Gram-Scale Synthesis of β-(Hetero)arylethenesulfonyl Fluorides via a Pd(OAc)2 Catalyzed Oxidative Heck Process with DDQ or AgNO3 as an Oxidant

Article abstract of DOI:10.1002/adsc.201700688

A practical oxidative Heck reaction between organoboronic acids and ethenesulfonyl fluoride (ESF) is developed. Aryl- and heteroaryl-boronic acids react efficiently and stereoselectively with ESF in the presence of a catalytic amount of Pd(OAc)₂ and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) or AgNO₃ in AcOH to afford the corresponding E-isomer of β-arylethenesulfonyl fluoride products. The utility of this reaction is exemplified by an expanded scope of 47 examples including N-, O-, and S-containing heteroaromatics, demonstrating chemoselectivity over aryliodides, and gram-scale operation without the requirement for strict anhydrous or oxygen-free conditions. Furthermore, this procedure discriminates against the formation of arylboronic acids homo-coupling byproducts. In addition, the preparation of the first aryl vinylsulfonate polymer, a material with functionalizable Michael acceptor sites, from a starting arylboronic acid is described. (Figure presented.).

Full text of DOI:10.1002/adsc.201700688

Title: Gram-scale Synthesis of β-(Hetero)arylethenesulfonyl Fluorides
via a Pd(OAc)2(cat.)/DDQ or AgNO3 Mediated Oxidative Heck
Process
Authors: Gao-Feng Zha, Grant Bare, Jing Leng, Zhen-peng Shang,
Zhixiong Luo, and Huali Qin
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700688
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10.1002/adsc.201700688
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Gram-Scale Synthesis of β-(Hetero)arylethenesulfonyl Fluorides
via a Pd(OAc)2 Catalyzed Oxidative Heck Process with DDQ or
AgNO3 as an oxidant
Gao-Feng Zha,a Grant A. L. Bare,b Jing Leng,a Zhen-Peng Shang,a Zhixiong Luo,a and
Hua-Li Qina*
a
State Key Laboratory of Silicate Materials for Architectures; and School of Chemistry, Chemical Engineering and Life
Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan, Hubei Province, 430070, P. R. China
Fax: +86 27 87749300; e-mail: qinhuali@whut.edu.cn
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A practical oxidative Heck reaction between
organoboronic acids and ethenesulfonyl fluoride (ESF) is
developed. Aryl- and heteroaryl-boronic acids react
efficiently and stereoselectively with ESF in the presence
of a catalytic amount of Pd(OAc)2 and 2,3-dichloro-5,6-
dicyano-p-benzoquinone (DDQ) or AgNO3 in AcOH to
afford the corresponding E-isomer β-arylethenesulfonyl
fluoride products. The utility of this reaction is exemplified
by an expanded scope of 47 examples including N-, O-, and
S-containing
heteroaromatics,
demonstrated
chemoselectivity over aryliodides, and gram-scale
operation without the requirement for strict anhydrous or
oxygen-free conditions. Furthermore, this procedure
discriminates against the formation of arylboronic acid
homo-coupling byproducts. In addition, the preparation the
first aryl vinylsulfonate polymer,
a
material with
functionalizable Michael acceptor sites, from a starting
arylboronic acid is described.
Keywords: Arylethenesulfonyl fuorides; Oxidative Heck
reaction; Sulfur(VI) fluoride exchange; Palladium catalyst
Figure
1.
Synthetic
routes
accessing
β-
(hetero)arylethenesulfonyl fluorides.
