Chemoselective nucleophilic additions to perfluorocyclopentene: An efficient building block to highly fluorinated molecules

Article abstract of DOI:10.1016/j.jfluchem.2020.109454

A number of new fluorinated molecules were synthesized utilizing the chemoselective nucleophillic addition to perfluorocyclopentene (PFCP). These compounds were prepared under relatively mild conditions, requirering little or no further purification, and obtained in high yield. Furthermore, the compounds were designed to have reactive end groups for ease of incorporation into a polymer or material. As such, additional transformations were utilized to demonstrate this and are also presented. These molecules show the diverse pool of compounds and reactive monomers that can be prepared via this versatile starting material.

Full text of DOI:10.1016/j.jfluchem.2020.109454

Journal Pre-proof
Chemoselective nucleophilic additions to perfluorocyclopentene: An
efficient building block to highly fluorinated molecules
Ernest L. Alvino, Emeline C. Lochmaier, Scott T. Iacono, Abby R.
Jennings
PII:
S0022-1139(20)30005-1
DOI:
https://doi.org/10.1016/j.jfluchem.2020.109454
FLUOR 109454
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To appear in:
Journal of Fluorine Chemistry
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Revised Date:
Accepted Date:
26 September 2019
2 January 2020
5 January 2020
Please cite this article as: Alvino EL, Lochmaier EC, Iacono ST, Jennings AR,
Chemoselective nucleophilic additions to perfluorocyclopentene: An efficient building block to
highly fluorinated molecules, Journal of Fluorine Chemistry (2020),
doi: https://doi.org/10.1016/j.jfluchem.2020.109454
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Chemoselective nucleophilic additions to perfluorocyclopentene: an efficient building block
to highly fluorinated molecules
Ernest L. Alvino, Emeline C. Lochmaier, Scott T. Iacono, and Abby R. Jennings*
Department of Chemistry & Chemistry Research Center, United States Air Force Academy,
Colorado Springs, Colorado, 80840, USA. E-mail: abby.jennings@usafa.edu
Graphical abstract
Highlights
 Chemoselective nucleophilic additions to perfluorocyclopentene
 Products obtained in high yield, requiring little or no purification
 Reactive end groups for ease of incorporation into a polymer or material
 High stability and functional group tolerance
Abstract:

A number of new fluorinated molecules were synthesized utilizing the chemoselective
nucleophillic addition to perfluorocyclopentene (PFCP). These compounds were prepared under
relatively mild conditions, requirering little or no further purification, and obtained in high yield.
Furthermore, the compounds were designed to have reactive end groups for ease of incorporation
into a polymer or material. As such, additional transformations were utilized to demonstrate this
and are also presented. These molecules show the diverse pool of compounds and reactive
monomers that can be prepared via this versatile starting material.
Keywords: perfluorocyclopentene; nucleophilic addition; fluorinated molecules
1. Introduction
Fluorine has been incorporated into a number of different molecules, polymers and
composites for a variety of applications including, low surface energy materials, catalysis,
19
pharmaceuticals, sensing by F NMR, medical imaging, and many others [1-5]. In order
to develop fluorinated compounds for such specialized applications, it is important to
employ chemical transformations that are known to be efficient, high yielding, tolerant of
a variety of functional groups and solvents, and generate minimal/inoffensive by-products.
The use of orthogonal and chemoselective reactions have been demonstrated to be useful
synthetic tools, as they meet many of these requirements [6-9].
Chemoselective transformations that have been utilized for obtaining fluorinated
molecules and materials include, deoxo-, electrophilic, and nucleophilic fluorination [10-
12]. Alternatively, one can utilize perfluoro-alkyl or aryl starting materials, in combination
with other known selective reactions, to obtain highly fluorinated compounds. For example,

it has been shown by our group and others that perfluorocyclcopentene (PFCP) can be
utilized for obtaining fluorinated molecules and materials via the simultaneous nucleophilic
addition to the fluoroolefin at the 1- and 5-position [13-18]. By employing strong reaction
conditions, such as using heat or a strong base, symmetric fluorinated compounds can be
obtained (Pathway 1, Fig. 1). In contrast, there is only brief mention for controlling this
addition in a chemoselective fashion to achieve substitutions at only the 1- position, using
less forcing reaction conditions (Pathway 2, Fig. 1). In these examples, isolated compounds
are limited to only those prepared from bisphenols and, in one case, an aromatic di-amine
[19-22]. Additionally, in a study presented by Ishihara and co-workers, the authors
synthesized a number of highly fluorinated compounds by reacting PFCP with carbon
nucleophiles [23]. The authors demonstrated that the addition of the nucleophile, either at
the 1- or the 1- and 5- position, could be controlled by using either Grignard or
organolithium reagent, respectively. They also showed that by careful selection of the order
of these reagents, asymmetric compounds could be prepared, (Pathway 2, Fig. 1). Despite
19
this, their study only focused on carbon nucleophiles, most yields were determined by F
NMR, and many compounds required purification by column chromatography. It should
be noted that nucleophilic additions to fluorinated cyclic compounds are well known and
not unique to PFCP. Other systems that have been employed include, but are not limited
to, pentafluoropyridine [24-26], hexafluorobenzene [27-29], decafluorocyclohexene [17,
19, 30, 31], and dodecafluorocyclohexene [30]. However, the systems most closely
resembling PFCP, i.e. having a completely fluorinated ring containing only one vinylic
bond, do not appear to share PFCP’s chemoselectivity. In many cases the nucleophilic

additions result in a mixture of products or multiple additions around the fluorinated ring,
not just at the vinylic position.
As part of our quest for identifying new fluorinated compounds, our aim for this study was
to expand upon the chemoselective properties of PFCP using Pathway 2 (Fig. 1) and a
broader scope of nucleophiles.
Additionally, by employing a modulated lability approach, mono-substituted compounds
and, both symmetrical and asymmetrical, di-substituted compounds could be realized [6].
The nucleophiles utilized for this selective reaction were chosen to contain a wide range of
functional spacers (R) in an effort to control properties and stability of the resulting
compounds. Furthermore, the addition of latent reactive terminal end groups (R’) was
envisioned to allow ease of incorporation into a polymer or material for the applications
mentioned above.
2. Results and discussion
In order to obtain fluorinated compounds where the nucleophile only adds once to
the fluoro-olefin yielding mono-substituted compounds, the reaction is performed under
mild conditions, for example, using a mild organic base (trimethylamine, TEA) under
ambient conditions. Using this methodology, a number of new fluorinated molecules,
compounds 1-7 (Fig. 2), where easily synthesized in relatively high yields. In these
instances, an excess of the PFCP is utilized due to the volatility of this starting material
[32].
In addition to proceding under mild conditions, 1-5 are fully reacted, as observed by
GC-MS, after just 30 min. Compounds
6 and 7 are prepared through a nucleophilic mono-
addition, but three molecules of the PFCP are being reacted with a trifunctional nucleophile.

