One-Pot Synthesis of Fluorovinyl Acetates and β,β-Difluoro Carboxylates from a Hypervalent Iodine and Hydrogen Fluoride-Based Fluorination Reagent

Article abstract of DOI:10.1002/adsc.201600433

A new strategy for the synthesis of fluorovinyl acetates and β,β-difluoro carboxylates using a hypervalent iodine and hydrogen fluoride-based fluorination reagent is established through a silver-catalyzed one-pot reaction involving formation of carbon-oxygen and carbon-nitrogen bonds. The generated fluoroalkenes substituted with the carbon-oxygen and carbon-nitrogen bond on the β-position have the potential to be transformed into various products which would be difficult to obtain via direct fluorination. (Figure presented.).

Full text of DOI:10.1002/adsc.201600433

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DOI: 10.1002/adsc.201600433
One-Pot Synthesis of Fluorovinyl Acetates and b,b-Difluoro
Carboxylates from a Hypervalent Iodine and Hydrogen Fluoride-
Based Fluorination Reagent
Zhidong Songa and Wenbin Yia,*
a
Chemical Enginering college, Nanjing University of Science and Technology, 200 Xiao Ling Wei Street, Nanjing, Jiangsu,
Peopleꢀs Republic of China
Fax : (+86)-025-8431-5030; e-mail: yiwenbin@njust.edu.cn
Received: April 23, 2016; Revised: May 28, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600433.
Abstract: A new strategy for the synthesis of fluo-
rovinyl acetates and b,b-difluoro carboxylates using
a hypervalent iodine and hydrogen fluoride-based
fluorination reagent is established through a silver-
catalyzed one-pot reaction involving formation of
carbon-oxygen and carbon-nitrogen bonds. The gen-
erated fluoroalkenes substituted with the carbon-
oxygen and carbon-nitrogen bond on the b-position
have the potential to be transformed into various
products which would be difficult to obtain via
direct fluorination.
lenes are biologically active as shown in Figure 1,[5]
advances in synthetic methods for their construction
have not been thoroughly investigated to date and
only few strategies were published. Jiang et. al report-
ed the synthesis of b-bromofluoroalkenes by bromo-
fluorination of terminal alkynes using AgF as fluorine
source.[6] Schlosser et al. disclosed a multi-step proce-
dure for converting the pre-prepared 2-bromo-1,1-di-
fluoroethylarenes to b,b-difluoro carboxylates,[7]
which could also be typically synthesized by the reac-
tions between the a-functionalized carbonyl com-
pounds and diethylaminosulfur trifluoride (ꢁDASTꢀ)
or sulfur tetrafluoride.[8,2d] You et al. reported the syn-
thesis of 3-fluoroindoles and 3,3-difluoro-3H-indoles
by cyclization/fluorination of 2-alkynylanilines with
a silver catalyst.[9]
Keywords: b,b-difluoro carboxylates; fluorovinyl
acetates; hydrogen fluoride-based reagent; hyperva-
lent iodine; silver
The incorporation of fluorine or fluorine-containing
functional groups could effectively improve the physi-
cochemical properties of parent molecules. As
a result, fluorinated compounds were widely used in
pharmaceuticals, agrochemicals and materials scien-
ces.[1] Among these compounds, fluoroalkenes and
gem-difluoromethylenes were important building
blocks and targets in organic synthesis.[2] The fluoroal-
kene group serves as an isopolar and isosteric mimic
of an amide and possesses distinct biophysical proper-
ties, including decreasing H-bond donating and ac-
cepting abilities.[3] The a,a-difluorobenzyl unit
(ArCF2-) was widely used in the design of enzyme in-
hibitors.[4] Given the well-known ability of C O and
C N bonds to be converted into a variety of other
À
À
moieties, there were many interesting and potentially
useful possibilities presented by the incorporation of
C F bonds into C O and C N bond-containing or-
À
À
À
ganic compounds by a one-pot means. Although b-
Figure 1. Biologically interesting b-functionalized fluoroal-
functionalized fluoroalkenes and gem-difluoromethy- kenes and gem-difluoromethylene compounds.