Sulfur(VI) fluoride exchange (SuFEx) is
a rapidly
These
β-arylethenesulfonyl
fluorides
possess
developing iteration of click chemistry.[1] An attractive and
central feature of SuFEx click chemistry is in its utilization
of only a few simple canonical reagents, namely sulfuryl
fluoride,[1b] thionyl tetrafluoride,[1a] and ethenesulfonyl
fluoride (ESF),[1b,2] to introduce diverse sulfur-based
functional groups and connectivity in a modular synthetic
sense. Recently, the previously difficult to access β-
arylethenesulfonyl fluorides have been added to the SuFEx
toolkit via an E-stereoselective palladium-catalyzed Heck-
Matsuda process starting from appropriate aryldiazonium
tetrafluoroborate salts and ESF (Figure 1).
exceptional reactivity as selectively addressable bis-
electrophiles, undergoing Michael addition at either the
alkenyl position in the presence of a secondary amine or
fluoride exchange at the sulfur atom using DBU catalyst.[3a]
Moreover, β-arylethenesulfonyl fluorides may find
application as novel scaffolds and covalent probes in drug
discovery.[4] Limitations on scope and hazards associated
with working with aryldiazonium salts as starting materials
have been alleviated through the expansion of palladium-
catalyzed Heck processes with ESF to include the organic
iodides when stoichiometric AgTFA is used as a halide
scavenger giving way to heteroaryl and alkenyl
couplings.[5] In comparison to organic halides, the
organoboronic acids exist as another cheap, accessible,
1
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10.1002/adsc.201700688
Advanced Synthesis & Catalysis
diverse, and certainly indispensable class of substrates
used in transition metal-catalyzed reactions, which are a
mainstay in modern organic synthesis.[6] Nevertheless,
discovering oxidants and conditions suitable to couple two
'nucleophilic' partners with regeneration of the Pd(0)
catalytic species remains a challenge when boronic acids
or other organoboranes are used in catalytic Heck-type
reactions.[7] A very recent report by Arvidsson and
coworkers describing a Heck oxidative coupling between
and are conceptually simple in design, systematic
screening efforts were carried out in our laboratory when
ESF was selected as the vinyl component.[11] We began our
investigation by examining the reaction of excess ESF 1
and phenylboronic acid 2 in the presence of 5 mol%
Pd(OAc)2 as catalyst and 2 equivalents of oxidant (Table
1). The versatile oxidant DDQ was a suitable selection
based on an observation of its use in an efficient Heck-type
C-glycosylation of glycals starting from phenyl boronic
arylboronic acids and ESF (3eq) makes use of THF solvent, acid.[12] Solvents initially screened over the course of 12 h
catalytic Pd(OAc)2, and stoichiometric amounts of
Cu(OAc)2 and LiOAc as the oxidant and base,
respectively.[8] It has been revealed previously that when
Cu(OAc)2 is used in the reaction system, arylboronic acids
reaction time at 100 °C in a pressure tube including
acetone, THF, and MeCN, gave only unsatisfactory yields
(3−11%) of the desired β-phenylethenesulfonyl fluoride E-
isomer product 3a, while in protic isopropanol solvent,
product was not detected at all (Table 1, entries 1−4). In
contrast, AcOH proved to be an ideal solvent under these
conditions, and 96% yield of product 3a was determined
(entry 5). Previous studies indicate that DDQ is
dramatically activated toward electron transfer processes in
acid.[13] Of note was that significant product was not
detected in AcOH / H2O mixtures until a ratio of 15:1 was
reached (entry 6, see supporting information). The
necessity of base such as metal acetates and carbonates in
many examples of oxidative Heck processes potentially
compromising the labile nature of vinylsulfonyl fluorides
to undergo unwanted Michael addition or substitution /
hydrolysis at the S-F bond was fortuitously avoided
here.[7c,8] Moreover, strict reliance on anhydrous conditions
or an inert oxygen-free atmosphere was also precluded.