Thus, these compounds require 16 h of stirring under ambient conditions to reach full
conversion.
Expanding on this chemoselectivity, it was determined that compounds 1-6, could
be further reacted as they contain a fluoro-olefin that is still susceptible to nucleophilic
addition. For symmetrical compounds where the nucleophile adds to the 1- and 5- position,
they can be obtained directly using a one pot modulated lability synthesis. To begin, the
reactions are carried out in a 2:1 mol ratio of nucleophile:PFCP using mild reaction
conditions. Once the addition at the 1-position is observed and complete by GC-MS and
19F NMR, more forcing conditions, such as a stronger base and sometimes heat, is applied
to obtain addition at the 5-position, compounds 9-13 (Fig. 3). All though two equivalents
of nucleophile are used initially, if mild conditions are utilized, such as using TEA as a base
at room temperature, only the mono-substituted molecule and unreacted nucleophile are
observed in the GC-MS. Once more forcing conditions are used, such as a carbonate base
and/or heat, the di-substituted product is observed in the GC-MS. An example is included
for
Information).
Alternatively, asymmetrical di-substituted molecules can be prepared from a mono-
substituted starting material, compounds 14-19 Fig. 1). It should be noted that compounds
9 in the Supporting information sections (see Figures SI 84-91, Supporting
(
14-19 can be synthesized utilizing a one pot reaction, however, care must now be taken to
control the addition of the different nucleophiles through reaction conditions, as well as,
stoichiometry. For example, when synthesizing 14 in a one pot reaction (see 4.5.1.,
Experimental) eugenol and PFCP are added in a 1:1 mol ratio using TEA as a base. Once

19
converted to
1 via GC-MS and F NMR, 2-mercaptoethanol and more base are added to
obtain 14.
When monitored by GC-MS, Compounds 9-19 showed complete conversion within
24-48 h. With the incorporation of fluorine into the framework of 1-19, the conversion of
PFCP into the compounds shown in Fig. 2 -4 can be easily verified using 19F NMR, even
at very low concentrations and also from crude reaction mixtures (Fig. 5). For example, by
reacting PFCP (bottom spectrum) with 1 equivalent of bromophenol via pathway 2 to
obtain 3, the signal near -117 ppm splits into two doublets near -115 ppm, that integrate for
2 fluorine atoms each, while the signal at -129 ppm remains relatively unchanged and the
vinylic fluorine signal at -148 ppm no longer integrates for two fluorine atoms (middle
spectrum). Upon reacting 3 with another equivalent of bromophenol using Cs2CO3 to obtain
11, the doublets merge into one signal, which integrates to 4 fluorine atoms, while the
vinylic fluorine at -148 ppm disappears (top spectrum).
Compounds 1-19 are isolated by washing the reaction solutions with brine and then
performing an extraction with ether. Analysis of the isolated products by GC-MS and multi-
nuclear NMR spectroscopy indicate that the crude materials have a high-level of purity,
with most compounds requiring no further purifications. If purification was necessary, they
could be achieved using non-chromatographic methods. With the exception of
6 and 13,
yields obtained for products were all above 60%. Furthermore, compounds 1-19 clearly
demonstrate that the chemoselective nucleophilic addition to PFCP can be utilized to
achieve fluorinated compounds with unique architectures.
In order to use fluorinated compounds for the applications mentioned above, they
need to be stable, inherently reactive, and tolerant of other functional groups. Compounds

19
1
1-19 are stable, with F and H NMR spectra remaining unchanged for several months
with storage under ambient conditions. Upon long term storage, (6+ months), the
appearance of very small impurity peaks in the 19F NMR begin to appear, although the 1H
NMRs remain unchanged. These changes are attributed to minimal compound degradation.
Although relatively slow due to the strength of the C-F bond, it is known that perfluorinated
compounds undergo degradation by a number of different pathways over time [33, 34].
To demonstrate the inherent reactivity and versatility of 1-19 and their ease of
incorporation into a polymer or material, selected compounds were transformed into
reactive silanes (via metal-catalysed hydrosilylation), thiol-ene adducts (via UV thiol-ene
coupling), and polymerizable monomers (via carbonyl substitution/acylation), respectively
(
Scheme 1). This not only validates their built in reactivity, but illustrates their stability and
functional group tolerance in their synthesis. With these things, it is anticipated that the
utilization of PFCP as a building block will provide a pathway to efficiently obtain
fluorinated materials and polymers. Additionally, by using PFCP one might expect the
resulting materials to encompass properties similar to those of other fluorinated materials,
such as, low surface energies, increased thermal stability, low refractive indices, and
enhanced chemical resistance [35]. However, care must be taken when selecting
nucleophiles, as the effects of polar functional groups might affect some of these anticipated
properties [36]. Furthermore, although the nucleophilic additions to PFCP are well
controlled and predictable under the conditions presented in this manuscript, it has been
demonstrated that reactions can take place at other positions on the PFCP ring [37, 38]. As
such, this could be utilized as a crosslinking point in a material or polymer that is made
from a PFCP based compound, similar to those described in this paper.

3. Conclusions
In summary, a number of new mono- and di-functional fluorinated compounds were
synthesized through the chemoselective nucleophilic addition to PFCP. The reaction
conditions are mild and products are obtained in relatively high yields. Furthermore, by
incorporating reactive end groups into the newly synthesized compounds, they can easily
be transformed and incorporated into highly fluorinated materials by a number of different
pathways including, but not limited to, reactive silanes, thiol-ene click reactions, and
polymerizable end groups.
4.
Experimental
4.1.
General experimental details
All reagents and materials were obtained from commercial sources and used as received
unless states otherwise. The triethylamine (TEA) was distilled from calcium hydride prior to use.
Gas chromatography mass spectrometry (GC-MS) samples were obtained using an Agilent
Technologies 7890A GC system equipped with an Agilent Technologies 5975C Inert XL EI/CI
1
MSD w/triple axis detector, or a Shimadzu single quadrupole GCMS-QP2010 SE. H, 13C, DEPT,
19
and F were obtained on either a Varian Mercury 300 MHz, a Varian Mercury 400 MHz Plus
29
broadband spectrometer, or a JEOL 500 MHz spectrometer. Si NMR and 2D NMR (COSY,
HMBC, and HMQC) were obtained on a JEOL 500 MHz spectrometer. 1H NMR chemical shifts
were internally referenced to CDCl3 ( 7.26 ppm), 13C NMR chemical shifts were reported relative
to the center peak of the triplet for CDCl3 ( 77.0 ppm) or (CD3)2CO ( 29.8 and 206.3 ppm),
chemical shifts for 19F NMR and 29Si are reported in parts per million from CFCl3 ( 0.0 ppm) and
tetramethylsilane ( 0.0 ppm), as the external standards, respectively. In some cases 2D NMR

