Transition-Metal-Free Defluorosilylation of Fluoroalkenes with Silylboronates

Article abstract of DOI:10.1002/cjoc.201900310

Silylated fluoroalkenes are important synthetic intermediates with complementary reactivity, which play a key role in the construction of natural products, pharmaceuticals, and manmade materials. Converting the normally highly stable fluoroalkenes into si

Full text of DOI:10.1002/cjoc.201900310

Chinese Journal
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Title: Transition-Metal-Free Defluorosilylation of Fluoroalkenes with Silylboronates
Authors: Pan Gao, Guoqiang Wang, Longlong Xi, Minyan Wang, Shuhua Li*, and
Zhuangzhi Shi*
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DOI: 10.1002/cjoc.201800XXX
Transition-Metal-Free Defluorosilylation of Fluoroalkenes with
Silylboronates
Pan Gaoa†, Guoqiang Wangb†, Longlong Xia, Minyan Wanga, Shuhua Lib*, and Zhuangzhi Shia*
ABSTRACT Silylated fluoroalkenes are important synthetic intermediates with complementary reactivity which play a key role in the construction
of natural products, pharmaceuticals, and manmade materials. Converting the normally highly stable fluoroalkenes into silylated fluoroalkenes by
selective defluorosilylation is a challenging task. Here, we report a simple, inexpensive and robust defluorosilylation of a variety of fluoroalkenes with
silylboronates in the presence of alkoxy base to directly synthesize various silylated fluoroalkenes. The protocol features mild and safe reaction conditions
that avoid a catalyst, a transition metal, a ligand, and high reaction temperature and tolerates a wide scope of fluoroalkene substrates without
compromising the efficiency. Density functional theory calculations show that transient silyl anion complex undergoes a SN2’ or SNV substitution which is
responsible for this base-mediated defluorosilylation.
KEYWORDS metal-free , silane , fluorine, DFT, C-F activation
Introduction
Organic compounds containing a C–F bond play important roles in
a variety of fields ranging from organic materials to drug discovery
to agrochemical science.[1] These features have triggered the
development of synthetic methods to complement existing
strategies accessing these compounds. With the steady progress
of methods for the preparation them, defluorinative
functionalization of easily accessible fluorine-containing
compounds[2] can provide facile access to complex fluorinated
molecules, which have recently attracted increasing
attention.[3]Among them, defluorosilylation has shown promises,
because silyl groups can be readily converted into a wide variety
of other functional groups.[4] In 2018, Shibata and coworkers
reported the first Ni-catalyzed ipso-silylation of aryl fluorides via
cleavage of unactivated C–F bonds, thereby streamlining access to
aromatic silanes.[5]Interestingly, they found that alkyl fluorides
could directly convert into the corresponding alkyl silanes
mediated by an alkoxy base in the absence of the Ni catalyst. A
catalyst-free strategy that does not require a transition metal to
achieve the defluorosilylation is of great interest to
chemists.[6]Shortly afterwards, Studer and Würthwein reported
Figure
1
Development of
a
transition-metal-free system for
the development of readily generated silyl lithium reagents with
defluorosilylation of fluoroalkenes.
aryl fluorides to provide the corresponding aryl silanes.[7]
electronic profiles to these substituents.[11] As early in 1997,
Tellier and coworkers reported a pioneering work on synthesis of
gem-difluoroallylsilanes by copper-mediated allylic substitution
of1-bromo-1,1-difluoro-2-alkenes with silyllithium reagents (Fig.
1a).[12] In 2018, copper-catalyzed defluorosilylative reaction of
fluoroalkene feedstocks was developed,[13] in which the
1,2-addition of a silylcopper intermediate to the fluoroalkene and
the subsequent selective β-F elimination is a key step for the
success (Fig. 1b). Herein, we describe the development of a
simple and universal method for the defluorosilylation of diverse
Meanwhile, Martin et al. developed
a
base-promoted
defluorosilylation of unactivated fluoroarenes and fluoroalkanes
by C-F bond cleavage.[8] Despite these advances,
transition-metal-free defluorosilylation of fluoroalkenes to build
silylated fluoroalkenes remains elusive.[9]
Fluoroalkenes are an important class of molecules, among
which, gem-difluoroalkenes[10] and monofluoroalkenes are
essential structural motifs in the design of medicinally active
compounds, and these moieties have been used extensively as
carbonyl and amide isosteres due to their similar steric and
aState Key Laboratory of Coordination Chemistry, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing 210093, China.
