. 2013, 135, 1997ꢀ2009. (l) Chen, K.; Li, H.; Lei, Z.ꢀ
Q.; Li, Y.; Ye, W.ꢀH.; Zhang, L.ꢀS.; Sun, J.; Shi, Z.ꢀJ. Angew. Chem.
Int. Ed. 2012, 51, 9851ꢀ9855. (m) Yu, D.ꢀG.; Wang, X.; Zhu, R.ꢀY.;
Luo, S.; Zhang, X.ꢀB.; Wang, B.ꢀQ.; Shi, Z.ꢀJ. J. Am. Chem. Soc.
.
,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4
.
,
2
012, 134, 14638ꢀ14641. (n) Lei, Z.ꢀQ.; Li, H.; Li, Y.; Zhang, X.ꢀS.;
Chen, K.; Wang, X.; Sun, J.; Shi, Z.ꢀJ. Angew. Chem. Int. Ed. 2012,
1, 2690ꢀ2694. (o) Tobisu, M.; Xu, T.; Shimasaki, T.; Chatani, N. J.
.
,
,
.
5
52, 4431ꢀ4434. (j) Liskey, C. W.; Hartwig, J. F. J. Am. Chem. Soc
Am. Chem. Soc. 2011, 133, 19505ꢀ19511. (p) Yu, D.ꢀG.; Li, B.ꢀJ.;
Zheng, S.ꢀF.; Guan, B.ꢀT.; Wang, B.ꢀQ.; Shi, Z.ꢀJ. Angew. Chem. Int.
Ed. 2010, 49, 4566ꢀ4570. (q) himasaki, T. S.; Tobisu, M.; Chatani, N.
Angew. Chem. Int. Ed. 2010, 49, 2929ꢀ2932. (r) Dreis, A. M.; Dougꢀ
las, C. J. J. Am. Chem. Soc., 2009, 131, 412ꢀ413. (s) Gooßen, L. J.;
Deng, G. Levy, L. M. Science 2006, 313, 662ꢀ664. (t) Li, Z.; Liu, L.
Chin. J. Catal. 2015, 36, 3ꢀ14.
2
012
,
134, 12422ꢀ12425. (k) Ros, A.; LópezꢀRodríguez, R.;
Estepa, B.; Álvarez, E.; Fernández, R.; Lassaletta, J. M. J. Am.
Chem. Soc 2012 134, 4573ꢀ4576. (l) Roosen, P. C.; Kallepalli,
V. A.; Chattopadhyay, B.; Singleton, D. A.; Maleczka, R. E.;
Smith, M. R. J. Am. Chem. Soc 2012 134, 11350ꢀ11353. (m)
Kawamorita, S.; Miyazaki, T.; Ohmiya, H.; Iwai, T.; Sawamura,
M. J. Am. Chem. Soc 2011 133, 19310ꢀ19313. (n) Robbins, D.
W.; Boebel, T. A.; Hartwig, J. F. J. Am. Chem. Soc 2010 132
068ꢀ4069. (o) Murphy, J. M.; Liao, X.; Hartwig, J. F. J. Am.
Chem. Soc 2010 132, 11389ꢀ11391.
(14) For selected recent examples on CꢀH silylation reactions, see:
.
,
.
,
.
,
(2) For some recent nickelꢀcatalyzed reactions, see: (a) Fang, X.;
.
,
,
Yu, P.; Morandi, B. Science 2016
Nathel, N. F. F.; Shah, T. K.; Baker, E. L.; Hong, X.; Yang, Y.ꢀF.;
Liu, P.; Houk, K. N.; Garg, N. K. Nature 2015 524, 79ꢀ83. (c)
Tasker, S. Z.; Standley, E. A.; Jamison, T. F. Nature 2014 509
99ꢀ399. (d) Zuo, Z.; Ahneman, D. T.; Chu, L.; Terrett, J. A.;
, 351, 832ꢀ836. (b) Hie, L.;
4
.
,
,
,
,
(a) Simmons, E. M.; Hartwig, J. F. J. Am. Chem. Soc
.
2010
7092ꢀ17095. (b) Tsukada, N.; Hartwig, J. F. J. Am. Chem. Soc
005
,
132
,
2
1
2
.
Doyle, A. G.; MacMillan, D. W. C. Science 2014, 345, 437ꢀ440.
,
127, 5022ꢀ5023. (c) Kakiuchi, F.; Matsumoto, M.; Tsuchiya,
(e) Tellis, J. C.; Primer, D. N.; Molander, G. A. Science 2014
433ꢀ436. (f) Sergeev, A. G.; Hartwig, J. F. Science 2011
39ꢀ443.