methods (COSY, HMBC, and/or HMQC) were utilized to assign peaks. If utilized, copies of these
spectra are also provided.
4.2.
General Synthetic method for 1-7
A 50 mL round-bottomed flask was charged with dimethylformamide (DMF), TEA, and
an excess of PFCP. The reaction was stirred at room temperature for 2-3 minutes and then the
respective nucleophile was added last. For compounds 1-5, a GC-MS was taken to verify the full
conversion to the desired product after 30 minutes. For compounds 6 and 7, the reaction was
monitored by 19F NMR and complete after 16 hours. The solution was washed with brine and the
organics extracted with ether. The ether was dried using magnesium sulfate and vacuum filtered.
Rotary evaporation was used to remove all volatiles from the filtrate. Unless stated, no further
purifications were needed.
4.2.1. 4-allyl-1-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-2-methoxy-benzene (1)
The synthesis of 1 and corresponding spectral data have been previously reported.[32]
4.2.2. (2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxybenzene (2)
Compound 2 was prepared using DMF(5.0 mL), TEA (0.56 mL, 4.04 mmol),
perfluorocyclopentene (PFCP, 0.60 mL, 4.47 mmol), and phenol (0.37 g, 3.93 mmol) and obtained
1
as a clear light yellow liquid (0.98 g, 87%). H NMR (CDCl3, 500 MHz, [ppm]): 7.43 (t,
aromatic, 2H, 3JHH = 8 Hz), 7.31 (t, aromatic, 1H, 3JHH = 7.5 Hz), 7.19 (d, aromatic, 2H, 3JHH
=
9.5 Hz13C NMR (CDCl3, 125 MHz, [ppm]): 153.9 (aromatic C), 130.0, (aromatic CH), 126.6
(aromatic CH), 118.5 (aromatic CH)19F NMR (CDCl3, 470 MHz, [ppm]): -115.8 to -116.0 (m,
4F), -129.9 (d, 2F, 3JFF = 25.4 Hz), -150.2 (bs, 1F)MS (EI, 70 eV): m/z (% relative intensity) 286
(M+, 47), 258 (11), 186 (9), 158 (11), 136 (5), 109 (3), 77 (100), 51 (34).
4.2.3. 1-bromo-4-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-benzene (3)

Compound 3 was synthesized using DMF (10 mL), TEA (0.35 mL, 2.52 mmol), PFCP
(0.50 mL, 3.73 mmol), and 4-bromophenol (0.36 g, 2.08 mmol) and obtained as a clear light yellow
liquid (0.71 g, 92%). 1H NMR (CDCl3, 500 MHz, [ppm]):  7.53 (d, aromatic, 2H, 3JHH = 9 Hz),
7.05 (d, aromatic, 2H, 3JHH = 8 Hz). 13C NMR (CDCl3, 125 MHz, [ppm]):  152.8 (aromatic C,),
19
133.1 (aromatic CH), 120.3 (aromatic CH), 119.7 (aromatic C). F NMR (CDCl3, 470 MHz,
3
3
[ppm]):  -115.4 (d, 2F, JFF = 11.3 Hz), -115.5 (d, 2F, JFF = 14.6 Hz), -129.4 (bs, 2F), -148.6
to -148.7 (m, 1F). MS (EI, 70 eV): m/z (% relative intensity) 364 (M+, 100), 345 (4), 257 (14), 185
(23), 157 (57), 75 (36), 50 (23).
4.2.4. 1,3,3,4,4,5,5-heptafluoro-2-octoxy-cyclopentene (4)
Compound 4 was synthesized using DMF (5.0 mL), PFCP (0.60 mL, 4.47 mmol), TEA
(0.45 mL, 3.25 mmol), and octanol (0.50 mL, 3.16 mmol) and obtained as a clear, faint yellow
liquid (0.98 g, 97%). 1H NMR (CDCl3, 500 MHz [ppm]): 4.36 (td, -OCH2CH2CH2-, 2H, 3JHH
4
3
= 6.6 Hz, JHH = 2.7 Hz), 1.76 (p, -OCH2CH2CH2-, 2H, JHH = 7.1 Hz), 1.43-1.28 (m, -
CH2CH2CH2CH2CH2CH3, 10H), 0.88 (t, -CH2CH2CH3, 3H, 3JHH = 7 Hz). 13C NMR (CDCl3, 100
MHz, [ppm]): 73.6 (-OCH2CH2CH2-), 31.6 (-OCH2CH2CH2-), 29.0 (-OCH2CH2CH2-), 28.9 (-
CH2CH2CH2CH2CH3),
28.8
(-CH2CH2CH2CH3),
25.1
(-CH2CH2CH2CH3),
22.5(-
19
CH2CH2CH2CH3), 13.7 (-CH2CH2CH2CH3). F NMR (CDCl3, 470 MHz, [ppm]):  -115.8 (d,
2F, JFF = 14.6 Hz), -117.2 (d, 2F, JFF = 7.1 Hz), -130.67 (2, 2F), -164.1 (m, 1F). MS (EI, 70 eV):
m/z (% relative intensity) 322 (M+, 1), 193 (6), 143 (5), 93 (5), 71 (84), 57 (100), 43 (82).
4.2.5. 1,3,3,4,4,5,5-heptafluoro-2-pent-4-enoxy-cyclopentene (5)
Compound 5 was synthesized using DMF (5.0 mL), PFCP (0.50 mL, 3.73 mmol), TEA
(0.30 mL, 2.16 mmol), and 4-penten-1-ol (0.20 mL, 1.94 mmol) and obtained as a clear, faint
1
yellow liquid (0.48 g, 89%). H NMR (CDCl3, 400 MHz, [ppm]): 5.81-5.74 (m, vinyl, 1H),