E-mail: shiz@nju.edu.cn
Engineering, Nanjing University, Nanjing, 210093, China
E-mail: shuhua@nju.edu.cn
†The authors P. G. and G. W. contributed equally to this work.
bKey Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of
Theoretical and Computational Chemistry, School of Chemistry and Chemical
This article has been accepted for publication and undergone full peer review but has not been through
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fluoroalkenes with silylboronates[14] to generate various silylated
fluoroalkenes mediated by an only alkoxy base (Fig. 1c). Density
functional theory calculations revealed that transient silyl anion
complex undergoes SN2’ or SNV substitution was responsible for
this base-mediated defluorosilylation reaction, thus obviating the
need for copper salts.
moieties, still underwent defluorosilylation to afford desired
products 6-7b in good yields. Whenβ-aryl-containing
1-(trifluoromethyl)alkenes such as 8a were subjected to the
optimized reaction conditions, we isolated defluorosilylative
product 8b in 32% yield. Interestingly, substrate 9a, with an
adjacent sterically bulky group, still afforded product 9b in 43%
yield.
Results
Cu-catalyzed
defluorosilylation
of
Reaction discovery. To begin our studies, we chose
1-(trifluoromethyl)alkene 1a and commercially available
Me2PhSi-Bpin(I)as the model substrates (Table 1). After
systematic optimization, using 1.5 equiv of NaOMe as a base, at
45 °C under an argon atmosphere in THF, defluorosilylation
product 1b was generated in 95% yield (entry 1). Other bases
such as LiOtBu were also effective for this transformation (entry 2),
but using NaOAc (entry 3) or Na2CO3 (entry 4) led to no
conversion. A control experiment confirmed that the silylation
process did not occur in the absence of the NaOMe (entry 5).
These results indicated that the use of alkoxy bases were critical
for success. The solvent effect was also pronounced. Other ether
solvents like1,4-dioxane (entry 6) provided 1b in excellent yield
as well, but the reactions in DMF (entry 7) or toluene (entry 8) led
to much lower conversions. Notably, lowering the reaction
temperature to room temperature could also maintain a good
reactivity (entry 9). Finally, the reaction could be conducted well
in the dark, excluding a visible-light-driven process (entry 10).
(3,3,3-trifluoroprop-1-en-2-yl)benzene (10a) with Me2PhSi-Bpin (I)
could produce product 10b in excellent yield.[13a] Significantly, our
catalyst-free system could perform the same transformation and
provide 76% yield of 10b in gram-scale (Table 2b). Other styryl
substrates bearing meta- and ortho-methyl (11-12b), phenyl (13b),
methoxy (14b), and 1,3-benzodioxole (15b) groups were all
effectively
transformed
into
their
corresponding
gem-difluoroalkenes. We also found that an array of π-extended
systems participated in the reaction to afford defluorosilylative
products 16-18b in good yields. Moreover, the presence of
heterocycles 19-20b did not interfere with productive C–F bond
cleavage. Besides that, benzyl substituted substrate 21a was also
tolerated. In addition, 2-trifluoromethyl-1,3-enynes underwent
successful silylation to afford 22-23b without concomitant
addition to the alkynyl moiety. Notably, internal trifluoromethyl
alkenes such as 24-25a provided desired products 24-25b in 73-98%
yields (Table 2c).
This reaction system was not limited to trifluoromethylalkenes,
gem-difluoroalkenes could also be compatible (Table 2d).
Compared to the reported copper-catalyzed process,[13] our
catalyst-free process exhibits some special reactivities and
functional-group tolerances. This strategy is uniquely suited to
sterically hindered tetrasubstituted gem-difluoroalkenes, such as
Table 1. Reaction optimization.a
Yield of
26-27a,
which
are
difficult
substrates
for
Entry
Variation from the “standard conditions”
1b (%)b
95
92
0
transition-metal-catalyzed reactions. When gem-difluoroalkene
28a was used, the reaction proceeded efficiently and generated
the corresponding monodefluorosilylated product 28b as a
mixture of the Z/E regioisomers (1.3/1). Gratifyingly, with the
additional alkyl-substituents (29-31a) installed, the ratio of
Zselectivity was dramatically increased. Moreover, alkyl
substituted gem-difluoroalkene such as 32a also generated a
Z-selective product 32b in high stereoselectivity.[15] Unfortunately,
the use of diene 33a did not afford 33b under our conditions.