3) For Chatani’s Suzuki–Miyaura coupling of activated pyridyl
esters using palladium catalyst, see: Tatamidani, H.; Kakiuchi, F.;
Chatani, N. Org. Lett 2004 , 3597ꢀ3599.
4) Yamamoto, T.; Ishizu, J.; Kohara, T.; Komiya, S.; Yamamoto,
,
345
,
K.; Igi, K.; Hayamizu, T.; Chatani, N.; Murai, S. J. Organomet.
Chem 2003 686, 134ꢀ144. (d) Ishiyama, T.; Saiki, T.; Kishida, E.;
Sasaki, I.; Ito, H.; Miyaura, N. Org. Biomol. Chem 2013 11
162ꢀ8165.
(15) For selected recent examples on CꢀN borylation reactions,
see: (a) Tobisu, M.; Nakamura, K.; Chatani, N. J. Am. Chem. Soc
014 136, 5587ꢀ5590. (b) Zhang, H.; Hagihara, S.; Itami, K.
Chem. Eur. J 2015 21, 16796ꢀ16800. (c) Basch, C. H.; Cobb, K.
M.; Watson, M. P. Org. Lett 2016 18, 136ꢀ139. (d) Hu, J.; Sun,
H.; Cai, W.; Pu, X.; Zhang, Y.; Shi, Z. J. Org. Chem 2016 81
4ꢀ24.
,
332
,
.
,
4
(
.
,
,
8
.
, 6
.
(
2
,
A. J. Am. Chem. Soc. 1980, 102, 3758ꢀ3764.
.
,
(5) Amaike, K.; Muto, K.; Yamaguchi, J.; Itami, K. J. Am. Chem.
Soc 2012 134, 13573ꢀ13576.
6) Muto, K.; Yamaguchi, J.; Musaev, D. G.; Itami, K. Nat. Com-
mun 2015 , 7508ꢀ7815.
7) Hie, L.; Nathel, N. F. F.; Hong, X.; Yang, Y.ꢀF.; Houk, K. N.;
Garg, N. K. Angew. Chem. Int. Ed 2016 55, 2810ꢀ2814.
.
,
.
,
.
,
,
(
1
.
, 6
(16) For selected recent examples on CꢀO borylation reactions,
see: (a) Huang, K.; Yu, D.ꢀG.; Zheng, S.ꢀF.; Wu, Z.ꢀH.; Shi, Z.ꢀJ.
(
.
,
Chem. Eur. J
Chatani, N. J. Am. Chem. Soc
(
(
.
2011
,
17, 786ꢀ791. (b) Kinuta, H.; Tobisu, M.;
2015 137, 1593ꢀ1600.
17) For selected recent examples on CꢀF borylation reactions, see:
a) Zhou, J.; KuntzeꢀFechner, M. W.; Bertermann, R.; Paul, U. S.
(8) (a) N. Miyaura, Top. Curr. Chem. 2002, 219, 11ꢀ59. (b) S.
Kotha, K. Lahiri, D. Kashinath, Tetrahedron 2002, 58, 9633ꢀ9640.
.
,
(
9) (a) Bains, W.; Tacke, R. Curr. Opin. Drug Discovery Dev
003 , 526ꢀ543. (b) Showwell, G. A. Mills, J. S. Drug Discovery
Today 2003 , 551ꢀ556. (c) You, Y.; An, C.ꢀG.; Kim, J.ꢀJ.; Park,
S. Y. J. Org. Chem 2007 72, 6241ꢀ6246. (d) Liu, X.ꢀM.; He, C.;
Haung, J.; Xu, J. Chem. Mater. 2005 17, 434ꢀ441.
.
2
, 6
D.; Berthel, J. H. J.; Friedrich, A.; Du, Z.; Marder, T. B.; Radius,
U. J. Am. Chem. Soc 2016 138, 5250ꢀ5253. (b) Liu, X.ꢀW.; Ecꢀ
havarren, J.; Zarate, C.; Martin, R. J. Am. Chem. Soc 2015 137
2470ꢀ12473. (c) Niwa, T.; Ochiai, H.; Watanabe, Y.; Hosoya, T.
J. Am. Chem. Soc 2015 137, 14313ꢀ14318. (d) Guo, W.ꢀH.; Min,
Q.ꢀQ.; Gu, J.ꢀW.; Zhang, X. Angew. Chem. Int. Ed. 2015, 54,
075ꢀ9078.