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The hydrogen fluoride-based (HF-based) reagents cleophilic fluorination reagents (KF,[16] CsF,[17] AgF,[6]
such as triethylamine/HF (TEA·3HF) and pyridine/ TEA·3HF) were tested, and only TEA·3HF gave the
HF (Py·HF) complexes were a kind of ideal fluorina- fluorovinyl acetate (entries 4–6). After screening cata-
tion source in terms of operability, cost and atom lyst loading (entries 7–10) and solvents (entries 10–
economy.[10] They have been successfully applied in 13), the best result was achieved by using 20 mol%
the hydrofluorination of alkynyl(phenyl)iodonium Ag2CO3 in MeCN at 808C for 6 h, giving fluorovinyl
salts,[11b] unactivated[11a,c] or directing-group-decora- acetate 3a in 90% yield (entry 10). Pyridine·HF also
ted[11e] alkynes and ynamides.[11d,f] On the other hand, gave the corresponding product with satisfactory yield
hypervalent iodine compounds have ability to activate (entry 14). The reaction of 1a with 2a on a 10-mmol
ꢀ
the C C triple bond, and offer oxygen and nitrogen- scale was conducted, giving the similar yield and Z/E
containing groups.[12] More recently, several protocols to that on a smaller scale (entry 15).
for the synthesis of b-haloenol acetates by PhI(OAc)2
With these optimized reaction conditions in hand,
have been reported.[13] Deng et al. developed a sil- we set out to test the generality and limitations of this
ver(I)-catalyzed reaction of terminal alkynes with (di- reaction (Scheme 1). Different types of substrates in-
acetoxyiodo)benzene which afforded a-acetoxy ke- cluding aromatic (3a–3m, 3q–3s) and aliphatic alkynes
tones.[14] Based on these results and our continuing ef- (3u–3x) were investigated. It was found that this one-
forts on the development of one-pot syntheses of or- pot reaction served as an efficient route for the syn-
ganofluorine molecules,[15] we speculated that the for- thesis of fluorovinyl acetates (benzoates) in good
À
À
mation of C F and C X (X=O, N) bonds in the yields and stereoselectivities (up to 95% yield and
presence of hypervalent iodine and an HF-based fluo- 99:1 Z/E). Boc-protected 4-ethynylaniline could
rination reagent could happen simultaneously, which endure these conditions (3q). Reactions of arylacety-
would provide a novel strategy for the synthesis of lenes bearing electron-rich groups gave the corre-
fluorovinyl acetates and b,b-difluoro carboxylates.
sponding products 3b–3e and 3k in higher yield than
Our initial investigation was focused on the model that bearing electron-deficient groups (3f–3i, 3j, 3l).
reaction of phenylacetylene 1a and iodosobenzene di- Unfortunately, the highly electron-deficient groups
acetate 2a (Table 1). No desired product was found in (3n, 3o, 3p) gave low yields (b,b-difluoro carboxylates
the absence of Ag(I) (entries 1–3). A number of nu- (benzoates) formed as major products). 2-Ethynylpyr-
idine was able to undergo this reaction and gave the
product 3s in 67%, but the 3-ethynylpyridine only
gave a trace of fluorovinyl product under the same
conditions. Reaction of 2-ethynylthiophene went
Table 1. Optimization of the synthesis of fluorovinyl acetate
3a.[a]
smoothly and produced 3r in 91% yield and excellent
99:1 Z/E. The 3-ethynyl-1-methylindole was not
a viable substrate in the current reaction. The varia-
tion from acyloxy (2a) to benzyloxy (2b) group did
not affect the outcome of this reaction, producing the