1
2
none
Using LiOtBu instead of NaOMe
Using NaOAc instead of NaOMe
Using Na2CO3 instead of NaOMe
Without NaOMe
3
4
0
5
0
6
In 1,4-dioxane
93
56
35
86
94
Apparently,
gem-difluoroalkenes
obtained
from
7
In DMF
trifluoromethylalkenes can serve as substrates for further
defluorosilylation to afford fluoro(silyl)alkenes when excess
amounts of silylboronate are employed. For instance, dual
silylation of 2-(trifluoromethyl)alkene 10a could generate 10b' as
8
In toluene
9
At room temperature
In dark
10
aReaction conditions: 1a (0.20 mmol), I (0.30 mmol), and base (0.3
mmol) in solvent (1 mL) was stirred for 12 h at 45 °C under Ar.
bIsolated yield after chromatography.
Scope of the methodology. With the optimized reaction
conditions in hand, we first probed the reactivity of
1-(trifluoromethyl)alkenes with Me2PhSi-Bpin(I) (Table 2a).
Biphenyl (2a) and naphthyl (3a) groups on the substrates did not
hinder the reactivity, and the reaction afforded corresponding
the major product via intermediate 10b (Table 2e).
This strategy was also viable for the late-stage modification of
complex molecules (Table 2f). For example, furanose derivative
34a could undergo defluorosilylation with Me2PhSi-Bpin (I) to
produce product 34b in 70% yield. Substrate 35a, bearing a
tertiary propargylic alcohol, was also readily transformed into
1,1-difluoro-1,3-enyne 35b in 53% yield. Gem-difluoroalkene 36a
derived from Adapalene, a second-generation topical retinoid
primarily used in the treatment of mild-moderate acne, can also
be subjected to defluorosilylation to produce the
fluoro(silyl)alkene 36b in good yield.
products 2b-3b in73-82% yields.
Defluorosilylation of
1-(trifluoromethyl)alkenes with either OMe (4b) or OTBS
(5b)moieties on a distal position proceeded smoothly. Notably,
substrates with strongly coordinating groups, such as amine
2
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Table 2. Substrate scope of fluoroalkenes.a
aReaction conditions:A mixture of fluoroalkene a (0.20 mmol), silylboronate I (0.30 mmol), and NaOMe(0.30 mmol) in THF (1 mL) was
b
stirred for 12 h at 45 °C under Ar, isolated yield after chromatography. Fluoroalkene a (0.20 mmol), silylboronate I (0.60 mmol), and
c
d
e
f
NaOMe(0.60 mmol). At 60 °C. Isolated yield of the major product. Z/E ratio was deternined by19F NMR. Fluoroalkene a (0.20 mmol),
silylboronate I (1.2 mmol), and NaOMe(1.2 mmol) in THF (2 mL).
aDepartment, Institution, Address 1
cDepartment, Institution, Address 3
E-mail:
E-mail:
bDepartment, Institution, Address 2
E-mail:
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Several different silylboronates were also investigated as
reaction partners under the optimized reaction conditions
(Scheme 1). Alkyl-substituted silylboronates such as II-IV could
react with 1-(trifluoromethyl)alkene 1a to form a series of
gem-difluoroallylsilanes 1c-1e in good to excellent yields.
in our system.[19]
Scheme 1. Defluorosilylation of 1-(trifluoromethyl)alkene 1a with
different silylboronates II-IV.
Scheme 3.Mechanistic experiments.