The performance of the reaction in AcOH utilizing six
other important oxidants in organic synthesis is presented
in Table 1 (entries 7−12). Use of electron neutral
benzoquinone (BQ) in comparison to activated quinone
DDQ afforded poor yield (35%). The oxidants 2,2,6,6-
2
typically generate
a
mixture products of the
corresponding biphenyl 3', arene 4, phenol 5, symmetrical
diaryl ether 6, and acetoxylation product 7, among which
the homo-coupling biphenyl 3' were the major products
(Figure 2a).[9] Indeed, it is noteworthy to find that the
oxidative Heck reaction of phenylboronic acid and ESF
under the Pd(OAc)2/ Cu(OAc)2/ LiOAc catalyzed
condition provided homo-coupling biphenyl products in a
range of 1−20%, and the ratio of biphenyl to β-
arylethenesulfonyl fluorides increased to about 1/5 when
the arylboronic acid was added at once and the reaction
was operated open to air (Figure 2b).[10] Fortunately, the
formation of homo-coupling biphenyl products is reported
to be preventable through a precautionary handling
procedure. [8]
tetramethylpiperidinooxy
(TEMPO)
and
N-
fluorobenzenesulfonimide (NFSI) gave moderate to good
yield (49−76%) under various conditions. Of the silver (I)
species, the oxide Ag2O performed poorly (33%), whereas
AgNO3 gave excellent yield (86%) close to that of DDQ.
Milder conditions were tolerated for the final optimized
protocol of 1.5 equivalents of DDQ oxidant for 12 h at
80 °C affording an isolated yield of 93% or 86% when
potassium phenyltrifluoroborate was used as a surrogate of
phenylboronic acid. (Table 1, entries 14−15, see
supporting information for further screened conditions)
Figure 2. Products of Cu(OAc)2 catalyzed arylboronic acid
coupling reactions and the examination of the oxidative
Heck reaction of phenylboronic acid and ESF.
Undoubtedly, Arvidsson's small scale procedure (0.49
mmol) provided an additional way for assembly of β-
arylethenesulfonyl fluorides. However, the modest
substrate scope, up to only moderate yields, a reliance on
base and strict anhydrous and inert gas conditions limited
the application of the developed method. Therefore, the
development of scalable and reliable methodologies for the
synthesis of β-arylethenesulfonyl fluorides via oxidative
coupling of arylboronic acids and ESF without the
formation of the arylboronic acids homo-coupling
byproducts is rather desirable and of great importance.
Herein, we seek to disseminate an improved gram-scale
(10 mmol) E-stereoselective and chemoselective base-free
oxidative Heck process suitable for aryl- or heteroaryl-
boronic acids and ESF utilizing 2,3-dichloro-5,6-dicyano-
p-benzoquinone (DDQ) or AgNO3 as an oxidant in AcOH
with significant exclusion of arylboronic acid homo-
coupling side reactions.
Table 1. Optimization of oxidative Heck synthesis of β-
phenylethenesulfonyl fluoride.a
Oxidant
(equiv)
Yield
Yield
4a
Entry
Solvent
(3a, %)b (biphenyl, %)
1
2
DDQ (2.0) Acetone
DDQ (2.0) THF
3
<1
<1
Although Heck-type reactions utilizing boronic acids as
coupling partners have been known for several decades
11
2
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10.1002/adsc.201700688
Advanced Synthesis & Catalysis
equiv) or AgNO3 (20 mmol, 2 equiv), Pd(OAc)2 (112 mg,
5 mol%), and ESF (1, 6.6 g, 60 mmol, 6 equiv) and stirred
for 12 h at 80 °C. Concentration and silica gel
chromatography in EtOAc / hexanes affords pure product 3.