3
5
5.08-5.02 (m, vinyl, 2H), 4.38 (t,d, -CH2CH2CH2O-, 2H, JHH = 6.4 Hz, JHF = 2.8 Hz), 2.19 (q,
3
3
CH2=CHCH2-, 2H, JHH = 7.2 Hz), 1.87 (p, -CH2CH2CH2O- , 2H, JHH = 6.8 Hz). 13C NMR
(CDCl3, 100 MHz, [ppm]): 136.4 (CH2=CHCH2-), 115.7 (CH2=CHCH2-), 72.6 (-
19
CH2CH2CH2O-), 29.1 (-CH2CH2CH2O-), 28.1 (-CH2CH2CH2O-). F NMR (CDCl3, 376 MHz,
[ppm]):  -114.8 (m, 2F), -116.2 to -116.3 (m, 2F), -129.6 (q, 2F, 3JFF = ), -162.3 to -162.4 (m,
1F). MS (EI, 70 eV): m/z (% relative intensity) 248 (M+, 1.0), 220 (1), 200 (27), 181 (7), 148 (19),
131 (19), 109 (18), 100 (7), 93 (22), 81 (100), 69 (9).
4.2.6. 1,3,3,4,4,5,5-heptafluoro-2-prop-2-ynoxy-cyclopentene (6)
Compound 6 was synthesized using DMF (5.0 mL), PFCP (1.50 mL, 11.18 mmol), Cs2CO3
(0.93 g, 2.85 mmol), and propargyl alcohol (0.33 mL, 5.72 mmol). Compound 6 was obtained as
1
a clear, faint yellow liquid (0.76 g, 54%). H NMR(CDCl3, 400 MHz, [ppm]): 4.93 (s,
13
CHCCH2O-,2H), 2.71 (t, CHCCH2O-, 1H, 4JHH = 2.6 Hz). C NMR(CDCl3, 75 MHz, [ppm]):
78.0 (CHCCH2-), 74.4 (CHCCH2-), 59.9 (CHCCH2-). 19F NMR(CDCl3, 470 MHz, [ppm]):  -
115.0 (d, 2F, JFF = 14.6 Hz), -116.0 (d, 2F, JFF = 9.4 Hz), -129.4 (bs, 2F), -158.7 to -158.8 (m, 1F).
MS (EI, 70 eV): m/z (% relative intensity) 278 (M+, 13), 143 (15), 131 (18), 124 (9), 109 (27), 100
(8), 93 (28), 69 (90), 41 (100).
4.2.7. 1,3,3,4,4,5,5-heptafluoro-2-[3-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-2-
[(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxymethyl]-2-methyl-propoxy]cyclopentene (7).
Compound 7 was synthesized using DMF (3.0 mL), PFCP (0.55 mL, 4.10 mmol), TEA
(0.55 mL, 3.97 mmol), and trimethylolethane (0.16 g, 1.33 mmol). After workup, the concentrated
filtrate was added to a silica gel plug and washed with ether (150 mL/0.41 g of concentrated
filtrate). All volatiles were removed under reduced pressure and compound 7 was obtained as a
clear, faint yellow waxy solid (0.72 g, 79%). mp = 52-53 ºC. 1H NMR(CDCl3, 400 MHz, [ppm]):

5
4.37 (d, -(CH2)3CCH3, 6H, JHF = 2.4 Hz), 1.25 (s, -(CH2)3CCH3, 3H). 13C NMR (CDCl3, 100
MHz, [ppm]): 72.8 (-(CH2)3CCH3), 41.2 (-(CH2)3CCH3), 15.4 ((-(CH2)3CCH3). 19F NMR
4
3
(CDCl3, 376 MHz, [ppm]):  -115.3 (d, 6F, JFF = 13.5 Hz), -115.9 (d, 6F, JFF = 10.9 Hz), -
129.5 (bs, 6F), -158.6 to -157.0 (m, 3F).
4.2.8. 1-[1,1-bis[4-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxyphenyl]ethyl]-4-
(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-benzene (8)
Compound 8 was synthesized using DMF (3.0 mL), PFCP (0.50 mL, 4.10 mmol), TEA
(0.55 mL, 3.97 mmol), and 1,1,1-tris(4-hydroxyphenyl)ethane (0.38 g, 1.24 mmol). After workup,
The concentrated filtrate was added to a silica gel pad and then washed with hexane:DCM 9:1
solution (150 mL/0.41 g of concentrated filtrate). All volatiles were removed under reduced
pressure. Compound 8 was obtained as a clear, faint yellow solid (0.37 g, 90%). mp = 77-78 ºC.
1H NMR (CDCl3, 400 MHz, [ppm]): 7.07 (bs, 12H), 2.19 (s, 3H). 13C NMR (CDCl3, 100 MHz,
[ppm]): 151.3 (aromatic C), 145.6 (aromatic C), 129.1 (aromatic CH), 117.3 (aromatic CH),
50.7 (-CCH3), 29.6 (-CCH3). 19F NMR (CDCl3, 376 MHz, [ppm]): -115.5 to -115.6 (m, 12F,
3JFF = 13.5 Hz), -129.5 (s, 6F), -149.0 to -149.1 (m, 3F).
4.3. General synthetic method for 9-13
A 50 mL round-bottomed flask was charged with DMF, TEA, and the appropriate
nucleophile. The reaction was stirred at room temperature for 2-3 minutes and then the PFCP was
added last. After 30 minutes of stirring at ambient conditions, a GC-MS was taken to verify the
full conversion to the mono-substituted compound. Cesium carbonate (Cs2CO3) was added to the
reaction and it was stirred under ambient conditions overnight. The solution was washed with brine
and the organics extracted with ether. The ether was dried using magnesium sulfate and vacuum
filtered. Rotary evaporation was used to remove all volatiles from the filtrate. Any deviations from

the general procedure, for example, using heat, are noted. Unless stated, no further purifications
were needed.
4.3.1. 4-allyl-1-[2-(4-allyl-2-methoxy-phenoxy)-3,3,4,4,5,5-hexafluoro-cyclopenten-1-
yl]oxy-2-methoxy-benzene (9)
The synthesis of 9 and corresponding spectral data have been previously reported.[16]
4.3.2. (3,3,4,4,5,5-hexafluoro-2-phenoxy-cyclopenten-1-yl)oxybenzene (10)
Compound 10 was synthesized using DMF (6.0 mL), TEA (0.63 mL, 4.92 mmol), phenol
(0.85 g, 9.03 mmol), PFCP (0.61 mL, 4.55 mmol), and Cs2CO3 (0.80 g, 2.46 mmol). Compound
10 was obtained as a clear light yellow liquid (1.42 g, 87%). 1H NMR (CDCl3, 500 MHz, [ppm]):
7.14 (t, aromatic, 2H, 3JHH = 8 Hz), 7.03 (t, aromatic, 1H, 3JHH = 7.5 Hz), 6.69 (d, aromatic, 2H,
3JHH = 8 Hz13C NMR (CDCl3, 125 MHz, [ppm]): 154.4 (aromatic C), 129.5, (aromatic CH),
124.9 (aromatic CH), 117.0 (aromatic CH)19F NMR (CDCl3, 470 MHz, [ppm]): -114.6 (s, 4F),
-130.1 (s, 2F)MS (EI, 70 eV): m/z (% relative intensity) 360 (M+, 43), 314 (3), 247 (15), 203 (3),
152 (9), 77 (100), 51 (36).
4.3.3. 1-bromo-4[2-(4-bromophenoxy)-3,3,4,4,5,5-hexafluoro-cyclopenten-1-yl]oxy-
benzene (11)
Compound 11 was synthesized using DMF (6.0 mL), TEA (0.41 mL, 2.96 mmol),
bromophenol (0.95 g, 5.49 mmol), PFCP (0.40 mL, 2.98 mmol), and Cs2CO3 (0.93 g, 2.85 mmol).
1
Compound 11 was obtained as a clear light orange liquid (1.39 g, 98%). H NMR (CDCl3, 500
MHz, [ppm]): 7.31-7.28 (m, aromatic, 2H), 6.61-6.58 (m, aromatic, 2H)13C NMR (CDCl3,
125 MHz, [ppm]): 153.2 (aromatic C), 132.6, (aromatic CH), 118.9 (aromatic CH), 118.1
(aromatic C)19F NMR (CDCl3, 470 MHz, [ppm]): -114.5 (s, 4F), -130.0 (s, 2F)MS (EI, 70