18) For selected recent examples on CꢀCN borylation and silylaꢀ
tion of reactions, see: (a) Tobisu, M.; Kinuta, H.; Kita, Y.;
Rémond, E.; Chatani, N. J. Am. Chem. Soc 2012 134, 115ꢀ118. (
Tobisu, M.; Kita, Y.; Chatani, N. J. Am. Chem. Soc 2006 128
,
8
.
,
.
,
.
,
,
,
1
(10) (a) Hall, D. G. Boronic Acids, Wiley, New York, 2005. (b)
Hall, D. G. Boronic Acids: Preparation and Applications in Or-
ganic Synthesis and Medicine, WileyꢀVCH, Weinheim, 2005. (c)
Patai, S.; Rappoport, Z. The Chemistry of Organic Silicon Com-
.
,
9
(
pounds, Eds.. Wiley & Sons: New York, 2000
11) For selected references: (a) Ishiyama, T.; Murata, M.;
Miyaura, N. J. Org. Chem 1995 60, 7508ꢀ7510. (b) Ishiyama, T.;
Itoh, Y.; Kitano, T.; Miyaura, N. Tetrahedron Lett 1997 38
3447ꢀ3450. (c) Takagi, J.; Takahashi, K.; Ishiyama, T.; Miyaura,
N. J. Am. Chem. Soc 2002 124, 8001ꢀ8006. (d) Billingsley, K. L.;
Barder, T. E.; Buchwald, S. L. Angew. Chem. Int. Ed 2007 46
359ꢀ5363. (e) Molander, G. A.; Trice, S. L. J.; Dreher, S. D. J.
Am. Chem. Soc 2010 132, 17701ꢀ17703.
12) For selected references: (a) Hamze, A.; Provot, O.; Alami, M.;
Brion, J.ꢀD. Org. Lett. 2006 , 931ꢀ934. (b) Yamanoi, Y. J. Org.
70, 9607ꢀ9609. (c) Yamanoi, Y.; Nishihara, H. J. Org.
2008, 73, 6671ꢀ6678. (d) McNeill, E.; Barder, T. E.; Buchꢀ
.
(
.
,
b)
.
,
.
,
,
.
,
,
8
152ꢀ8153. (c) Tobisu, M.; Kita, Y.; Ano, Y.; Chatani, N. J. Am.
Chem. Soc
19) Zarate, C.; Manzano, R.; Martin, R. J. Am. Chem. Soc
37, 6754ꢀ6757.
(20) Zarate, C.; Martin, R. J. Am. Chem. Soc
239.
21) Hu, J.; Zhao, Y.; Liu, J.; Zhang, Y.; Shi, Z. Angew. Chem. Int.
Ed 2016, 2016, 55, 8718ꢀ8722.
. 2008, 130, 15982ꢀ15989.
.
,
(
1
. 2015
,
.
,
,
5
.
2014, 136, 2236ꢀ
.
,
2
(
(
,
8
.
Chem
Chem
.
.
2005,
ACS Paragon Plus Environment

Page 7 of 22
ACS Catalysis
(
22) (a) Weires, N. A.; Baker, E. L.; Garg, N. K. Nature. Chem
.
Swift, E. C.; Jarvo, E. R. J. Am. Chem. Soc
(b) Yu, D.ꢀG.; Shi, Z.ꢀJ. Angew. Chem. Int. Ed
7100. (c) Taylor, B. L.; Harris, M. R.; Jarvo, E. R. Angew. Chem.
Int. Ed 2012 51, 7790ꢀ7793. (d) Tobisu, M.; Shimasaki, T.;
Chatani, N. Angew. Chem. Int. Ed 2008 47, 4866ꢀ4869. (e) Zhou,
Q.; Srinivas, H. D.; Dasgupta, S.; Watson, M. P. J. Am. Chem.
Soc 2013 135, 3307ꢀ3310.
(26) (a) Pérez García, P. M.; Ren, P.; Scopelliti, R.; Hu, X. ACS
Catal 2015 , 1164ꢀ1171. (b) Yi, J.; Lu, X.; Sun, Y.ꢀY.; Xiao, B.;
Liu, L. Angew. Chem. Int. Ed. 2013 52, 12409ꢀ14213. (c)
Gallego, G.; Brück, A.; Irran, E.; Meier, F.; Kaupp, M.; Driess, M.;
Hartwig, J. F. J. Am. Chem. Soc 2013 135, 15617ꢀ15626. (d)
Vechorkin, O.; Proust, V.; Hu, X. Angew. Chem. Int. Ed 2010 49
3061ꢀ3064. (e) Vechorkin, O.; Barmaz, D.; Proust, V.; Hu, X. J.