corresponding products 3m in 95% yield. Moreover,
reaction with aliphatic terminal alkynes could also
afford products 3u–3x in good yields, but with lower
Z/E ratios compared to the aromatic products
3a–3m. The X-ray crystal structure analysis confirmed
the structure and configuration of product 3m
(Figure 2).[18]
We observed the formation of product b,b-difluoro
carboxylate 4 during our study on the synthesis of flu-
oroalkenes. We inferred that further modification of
the reaction conditions would give the b,b-difluoro
carboxylate product 4 instead of fluorovinyl acetates
3. After a quick screening of the reaction conditions
(see the Supporting Information), we found that the
dihydrofluorination reaction occurred if 4 equiv. of
TEA·3HF were added at an increased temperature of
1208C for 20 h, the b,b-difluoro carboxylate product
4a was then obtained in 72% yield under these modi-
fied conditions (Scheme 2). We then turned to investi-
gate the scope and generality of this protocol. A vari-
ety of substituent groups (alkyl, halo, cyanide, nitro,
Entry [F]
Cat. (mol%) Solvent Yield
[%]
Z/E
1
2
TEA·3HF –
TEA·3HF Pd(OAc)2
MeCN nr
MeCN nr
–
–
(10)
3
TEA·3HF AgBF4 (50)
MeCN nr
MeCN nr
MeCN nr
MeCN trace
–
–
–
–
4
KF
Ag2CO3
Ag2CO3
–
5
6
CsF
AgF
7
8
TEA·3HF AgOAc (100) MeCN 26
TEA·3HF AgF (100) MeCN 63
83/17
75:25
91:9
89:11
83:17
85:15
91:9
91:9
87:13
9
TEA·3HF Ag2CO3 (50) MeCN 92
TEA·3HF Ag2CO3 (20) MeCN 90
TEA·3HF Ag2CO3 (20) DMSO 34
TEA·3HF Ag2CO3 (20) DMF
TEA·3HF Ag2CO3 (20) PhMe 67
10
11
12
13
14
41
Py·HF
Ag2CO3 (20) MeCN 89
15[b] TEA·3HF Ag2CO3 (20) MeCN 89
[a]
Reaction conditions: 1a (1.0 mmol), 2a (1.2 mmol), fluo-
rine source (2.0 mmol), solvent (2.0 mL). The yield and
Z/E ratio were determined by GC-MS.
[b]
The reaction was run on a 10-mmol scale.
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Scheme 1. Synthesis of fluorovinyl acetates. Reaction conditions: 1 (0.25 mmol), 2 (0.3 mmol), TEA·3HF (0.5 mmol),
Ag2CO3 (0.05 mmol), MeCN (1 mL), isolated yield. The Z/E ratio was determined by GC-MS.
ester, ketone) on the aromatic ring could be tolerated.
It was notable that the substrates bearing highly elec-
tron-deficient aryl substituents and 3-ethynylpyridine
were able to give products 4 (4j, 4n, 4o, 4p) in good
yields.
To better understand the mechanism of this catalyt-
ic reaction, the reaction of 3a as starting substrate was
carried out under the conditions of Scheme 1 and
Scheme 2, respectively (Scheme 3). The reactions only
provided a slight amount of 4a, which points out the
minimal feasibility of the direct transformation from
fluorovinyl acetate to b,b-difluoro carboxylate. Thus,
possible mechanisms for the formation of fluorovinyl
acetates and b,b-difluoro carboxylate were proposed
based on our experimental results and comparison of
previous literature result.[6,14,19] Iodonium alkynes A
was firstly generated by the reaction between phenyl-
Figure 2. Single-crystal structure of 3m.
acetylene 1a and iodosobenzene diacetate. Cationic
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Scheme 2. Synthesis of b,b-difluoro carboxylates. Reaction conditions: 1 (0.25 mmol), 2 (0.3 mmol), TEA·3HF (1 mmol),
Ag2CO3 (0.05 mmol), MeCN (1 mL), isolated yields.
kynes with PhI(OAc)2 and TEA·3HF. This novel one-
pot process involving hydrofluorination and oxy- or
nitrogenation created a straightforward and efficient
access to novel and biologically relevant structures.