eV): m/z (% relative intensity) 518 (M+, 100), 358 (6), 325 (12), 282 (10), 266 (14), 230 (11), 155
(67), 76 (55), 63 (11), 50 (23).
4.3.4. 3,3,4,4,5,5-hexafluoro-1,2-bis(pent-4-enoxy)cyclopentene (12)
Compound 12 was synthesized using DMF (6.0 mL), PFCP (0.50 mL, 3.73 mmol), TEA
(0.50 mL, 3.61 mmol), 4-pentene-1-ol (0.77 mL, 7.46 mml), and Cs2CO3 (0.60 g, 1.84 mmol).
After adding the Cs2CO3, the reaction was heated (65 ℃) for 16h. After workup, the concentrated
filtrate was added to a silica gel plug and then washed with ether (125 mL/1.00 g of concentrated
filtrate). All volatiles were removed, with heat (100 ℃), under reduced pressure. Compound 12
1
was obtained as a clear, faint yellow solid (0.63 g, 57%). H NMR (CDCl3, 400 MHz, [ppm]):
5.79-5.75 (m, vinyl, 2H), 5.06-5.00 (m, H2C=CHCH2-, vinyl, 4H), 4.22 (t, -OCH2CH2CH2-, 4H,
3JHH = 6.4 Hz), 2.16 (q, -OCH2CH2CH2-, 4H, 3JHH = 7.2 Hz), 1.80 (p, -OCH2CH2CH2-, 4H, 3JHH
=
13
6.7 Hz). C NMR (CDCl3, 75 MHz, [ppm]):  136.0 (CH2=CHCH2-), 114.7 (CH2=CHCH2-),
19
70.8 (-CH2CH2CH2O-), 28.5 (-CH2CH2CH2O-), 27.7 (-CH2CH2CH2O-). F NMR (CDCl3, 376
MHz, [ppm]): -111.7 (t, 4F, 3JFF = 5.5 Hz), -129.4 (p, 2F, 3JFF = 5.2 Hz). MS (EI, 70 eV): m/z
(% relative intensity) 344 (M+, 1), 70 (5), 68 (25), 69 (81), 41 (100).
4.3.5. 3,3,4,4,5,5-hexafluoro-1,2-bis(prop-2-ynoxy)cyclopentene (13)
Compound 13 was synthesized using DMF (5 mL), propargyl alcohol (0.43 mL, 7.46
mmol), Cs2CO3 (0.60 g, 1.84 mmol), and PFCP (0.5 mL, 3.73 mmol) was added last. Once
converted to the monosubstituted material as confirmed by GC-MS, more Cs2CO3 (0.60 g, 1.84
mmol) was added. Compound 13 was obtained as a clear light golden-yellow liquid (0.64 g, 61%).
4
1H NMR (CDCl3, 400 MHz, [ppm]): 4.88 (d, CHCCH2O-, 4H, JHH = 2.4 Hz), 2.66 (t,
CHCCH2O-, 2H, 4JHH = 2.2 Hz). 13C NMR (CDCl3, 100 MHz, [ppm]): 77.5 (CHCCH2-), 76.0
3
(CHCCH2-), 60.1 (CHCCH2-). 19F NMR (CDCl3, 376 MHz, [ppm]):  -112.7 (t, 4F, JFF = 3.9

3
Hz), -129.8 (p, 2F, JFF = 4.4 Hz). MS (EI, 70 eV): m/z (% relative intensity) 284 (M+, 32), 245
(100), 229 (10), 156 (25), 127 (33), 100 (74), 78 (69), 52 (32), 40 (13).
4.4. Experimental for reaction monitoring of compound 9
A 50 mL round-bottomed flask was charged with DMF (5 mL), TEA (1.10 mL, 7.94
mmol), and eugenol (1.15 mL, 7.42 mmol). The reaction was stirred at room temperature for 2-3
minutes and then the PFCP was added last (0.50 mL, 3.72 mmol). After 1 hour of stirring at
ambient conditions, a GC-MS was taken to verify the full conversion to the mono-substituted
compound. Cesium carbonate (0.65 g, 1.99 mmol) was added to the reaction and it was gently
heated (60 ̊C). Another GC-MS was taken after heating for 5 hours to monitor the conversion to
9. After heating overnight, another GC-MS was taken to verify the conversion to the di-substituted
product.
4.5. General Synthetic method for 14-19
A 50 mL r.b. flask, equipped with a stir bar, was charged with DMF, the appropriate
nucleophile, and base. The solution was stirred under ambient conditions for 2-3 minutes and then
1 was added. The solution was stirred under ambient conditions and the conversion to the desired
product was monitored by GC-MS. The solution was washed with brine and the organics
extracted with ether. The ether was dried using magnesium sulfate and vacuum filtered. Rotary
evaporation was used to remove all volatiles from the filtrate. Any deviations from the general
procedure, for example, using heat, are noted. Unless stated, no further purifications were needed.
4.5.1. 2-[2-(4-allyl-2-methoxy-phenoxy)-3,3,4,4,5,5-hexafluoro-cyclopenten-1-
yl]sulfanylethanol (14)
Compound 14 was synthesized using DMF (1.0 mL), TEA (93 µL, 0.67 mmol), 2-
mercaptoethanol (0.47 µL, 0.67 mmol), and 1 (0.24 g, 0.67 mmol). The reaction was complete