We found that the reaction was well tolerant to both
electron-donating and electron-withdrawing substitution at
the ortho-, meta-, or para-positions on the arylboronic acid
coupling partner giving rise to gram quantities of diverse
structures belonging to the β-arylethenesulfonyl fluoride
class. For example, para-substituted β-arylethenesulfonyl
fluorides were obtained in good to excellent yield (3a–r,
60–99%) for a large range of 18 R-groups including I, SMe,
and SO2Me groups that have not yet been accessed by Pd-
catalyzed cross-coupling reactions with ESF. Comparably,
substitution at the meta-position provided products with
moderate to excellent yield (3s–ae, 55–96%). Remarkable
here is that both para- and meta-iodophenylboronic acids
(3h and 3y; 62% and 74% yield, respectively) did not
undergo significant oxidative addition to Pd despite being
a site of reactivity in the most recent report of Heck
coupling between organic iodides and ESF.[5] The
untouched aryl iodide in this context is a subsequent access
point for later stage cross-coupling to introduce further
complexity in β-arylethenesulfonyl fluorides. Ortho-
substituted arylboronic acids in contrast frustrated the
reaction and generally gave poor yields and narrow scope
(3af–ai, 26–44%). Di-substituted aryl and naphthalenyl
boronic acids reacted satisfactorily. It is noteworthy that 2
equivalents of AgNO3 typically was the oxidant of choice
in place of DDQ when EWGs (Cl-, CF3-, or MeSO2- for
example) were present on the aromatic ring of the
arylboronic acids (3aj−aq). The preparations of β-
heteroarylsulfonyl fluorides 3ar−au including oxygen-
containing 3as and pyridinyl 3at and 3au that are novel
additions to oxidative Heck reaction products of ESF were
also performed with AgNO3 as the preferred oxidant. On
the other hand, the oxidative Heck reaction typically
provided improved yields when EDGs (OMe, OPh, Me, iPr)
were present on the aromatic ring of the arylboronic acids
by employing DDQ as the oxidant (3c, 3s, 3t, 3u, 3ak, for
example). It has to be mentioned that aryl(hetero)boronic
acids bearing acid sensitive functional groups are not
suitable for the synthesis of their corresponding β-
arylethenesulfonyl fluorides under the currently developed
oxidative Heck conditions.
3
4
5
DDQ (2.0) Isopropanol
0
6
<1
<1
<1
DDQ (2.0) MeCN
DDQ (2.0) AcOH
95
AcOH:H2O
(15:1)
6
7
8
DDQ (2.0)
BQ (2.0)
10
35
76
<1
<1
<1
AcOH
TEMPO
(2.0)
AcOH
AcOH
TEMPO
9
49
8
(0.1) / O2
10
11
12
13
14c
NFSI (2.0) AcOH
AgNO3(2.0) AcOH
Ag2O (2.0) AcOH
DDQ (1.5) AcOH
DDQ (1.5) AcOH
59
86
<1
<1
4
33
96
<1
<1
<1
95 (93)
88 (86)
15c,d DDQ (1.5) AcOH
a)
Reaction conditions: Phenylboronic acid (2, 0.2mmol,
1.0 equiv), ESF (1, 1.2 mmol, 6.0 equiv), Pd(OAc)2 (0.01
mmol, 5 mol%), solvent (1.5 mL). Oxidants were added to
a reaction tube (20 mL) and the mixture was stirred at
100 °C for 12 h. b) Yields were determined by HPLC using
3a and biphenyl as external standards, t3a = 4.3 min, λmax
270.1 nm; tbiphenyl = 10.9 min, λmax = 247.6 nm, methanol /
=
water = 75 : 25 (v / v). Isolated yields on a 2 mmol scale
are reported in parentheses. c) Reaction performed at 80 C
°
Subsequently, we turned our attention toward
application of the oxidative Heck process herein to the
synthesis of functional materials and polymers.
for 12 h. d)Potassium phenyltrifluoroborate used as the
boron
souce.
DDQ
=
2,3-dicyano-5,6-
dichlorobenzoquinone, BQ = 1,4-benzoquinone, TEMPO =
2,2,6,6-tetramethylpiperidinooxy,
fluorobenzenesulfonimide.