Scheme 3. Verifying the feasibility of the transformation
from 3a to 4a.
silver species have been regarded as effective catalysts
for the electrophilic activation of alkynes toward a va-
riety of nucleophiles.[20] Thus, the silver cation at-
tacked on the triple bond of iodonium alkyne to form
p-complex B. Based on the anti-addition rule, the ad-
dition of hydrofluoric acid molecules to the com-
plexes gave the (b-fluoro) iodonium C. When the io-
donium C dissociated, 3a was produced with the re-
ductive elimination of PhI. The further hydrofluorina-
tion of C generated the intermediate D, which
smoothly transformed to 4a Scheme 4)
We next envisaged that the use of hypervalent
À
iodine reagents containing an I N bond would allow
the fluorination and amination of alkynes in a similar
manner.[12] (Scheme 5). The attempts using phthali-
mide as a nitrogen source were run under the same
reaction conditions as given in Scheme 1. The corre-
sponding fluoroalkenes 5a–c were obtained in 62–
70% respectively.
In conclusion, a new route to fluorovinyl acetates
and b,b-difluoro carboxylates was developed via
silver-catalyzed difunctionalization of terminal al- vinyl acetates and b,b-difluoro carboxylates.
Scheme 4. Possible mechanisms for the formation of fluoro-
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Ag2CO3 (13.8 mg, 0.05 mmol), MeCN (1 mL) and reflushed
with nitrogen (1 atm). TEA·3HF (81.5 mL, 0.5 mmol) was
added to the sealed reaction vessel by syringe. The resulting
solution was stirred at 808C for 6 h. After cooling to room
temperature, the reaction was quenched with saturated
sodium bicarbonate. The mixture was extracted with ethyl
acetate and washed with brine; the organic layer was col-
lected, dried over anhydrous Na2SO4 and filtered. The sol-
vent was removed under reduced pressure and the residue
was subjected to flash column chromatography purification
to give products 5.
Acknowledgements
We gratefully acknowledge Fundamental Research Funds for
the Central Universities (30916011102), the National Natural
Science Foundation of China (21476116), Natural Science
Foundation of Jiangsu (BK20141394), Qing Lan Project, and
the Center for Advanced Materials and Technology in Nanj-
ing University of Science and Technology for financial sup-
port.
Scheme 5. Synthesis of phthalimide derivatives. Reaction
conditions:
1
(0.25 mmol),
2
(0.3 mmol), phthalimide
(0.375 mmol), TEA·3HF (0.5 mmol), Ag2CO3 (0.05 mmol),
MeCN (1 mL), isolated yield.
Experimental Section
General Procedure for the Synthesis of Fluorovinyl
Acetates
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Carboxylates
A 10-mL oven-dried reaction vessel (sealed tube) was
charged with alkyne 1 (0.25 mmol), hypervalent iodine(III)
reagent 2 (0.3 mmol), Ag2CO3 (13.8 mg, 0.05 mmol), MeCN
(1 mL) and reflushed with nitrogen (1 atm). TEA·3HF
(163 mL, 1 mmol) was added to the sealed reaction vessel by
syringe. The resulting solution was stirred at 1208C for 20 h.
After cooling to room temperature, the reaction was
quenched with saturated sodium bicarbonate. The mixture
was extracted with ethyl acetate and washed with brine; the
organic layer was collected, dried over anhydrous Na2SO4
and filtered. The solvent was removed under reduced pres-
sure and the residue was subjected to flash column chroma-
tography purification to give b,b-difluoro c arboxylates 4.
General Procedure for the Synthesis of 5a, 5b, and 5c
A 10-mL oven-dried reaction vessel (sealed tube) was
charged with alkyne 1 (0.25 mmol), hypervalent iodine(III)
reagent 2 (0.3 mmol), phthalimide (55.1 mg, 0.375 mmol),
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One-Pot Synthesis of Fluorovinyl Acetates and b,b-Difluoro
Carboxylates from a Hypervalent Iodine and Hydrogen
Fluoride-Based Fluorination Reagent
7
Adv. Synth. Catal. 2016, 358, 1 – 7
Zhidong Song, Wenbin Yi*
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