after stirring under ambient conditions for 1.5 h. Compound 14 was obtained as a hazy orange
1
3
liquid (0.24 g, 86%). H NMR (CDCl3, 500 MHz, [ppm]): 7.07 (d, aromatic, 1H, JHH = 8.5
Hz), 6.77-6.76 (m, aromatic, 2H), 5.98-5.90 (m, vinyl, 1H), 5.11-5.06 (m, vinyl, 2H), 3.83 (s, -
OCH3, 3H), 3.68 (t, -SCH2CH2OH, 2H, 3JHH = 5.7 Hz), 3.38 (d, CH2=CHCH2C-, 2H, 3JHH = 6.0
Hz), 2.99 (t, -SCiCH2OH, 2H, 3JHH = 5.7 Hz), 1.87 (bs, -CH2CH2OH, 1H). 13C NMR (CDCl3, 100
MHz, DEPT, [ppm]): 150.6 (aromatic C), 140.8 (aromatic C), 139.8 (aromatic C), 136.7
(CH2=CHCH2-), 120.7 (aromatic CH), 120.6 (aromatic CH), 116.2 (CH2=CHCH2-), 112.7
(aromatic CH), 60.9 (-OCH2CH2S-), 55.2 (-OCH3), 39.8 (CH2=CHCH2-), 35.1 (-OCH2CH2S-). 19F
NMR (CDCl3, 470 MHz, [ppm]):  -106.7 (s, 2F), -115.4 (s, 2F, 3JFF = 2.6 Hz), -130.0 to -130.1
3
(m, 2F, JFF = 5.0 Hz). MS (EI, 70 eV): m/z (% relative intensity) 414 (M+, 100), 370 (13), 337
(13), 309 (19), 231 (9), 161 (22), 148 (51), 131 (23), 115 (30), 103 (22), 91 (33), 77 (14), 45 (11).
4.5.2. 6-[2-(4-allyl-2-methoxy-phenoxy)-3,3,4,4,5,5-hexafluoro-cyclopenten-1-
yl]sulfanylhexan-1-ol (15)
Compound 15 was synthesized using DMF (2.0 mL), TEA (0.46 mL, 3.25 mmol), 6-
mercaptoethanol (0.45 mL, 3.23 mmol), and 1 (1.17 g, 3.28 mmol). The reaction was complete
after stirring under ambient conditions for 1.5 h. Compound 15 was obtained as a yellow liquid
(1.47 g, 95%).1H NMR (CDCl3, 500 MHz, [ppm]): 7.01 (d, aromatic, 1H, 3JHH = 8.0 Hz), 6.74-
6.71 (m, aromatic, 2H), 5.99-5.91 (m, vinyl, 1H), 5.11-5.04 (m, vinyl, 2H), 3.81 (s, -OCH3, 3H),
3.61 (t, -CH2CH2CH2OH, 2H, 3JHH = 6.5 Hz), 3.37 (d, CH2=CHCH2C-, 2H, 3JHH = 6.5 Hz), 2.83
3
(t, -SCH2CH2CH2-, 2H, JHH = 7.5 Hz), 1.55-1.49 (m, -SCH2CH2CH2-, -CH2CH2CH2OH 4H),
1.34-1.32 (m, -SCH2CH2CH2-, -CH2CH2CH2OH 4H), 1.21 (bs, HOCH2CH2CH2-, 1H). 13C NMR
(CDCl3, 125 MHz, DEPT, [ppm]): 150.7 (aromatic C), 140.8 (aromatic C), 139.4 (aromatic C),
136.9 (CH2=CHCH2-), 120.7 (aromatic CH), 120.6 (aromatic CH), 116.2 (CH2=CHCH2-), 112.8

(aromatic CH), 62.4 (HOCH2CH2CH2-), 55.6 (-OCH3), 39.9 (CH2=CHCH2-), 32.4
HOCH2CH2CH2-, 32.2 (-CH2CH2CH2S-), 29.6 (-CH2CH2CH2S-), 28.2 (-CH2CH2CH2S-), 25.2
HOCH2CH2CH2-). 19F NMR (CDCl3, 376 MHz, [ppm]):  -106.4 (s, 2F), -115.0 (bs, 2F, 3JFF =
2.6 Hz), -129.9 to -130.0 (m, 2F). MS (EI, 70 eV): m/z (% relative intensity) 470 (M+, 24), 370
(23), 147 (100), 115 (16), 91 (18), 55 (34), 41 (28).
4.5.3. 3-[2-(4-allyl-2-methoxy-phenoxy)-3,3,4,4,5,5-hexafluoro-cyclopenten-1-
yl]sulfanylpropane-1,2-diol (16)
Compound 16 was synthesized using DMF (3.0 mL), TEA (0.42 mL, 3.03 mmol), alpha-
thiolglycerol (0.26 mL, 3.00 mmol), and 1 (1.05 g, 2.95 mmol). The reaction was complete after
stirring under ambient conditions for 1.5 h. After workup, The concentrated filtrate was added to
a silica gel pad and then washed with a ethyl acetate:hexane 4:1 solution (100 mL/1.00 g of
concentrated filtrate). All volatiles were removed under reduced pressure. Compound 19 was
1
obtained as a clear, faint yellow solid viscous gel (0.98 g, 82%). H NMR (CDCl3, 400 MHz,
3
[ppm]): 7.07 (d, 1H, JHH = 8.8 Hz), 6.77-6.75 (m, aromatic, 2H), 5.99-5.87 (m, vinyl, 1H),
5.12-5.05 (m, vinyl, 2H), 3.82 (s, -OCH3, 3H), 3.73-3.63 (m, 2H, HOCH2CH- ), 3.51-3.45 (m, 1H,
HOCH(CH2)2-), 3.37 (d, CH2=CHCH2C-, 2H, 3JHH = 6.8 Hz), 3.06-3.02 (m, 1H, -SCH2CH-), 2.81-
2.76 (m, -SCH2CH-, 1H), 2.53 (d, 1H, HOCH(CH2)2, 3JHH = 4 Hz), 1.97 (t, 1H, HOCH2CH-, 3JHH
13
= 6.4 Hz). C NMR (CDCl3, 100 MHz, DEPT, [ppm]): 150.5 (aromatic C), 140.5 (aromatic
C), 139.8 (aromatic C), 136.7 (CH2=CHCH2-), 120.8 (aromatic CH), 120.7 (aromatic CH), 116.4
(CH2=CHCH2-), 112.8 (aromatic CH), 70.9 (HOCH(CH2)2-), 64.7 (HOCH2CH-), 55.7 (-OCH3),
39.9 (CH2=CHCH2-), 35.2 (-SCH2CH-). 19F NMR(CDCl3, 376 MHz, [ppm]): -106.7 (q, 2F, JFF
= 273.5 Hz), -115.4 (q, 2F, JFF = 254.9 Hz), -130.2 (p, 2F, 3JFF = 5.1 Hz). MS (EI, 70 eV): m/z (%