Then, density-functional theory (DFT) with the M06-2X
functional[20]was performed to probe the possible mechanism of
this base-mediated defluorosilylation (see Supporting Information
for details). As shown in Fig. 2, the heterolytic cleavage of B-Si
bond in IN1 generates silyl sodium with MeOBpin coordinated to
the sodium cation IN2, which proceeds via TSIN1/IN2 with a barrier
of 18.1 kcal mol-1. The formation of IN2 is endergonic by 16.7 kcal
mol-1, which is consistent with the experimental results that only a
new signal corresponding to [(PhMe2Si)(MeO)Bpin]-(IN1) at 3.9
ppm could be detected by means of the 11B NMR experiment and
the 1:1 ratio of PhMe2SiBpin (δ = 33.1 ppm) and NaOMe in
[D8]THF.[21] Next, the release of (MeO)Bpin accompany by the
association of 1-(trifluoromethyl)alkene 1a with PhMe2Si-Na+
forms a loose complex IN3.[22] The subsequent nucleophilic attack
of silyl anion on 1a via TSIN3/1b generates deflurorosilylation
product 1b and NaF (pathway I). The TSIN3/1b, the nucleophilic
addition of PhMe2Si‒ to C=C bond and the elimination F anion
occurs simultaneously, and therefore, could be characterized to a
classical SN2’ transition state. The activation barrier this transition
state is 27.4 kcal mol-1, and the whole defluorosilylation reaction
is exergonic by 26.6 kcal mol-1. These results suggest that the
studied reaction is thermodynamically and kinetically feasible
under the experimental conditions. However, the alternative
pathway involves the direct nucleophilic attack of the silyl atom of
IN1 on the double bond of 1a can be excluded by its high
activation barrier (pathway II, ΔG ≠ for TSIN1/1b>43.7 kcal mol-1).
On the basis of these results, the pathway involving the transient
silyl anion complex through a SN2’ substitution is responsible for
Synthetic applications. The highly electron-rich allylic C-Si bond
in the generated gem-difluoroallylsilanes can stabilize a positive
charge at the β position through hyperconjugation. Electrophilic
additions to these species can take advantage of this, and site
selectivity generally reflects this property-electrophiles bind to
the difluoromethylene γ to the silyl group. For instance, when
generated product 2b was treated with NBS, we isolated valuable
1-bromo-1,1-difluoro-2-alkene 37 in 88% yield (Scheme 2a).[16]
Treatment of compound 10b with benzaldehyde in the presence
of TBAF could form
a homoallylic alcohol 38 in 74%
yield(Scheme2b). In addition, the reaction of silylated
fluoroalkene
13b
with
water
and
TBAF
good
could
yield
affordCF2H-substituted
counterpart39in
(Scheme2c).[17]Therefore, this defluorosilylative process can act as
a key step in the synthesis of various CF2-substituted vinyl targets
from easily accessible trifluoromethylalkenes.
this
base-mediated
defluorosilylation
reaction
of
trifluoromethylalkenes.
Notably, defluorosilylation of gem-difluoroalkenes is calculated
to proceed via a SNV pathway,[23] which is mechanistically different
from trifluoromethylalkenes. As shown in Fig. 3a, two
four-membered transition states, Z-TSIN4/29b and E-TSIN4/29b, are
responsible for the formation of Z-29b and E-29b, respectively.
With the gem-difluoroalkene 29a as the model substrate, the
Z-defluorosilylation pathway (Z-TSIN4/29b) is kinetically more
favorable than the E-defluorosilylation pathway (E-TSIN4/29b) by
1.1 kcal mol-1. The stabilization of Z-TSIN4/29b benefits from
delocalization of the negative charge in the transition state,
indicated by small dihedral angle (-0.3o in Z-TSIN4/29b versus
-29.8o in E-TSIN4/29b, see Fig. 3b). Therefore, the more stabilized
Z-SNV transition state leads to a preference for the occurrence of
defluorosilylation reaction at the steric congested side of
gem-difluoroalkenes.
Scheme 2. Synthetic applications.
To investigate the reaction mechanism, we first explored a
radical clock experiment by performing the reaction on
(1-cyclopropyl-2,2-difluorovinyl)benzene (40a). Under the
standard conditions, we obtained normal silylated product 40b in
44% yield, and no ring-opening product was detected (Scheme 3a).
This result indicates that this silyl substitution reaction is not a
radical-mediated pathway. Inspired by
a recent work on
defluorosilylation of fluoroarenes with silyl lithium, we utilized a
pre-generated Me2PhSiLi reagent (42)[18] in this reaction affording
the desired product 2b in 45% yield (Scheme 3b). The result
indicates that this free sily anion could be a possible intermediate
aDepartment, Institution, Address 1
cDepartment, Institution, Address 3
E-mail:
E-mail:
bDepartment, Institution, Address 2
E-mail:
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Chin. J. Chem.
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Figure 2.Computed free-energy surfaces for the model reaction between 1-(trifluoromethyl)alkene 1a and silyborane/alkoxy base complex IN1 (in kcal
mol-1).