Bisfunctionalized
monomer
1,3-phenylene
NFSI
=
N-
bisethenesulfonyl fluoride 8, reported previously through
direct fluorosulfonylvinyllation of 1,3-diiodobenzene,[5]
was also obtained in a two step protocol exploiting
chemoselectivity upon 3-iodophenylboronic acid starting
material 2y (Figure 3). Noting that two sulfonyl fluoride
groups were present in molecule 8, we attempted to utilize
it in the preparation of a new class of polymer,[1b,14]
poly(aryl vinylsulfonate) poly-10. To a stirred solution at
130 °C of 1:1 bisfunctionalized ESF monomer 8 and
An extensive evaluation of the scope for a scaled-up
procedure of the optimized Pd(OAc)2 catalyzed oxidative
Heck process in AcOH between ESF and
(hetero)arylboronic acids using DDQ or AgNO3 as the
oxidant was carried out (Table 2). The gram-scale
procedure is operationally simple and is typically
performed as follows: a dry standard round bottom flask
(150 mL) equipped with a condenser apparatus open to the
atmosphere is charged with AcOH (50 mL),
(hetero)arylboronic acid (2, 10 mmol), DDQ (15 mmol, 1.5
bisphenol
A derived silyl ether 9 in N-methyl-2-
pyrrolidone (NMP) solvent was added 1 mol% catalyst
tetrabutyl ammonium bifluoride dissolved in MeCN
3
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10.1002/adsc.201700688
Advanced Synthesis & Catalysis
(Figure 4). The polycondensation process was triggered
instantly upon the addition of the catalyst and gave poly-10
in quantitative yield after 1 h with decent molecular weight
and narrow polydispersity (Mn = 30763 and PDI = 1.6).
Poly-10 represents the first of its kind, a poly(aryl
vinylsulfonate), and as such contains multiple Michael
acceptor spots on the polymer chain widely accessible for
further modification.[15]
Table 2. Synthesis of β-(hetero)arylethenesulfonyl fluorides. a
a)Reaction conditions: (Hetero)arylboronic acid (2, 10.0 mmol, 1 equiv), ESF (1, 60.0mmol, 6.0equiv), Pd(OAc)2 (5 mol%),
°
AcOH (50 mL), DDQ (15.0 mmol, 1.5 equiv) were added to a reaction flask (150 mL) and the mixture was stirred at 80 C
for 12 h. b)AgNO3 (2.0 equiv) was used as the oxidant.
fluorosulfonylvinylation of (hetero)arylboronic acids with
ESF under oxidative conditions provided by DDQ or
AgNO3 additives is described. A variety of (hetero)aryl
boronic acids can be applied in this reaction, which makes
it a general method for the stereoselective synthesis of such
trans
β-(hetero)arylethenesulfonyl
fluorides
from
Figure 3. Two-step synthesis of 1,3-phenylene
bisethenesulfonyl fluoride.
organoborane precursors, a pivotal and widely accessed
class of compounds in modern organic chemistry
laboratories. The utility of this reaction was demonstrated
in the preparation of a novel functionalizable aryl
vinylsulfonate polymer. Further investigations on the
potential bioactivities of these compounds are ongoing in
our laboratory.
Experimental Section
Figure 4. Synthesis of poly(aryl vinylsulfonate).
General
procedures
for
synthesis
of
β-
(hetero)arylethenesulfonyl fluorides (3)
General procedure A
In conclusion, the successful development of a practical
and
scalable
base-free
palladium-catalyzed
4
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10.1002/adsc.201700688
Advanced Synthesis & Catalysis
To an oven-dried reaction flask (150 mL) charged with [5] G.-F. Zha, Q. Zheng, J. Leng, P. Wu, H.-L. Qin, K. B.
AcOH (50 mL), arylboronic acid (2, 10 mmol), 2,3-
dicyano-5,6-dichlorobenzoquinone (DDQ, 15.0 mmol, 1.5
equiv), Pd(OAc)2 (112 mg, 5 mol%), and ethenesulfonyl
fluoride (ESF, 1, 6.60 g, 60.0 mmol, 6.0 equiv) were added
successively. The flask was equipped with a condenser
apparatus open to the atmosphere, and the resulting mixture
Sharpless, Angew. Chem. 2017, 129, 4927–4930;
Angew. Chem. Int. Ed. 2017, 56, 4849–4852.
[6] D. G. Hall, Boronic Acids: Preparation and
Applications in Organic Synthesis, Medicine and
Materials, vols. 1 and 2, Wiley–VCH, 2011.