relative intensity) 444 (M+, 8), 384 (13), 370 (38), 337 (20), 309 (22), 229 (10), 161 (29), 148
(100), 131 (28), 117 (41), 103 (27), 91 (45), 77 (20), 65 (8).
4.5.4. 4-allyl-1-[3,3,4,4,5,5-hexafluoro-2-[2,2,2-trifluoromethyl)ethoxy]cyclopenten-1-
yl]oxy-2-methoxy-benzene (17)
Compound 17 was synthesized using DMF (5.0 mL), 1,1,1,3,3,3-hexafluoro-2-propanol
(0.15 mL, 1.14 mmol), Cs2CO3 (0.22 g, 0.68 mmol), and 1 (0.38 g, 1.07 mmol). The reaction was
complete after stirring under ambient conditions for 1.5 h. Compound 17 was obtained as a hazy
orange liquid (0.41 g, 77%). 1H NMR (CDCl3, 400 MHz, [ppm]): 7.16 (d, aromatic, 1H, 3JHH
= 8.8 Hz), 6.79-6.77 (m, aromatic, 2H), 5.97-5.88 (m, vinyl, 1H, -OCH(CF3)2, 1H), 5.12-5.03 (m,
vinyl, 2H), 3.82 (s, -OCH3, 3H), 3.38 (d, CH2=CHCH2C-, 2H, 3JHH = 6.8 Hz). 13C NMR (CDCl3,
100 MHz, [ppm]): 150.5 (aromatic C), 140.8 (aromatic C), 140.2 (aromatic C), 136.5
(CH2=CHCH2-), 121.5 (aromatic CH), 121.0 (aromatic CH), 116.3 (CH2=CHCH2-), 112.5
2
19
(aromatic CH), 73.8 (hep, -OCH(CF3)2, JCF = 34.5), 55.2 (-OCH3), 39.9 (CH2=CHCH2-). F
NMR (CDCl3, 376 MHz, [ppm]):  -74.2 (d, 6F, 3JHF = 5.3), -112.3 to -112.4 (m, 2F), -115.0 (bs,
2F), -129.9 (p, 2F, 3JFF = 3.3). MS (EI, 70 eV): m/z (% relative intensity) 504 (M+, 100), 489 (3),
210 (3), 162 (8), 147 (23), 132 (8), 115 (15), 103 (10), 77 (7), 69 (9).
4.5.5. 4-allyl-1-(3,3,4,4,5,5-hexafluoro-2-octoxy-cyclopenten-1-yl)oxy-2-methoxy-benzene
(18)
Compound 18 was synthesized using DMF (5 mL), octanol (0.25 mL, 1.58 mmol), Cs2CO3
(0.66 g, mmol) and 1 (0.57 g, 1.60 mmol). The solution was gently heated (55 °C) and was
complete after 32 h. Compound 18 was obtained as a hazy orange liquid (0.48 g, 65%). 1H NMR
3
(Acetone-d6, 400 MHz, [ppm]): 7.12 (d, aromatic, 1H, JHH = 8.0 Hz), 6.99 (d, aromatic, 1H,
3JHH = 2.0 Hz), 6.81-6.79 (m, aromatic, 1H), 6.02-5.92 (m, vinyl, 1H), 5.12-5.03 (m, vinyl, 2H),

4.23 (t, -OCH2CH2-, 2H, 3JHH = 6.4 Hz), 3.86 (s, -OCH3, 3H), 3.39 (d, CH2=CHCH2C-, 2H, 3JHH
= 6.8 Hz), 1.56-1.53 (m, -OCH2CH2-, 2H), 1.28-1.24 (m, - CH2CH2CH2CH2CH2CH3, 10H), 0.86
(t, -CH2CH2CH3, 3H, 3JHH = 7.0 Hz). 13C NMR (Acetone-d6, 100 MHz, DEPT [ppm]): 150.5
(aromatic C), 142.0 (aromatic C), 138.8 (aromatic C), 137.2 (CH2=CHCH2-), 120.5 (aromatic CH),
119.5 (aromatic CH), 115.4 (CH2=CHCH2-), 113.1 (aromatic CH), 73.0 (-OCH2CH2CH2-), 55.2
(-OCH3), 39.6 (CH2=CHCH2-), 31.6 (-OCH2CH2CH2-), 29.2 (-OCH2CH2CH2-), 29.0 (-
OCH2CH2CH2CH2-), 28.9 (-CH2CH2CH2CH3), 25.1 (-CH2CH2CH3), 22.4 (-CH2CH2CH3), 13.5 (-
CH2CH2CH3). 19F NMR (Acetone-d6, 376 MHz, [ppm]):  -112.9 to -113.0 (m, 2F), -114.5 to -
3
114.6 (m, 2F), -130.8 (p, 2F, JFF = 4.7 Hz). MS (EI, EI, 70 eV): m/z (% relative intensity) 466
(M+, 44), 354 (100), 162 (7), 148 (29), 115 (18), 103 (9), 91 (14), 71 (32), 57 (37).
4.5.6. 4-allyl-1-(3,3,4,4,5,5-hexafluoro-2-pent-4-enoxy-cyclopenten-1-yl)oxy-2-methoxy-
benzene (19)
Compound 19 was synthesized using DMF (1.50 mL), Cs2CO3 (0.31 g, 0.95 mmol),
eugenol (0.20 mL, 1.29 mmol), and 5 (0.33 g, 1.19 mmol). The reaction was complete after stirring
at ambient conditions for 48 h. After workup, The concentrated filtrate was added to a silica gel
pad and then washed with 120 mL of a 1:2 DCM:hexane solution (120 mL/0.40 g of concentrated
filtrate). All volatiles were removed under reduced pressure and 20 was obtained as a clear, faint
yellow, liquid (0.38 g, 85%). 1H NMR(CDCl3, 500 MHz, [ppm]): 6.98 (d, aromatic, 1H, 3JHH
= 8.0 Hz), 6.75-6.71 (m, aromatic, 2H), 5.97-5.89 (m, vinyl, 1H), 5.74-5.66 (m, 1H, vinyl), 5.09-
5.06 (m, vinyl, 2H), 4.98-4.95 (m, 2H, vinyl), 4.22 (t, -CH2CH2O-, 2H, 3JHH = 6.3Hz), 3.83 (s, -
OCH3, 3H), 3.35 (d, -PhCH2CH=CH2, 2H, 3JHH = 7.0 Hz), 2.00 (q, CH2=CHCH2CH2-, 2H, 3JHH
=
3
13
7.5 Hz), 1.64 (p, CH2=CHCH2CH2-, 2H, JHH = 6.9 Hz). C NMR(CDCl3, 125 MHz, [ppm]):
150.3 (aromatic C), 142.5 (aromatic C), 138.3 (aromatic C), 137.1 (vinyl CH), 137.0 (vinyl CH),

120.7 (aromatic), 119.2 (aromatic CH), 116.3 (vinyl CH2), 115.6 (vinyl CH2), 113.0 (aromatic
CH), 72.3 (-CH2CH2CH2O-), 55.9 (-OCH3) 40.0 (-PhCH2CH=CH2), 29.4 (-CH2CH2CH2O-), 28.6
(-CH2CH2CH2O). 19F NMR(CDCl3, 470 MHz, [ppm]):  -112.2 (s, 2F), -114.1 (s, 2F), -129.8 (s,
2F). MS (EI, 70 eV): m/z (% relative intensity) 422 (M+, 47), 354 (25), 148 (35), 115 (22), 103
(14), 91 (20), 77 (10), 69 (55), 41 (100).
4.6. Example one pot reaction for compound 14
Compound 14 was synthesized in a one pot reaction by charging a 50 mL r.b. flask with
DMF (5.0 mL), TEA (0.22 mL, 1.59 mmol), eugenol (0.24 mL, 1.55 mmol), and PFCP (0.21 mL,
1.56 mmol). The reaction was stirred under ambient conditions and monitored by GC-MS and 19F
NMR. Once converted to 1, 2-mercaptoethanol (0.11 mL, 1.56 mmol) and more TEA (0.22 mL,
1.59 mmol) were added to the reaction flask. The reaction was monitored by GC-MS and 19F NMR.
19
Once converted to 14 as observed in GC-MS and F NMR, the solution was washed with brine
and the organics extracted with ether. The ether was dried using magnesium sulfate and vacuum
filtered. Rotary evaporation was used to remove all volatiles from the filtrate. Compound 14 was
obtained as a as a hazy orange liquid (0.60 g, 97%).
4.7. General procedure for compounds 20-23
A 25 mL r.b. flask, equipped with a stir bar, was charged with 1 and 1 drop of Karstedt’s
catalyst (Pt-divinyltetramethyl-disiloxane complex in xylene). The solution was stirred under N2,
and then the appropriate silane was added, using a syringe. The solution was gently heated (45-
1
50 °C), under N2. A H NMR was taken to verify the conversion of reactants to products. All
volatiles were removed under reduced pressure. Any deviations from the general procedure, for
example, using solvent, are noted. Unless stated, no further purifications were needed.