Figure 3.a Computed free-energy profiles of the reaction between gem-difluoroalkene 29a and silylboronate/alkoxy base complex IN2 (in kcal mol-1). b
3D-structures of Z- and E- SNV transition states.
fluoroalkenes. The distinct mechanistic platform and the resulting
Conclusions
mild and environmentally friendly reaction conditions allow the
incorporation of a variety of synthetically useful functional groups
In summary, we have developed an efficient catalyst-free
into the coupling partners. We anticipate that this
system that can activate the C–F bonds of diverse fluoroalkenes
transition-metal-free strategy based on well-developed silane
via a defluorosilylation process to produce a series of silylated
chemistry will simplify the synthesis and structural elaboration of
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gem-difluoroalkene and monofluoroalkene targets for research in
Watanabe, Y.; Hosoya, T. J. Am. Chem. Soc. 2015, 137, 14313; (o)
Guo, W.; Min, Q.; Gu, J.; Zhang, X. Angew. Chem. Int. Ed.2015,54,
9075; (p) Tian, Y.-M.; Guo X.-N; W. Kuntze-Fechner, M.;
Krummenacher, I.; Braunschweig, H.; Radius, U.; Steffen, A.; B.
Marder, T. J. Am. Chem. Soc. 2018, 140, 17612.
chemistry, biology and medicine.
Experimental
To a 25 mL Schlenk tube was purged with argon for three
times, and then added fluoroalkenes 1a (43.2 mg, 0.2 mmol),
PhMe2SiBpin (I, 78.6 mg, 1.5 equiv), NaOMe (16.2 mg, 1.5 equiv)
[4] (a) Langkopf, E.; Schinzer, D. Chem. Rev. 1995, 95, 1375; (b) Fleming,
I.; Barbero, A.; Walter, D. Chem. Rev. 1997, 97, 2063; (c) Hiyama, T.;
Organomet, J. Organomet. Chem.2002, 653, 58; (d) Komiyama, T.;
Minami, Y.; Hiyama, T. ACS Catal.2017, 7, 631.
o
and THF (1 mL). The formed mixture was stirred at 45 C under
argon for 12 h monitored by TLC. The solution was then cooled to
room temperature and the solvent was removed under vaccum
directly. The crude products were purified by column
chromatography on silica gel to afford product 1b (61.8 mg, 93%)
as a colorless liquid.
[5] Cui, B.-Q.; Jia, S.-C.; Tokunaga, E.; Shibata, N. Nat. Commun.2018, 9,
4393.
[6] (a) Douvris, C.; Ozerov, O. V. Science.2008, 321, 1188; (b) Allemann,
O.; Duttwyler, S.; Romanato, P.; Baldridge, K. K.; Siegel, J. S. Science.
2011, 332, 574; (c) Yoshida, S.; Shimomori, K.; Kim, Y.; Hosoya, T.
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
[7] Mallick, S.; Xu, P.; Würthwein, E.-U.; Studer, A. Angew. Chem. Int. Ed.
2019, 58, 283.
Acknowledgement
[8] Liu, X.-W.; Zarate, C.; Martin, R. Angew. Chem. Int. Ed.2019, 58,
2064.
We thank the National Natural Science Foundation of China
(Grants 2167020084 and 21673110) and the “Innovation &
Entrepreneurship Talents Plan” of Jiangsu Province for their
financial support. Parts for the calculations that were performed
using computational resources on an IBM Blade cluster system
from the High-Performance Computing Center (HPCC) of Nanjing
University.
[9] While this manuscript was under revision, Crimmin et al. reported a
related method on transition metal free generation of fluorinated
organosilanes from fluoroolefins using well-defined nucleophilic
silicon reagents: Coates, G., Tan, H. Y., Kalff, C., White, A. J. P.;
Crimmin,
M.
R.
Angew.
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DOI:10.1002/anie.201906825.
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Manuscript received: XXXX, 2017
Revised manuscript received: XXXX, 2017
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Entry for the Table of Contents
Page No.
Transition-Metal-Free Defluorosilylation
of Fluoroalkenes with Silylboronates
A mild, catalyst-free system has been established for the defluorosilylation of various
fluoroalkenes with silylboronates via C-F activation. This route employs an inexpensive
alkoxy base and can be used to generate silylated fluoroalkenes with a variety of
synthetically useful functional groups.
Pan Gaoa†, Guoqiang Wangb†, Longlong Xia,
Minyan Wanga, Shuhua Lib*, and Zhuangzhi
Shia*
8
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