°
was allowed to react at 80 C for 6-12 h (monitored by
[7] For recent reviews featuring oxidative transition metal
mediated carbon-carbon bond formation including
Heck-type processes see: a) D. V. Partyka, Chem. Rev.
2011, 111, 1529–1595. b) W. Shi, C. Liu, A. Lei, Chem.
Soc. Rev. 2011, 40, 2761–2776. c) B. Karimi, H.
Behzadnia, D. Elhamifar, P. F. Akhavan, F. K. Esfahani,
A. Zamani, Synthesis, 2010, 1399–1427. For some
recent examples of oxidative Heck reactions involving
organoboranes see: d) Y.-B. Zhou, Y.-Q. Wang, L.-C.
Ning, Z.-C. Ding, W.-L. Wang, C.-K. Ding, R.-H. Li,
J.-J. Chen, X. Lu, Y.-J. Ding, Z.-P. Zhan, J. Am. Chem.
Soc. 2017, 139, 3966–3969. e) J. H. Delcamp, P. E.
Gormisky, M. C. White, J. Am. Chem. Soc. 2013, 135,
8460–8463. f) S. K. Alamsetti, A. K. Å. Persson, T.
Jiang, J.-E. Bäckvall, Angew. Chem. 2013, 125, 13990
–13995; Angew. Chem. Int. Ed. 2013, 52, 13745–13750.
TLC) before concentrating under vacuum. The crude
product was purified by silica gel chromatography by
gradient elution with 5−20% EtOAc / petroleum ether to
give pure product 3 as a white solid in most cases.
General procedure B
To an oven-dried reaction flask (150 mL) charged with
AcOH (50 mL), (hetero)arylboronic acid (2, 10 mmol),
AgNO3 (20.0 mmol, 2.0 equiv), Pd(OAc)2 (112 mg, 5
mol%), and ethenesulfonyl fluoride (ESF, 1, 6.6 g, 60.0
mmol, 6.0 equiv) were added successively. The flask was
equipped with
a condenser apparatus open to the
atmosphere, and the resulting mixture was allowed to react
at 80 °C for 12 h before concentrating under vacuum. The
crude product was purified by silica gel chromatography by
gradient elution with 5−20% EtOAc / petroleum ether to
give pure product 3 as a white solid in most cases.
[8] P. K. Chinthakindi, K. B. Govender, A. S. Kumar, H. G.
Kruger T., Govender, T. Naicker, P. I. Arvidsson, Org.
Lett. 2017, 19, 480–483.
Acknowledgements
[9] a) D. A. Evans, J. L. Katz, T. R. West, Tetrahedron Lett.
1998, 39, 2937–2940. b) A. S. Demir, Ö. Reis, M.
Emrullahoglu, J. Org. Chem. 2003, 68, 10130–10134.
Financial support was provided by the Fundamental Research
Funds for the Central Universities (2016-YB-012), and Wuhan
University of Technology. We are grateful to Prof. K. B. Sharpless
(The Scripps Research Institute) for helpful discussion and advice.
We thank Dr. Bing Gao (The Scripps Research Institute) and Mr.
Qinheng Zheng (The Scripps Research Institute) for the synthesis
and analysis of the polymer.
[10] There are a variety of unidentified byproducts from
the oxidative Heck reaction of phenylboronic acid and
ESF under the Pd(OAc)2/ Cu(OAc)2/ LiOAc catalyzed
condition when operated under an open atmosphere,
which could be assigned as benzene, phenol and
symmetrical diphenyl ether according to reference 9.
See supporting information for further details.
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5
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10.1002/adsc.201700688
Advanced Synthesis & Catalysis
UPDATE
Gram-scale Synthesis of β-
(Hetero)arylethenesulfonyl Fluorides via a
Pd(OAc)2(cat.)/DDQ or AgNO3 Mediated
Oxidative Heck Process
Adv. Synth. Catal. Year, Volume, Page – Page
Gao-Feng Zha,a Grant A. L. Bare,b Jing Leng,a
Zhen-Peng Shang,a Zhixiong Luo,a and Hua-Li
Qina*
6
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