Am. Chem. Soc 2009 131, 12078ꢀ12079.
(27) Knapp, D. M.; Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc
2009 131, 6961ꢀ6963.
.
2013
,
135, 9083ꢀ9090.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2016
,
8
, 75ꢀ19. (b) Shi, S.; Meng, G.; Szostak, M. Angew. Chem.
.
2011 50, 7097ꢀ
,
Int. Ed
23) (a) Quasdorf, K. W.; AntoftꢀFinch, A.; Liu, P.; Silberstein, A.
L.; Komaromi, A.; Blackburn, T.; Ramgren, S. D.; Houk, K. N.;
Snieckus, V.; Garg, N. K. J. Am. Chem. Soc 2011 133, 6352ꢀ
363. (b)ÁlvarezꢀBercedo, P.; Martin, R. J. Am. Chem. Soc 2010
132, 17352ꢀ17353. (c) Quasdorf, K. W.; Riener, M.; Petrova, K.
V.; Garg, N. K. J. Am. Chem. Soc 2009 131, 17748ꢀ17749; (d)
Guan, B.ꢀT.; Xiang, S.ꢀK.; Wang, B.ꢀQ.; Sun, Z.ꢀP.; Wang, Y.;
Zhao, K.ꢀQ.; Shi, Z.ꢀJ. J. Am. Chem. Soc 2008 130, 3268ꢀ3269.
e) Guan, B.; Wang, Y.; Li, B.; Yu, D.; Shi, Z. J. Am. Chem. Soc
. 2016, 55, 6959ꢀ6963.
(
.
,
.
,
.
,
6
.
,
.
,
.
,
.
, 5
,
.
,
(
.
.
,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
008
,
130, 14468ꢀ14470. (f) Li, B.; Li, Y.; Lu, X.; Liu, J.; Guan,
2008 47, 10124ꢀ10127. (g) Li,
Z.; Zhang, S.ꢀL.; Fu, Y.; Guo, Q.ꢀX.; Liu, L. J. Am. Chem. Soc
.
,
,
B.; Shi, Z. Angew. Chem. Int. Ed
.
,
.
.
,
2009
(
,
,
131, 8815ꢀ8823.
.
24) (a) Muto, K.; Yamaguchi, J.; Itami, K. J. Am. Chem. Soc
.
,
2
012
134, 169ꢀ172. (b) Muto, K.; Yamaguchi, J.; Lei, A.; Itami,
2013 135, 16384ꢀ16387. (c) Xu, H.; Muto,
K.; Yamaguchi, J.; Zhao, C.; Itami, K.; Musaev, D. G. J. Am.
Chem. Soc 2014 136, 14834ꢀ14844.
25) The examples for πꢀextended systems greatly accelerated the
rate of CꢀO bond cleavage reactions: (a) Wisniewska, H. M.;
(28) WencelꢀDelord, J.; Glorius, F. Nature Chem
.
2013
,
5, 369ꢀ
K. J. Am. Chem. Soc
.
,
375.
(29) Rolewski, S. Dermatol. Nurs. 2003, 15, 447ꢀ450.
.
,
(30) Nickelꢀcatalyzed transformation of aldehydes into esters and
II
(
amides via an acylnickel intermediate, see: Whittaker, A. M.;
Dong, V. M. Angew. Chem. Int. Ed. 2015, 54, 1312ꢀ1315.
ACS Paragon Plus Environment

ACS Catalysis
Page 8 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
52x130mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 9 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
209x164mm (120 x 120 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 10 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
68x144mm (120 x 120 DPI)
ACS Paragon Plus Environment

Page 11 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9
7x77mm (300 x 300 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 12 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
27x78mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 13 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
102x29mm (300 x 300 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 14 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
180x62mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 15 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
194x224mm (300 x 300 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 16 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
19x29mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 17 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2
06x150mm (300 x 300 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 18 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
44x85mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 19 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
67x138mm (300 x 300 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 20 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
55x89mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 21 of 22
ACS Catalysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
27x121mm (300 x 300 DPI)
ACS Paragon Plus Environment

ACS Catalysis
Page 22 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
86x72mm (300 x 300 DPI)
ACS Paragon Plus Environment