4.7.1. Chloro-[3-[4-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-3-methoxy-
phenyl]propyl]-dimethylsilane (20)
The synthesis of 20 and corresponding spectral data have been previously reported.[36]
4.7.2. Dichloro-[3-[4-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-3-methoxy-
phenyl]propyl]-methylsilane (21)
Compound 21 was synthesized using 1 (0.50 g, 1.40 mmol), 1 drop of Karstedt’s catalyst,
and dichloromethylsilane (0.13 mL, 1.58 mmol). The reaction was complete after 1 h. Compound
1
21 was obtained as a clear and light yellow/brown liquid (0.62 g, 94 %). H NMR(CDCl3, 500
3
MHz, [ppm]):  7.11 (d, aromatic, 1H, JHH = 8.5 Hz), 6.78-6.74 (m, aromatic, 2H), 3.85 (s, -
3
OCH3, 3H), 2.69 (t, -SiCH2CH2CH2-, 2H, JHH = 7.8 Hz), 1.87-1.81 (m, -SiCH2CH2CH2-, 2H),
1.14-1.11 (m, -SiCH2CH2CH2-, 2H), 0.77 (s, Cl2Si(CH3)CH2-, 3H). 13C NMR(CDCl3, 125 MHz,
[ppm]):  150.5 (aromatic C), 141.7 (aromatic C), 140.8 (aromatic C), 120.7 (aromatic CH), 120.5
(aromatic CH), 112.7 (aromatic CH), 55.7 (-OCH3), 38.2 (-SiCH2CH2CH2-), 24.2 (-
19
SiCH2CH2CH2-), 21.0 (-SiCH2CH2CH2-), 5.0 (Cl2Si(CH3)CH2-). F NMR(CDCl3, 470 MHz,
[ppm]):  -115.2 (d, 2F, JFF = 14.6 Hz), -115.8 (d, 2F, JFF = 11.3 Hz), -129.4 (s, 2F), -156.9 to -
157.0 (m, 1F). 29Si (CDCl3, 99 MHz, [ppm]):  33.1. MS (EI, 70 eV): m/z (% relative intensity)
471 (M+, 5), 329 (100), 113 (21), 77 (6).
4.7.3. trichloro-[3-[4-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-3-methoxy-
phenyl]propyl]silane (22)
Compound 22 was synthesized ausing 1 (3.03 g, 8.51 mmol), 1 drop of Karstedt’s catalyst,
THF (5.00 mL) and trichlorosilane (1.50 mL, 14.84 mmol). The reaction was complete after 16h.
Compound 22 was obtained as a clear and light yellow liquid (3.91 g, 94%). 1H NMR(CDCl3, 500
3
MHz, [ppm]):  7.12 (d, aromatic, 1H, JHH = 8.0 Hz), 6.77-6.74 (m, aromatic, 2H), 3.85 (s, -

3
OCH3, 3H), 2.72 (t, -SiCH2CH2CH2-, 2H, JHH = 7.8 Hz), 1.94-1.88 (m, -SiCH2CH2CH2-, 2H),
1.43-1.39 (m, -SiCH2CH2CH2-, 2H).13C NMR(CDCl3, 125 MHz, [ppm]):  150.6 (aromatic C),
141.0 (aromatic C), 140.9 (aromatic C), 120.6 (aromatic CH, aromatic CH), 112.8 (aromatic CH),
55.8 (-OCH3), 37.6 (-SiCH2CH2CH2-), 24.0 (-SiCH2CH2CH2-), 23.7 (-SiCH2CH2CH2-). 19F
NMR(CDCl3, 470 MHz, [ppm]):  -115.1 (d, 2F, JFF = 15.0 Hz), -115.8 (d, 2F, JFF = 10.8Hz), -
129.5 (s, 2F), -156.6 to -156.7 (m, 1F). 29Si (CDCl3, 99 MHz, [ppm]):  13.1. MS (EI, 70 eV):
m/z (% relative intensity) 492 (M+, 12), 329 (100), 133 (41), 121 (5), 105 (7), 90 (8), 77 (11), 63
(7).
4.7.4. triethoxy-[3-[4-(2,3,3,4,4,5,5-heptafluorocyclopenten-1-yl)oxy-3-methoxy-
phenyl]propyl]silane (23)
Compound 23 was synthesized using 1 (1.00 g, 2.81 mmol), 1 drop of Karstedt’s catalyst,
and triethoxysilane (0.55 mL, 2.98 mmol). The reaction was complete after stirring at room
temperature for 16h. Compound 23 was obtained as a clear and light yellow liquid (1.26 g, 86 %).
3
1H NMR(CDCl3, 400 MHz, [ppm]):  7.06 (d, aromatic, 1H, JHH = 8.4 Hz), 6.77-6.72 (m,
3
aromatic, 2H), 3.83 (s, -OCH3, 3H), 3.81 (q, ((-OCH2CH3)3), 6H, JHH = 7.2 Hz), 2.63 (t, -
3
3
SiCH2CH2CH2-, 2H, JHH = 7.6 Hz), 1.73 (p, -SiCH2CH2CH2-, 2H, JHH = 8.0 Hz), 1.20 (t, ((-
3
13
OCH2CH3)3), 9H, JHH = 6.8 Hz), 0.65-0.61 (m, -SiCH2CH2CH2-, 2H). C NMR(CDCl3, 100
MHz, [ppm]):  150.2 (aromatic C), 142.5 (aromatic C), 140.3 (aromatic C), 120.5 (aromatic
CH), 120.1 (aromatic CH), 112.6 (aromatic CH), 58.1 (CH3CH2O-), 55.3 (-OCH3), 38.7 (-
SiCH2CH2CH2-), 24.6 (-SiCH2CH2CH2-), 17.9 (CH3CH2O-), 9.7 (-SiCH2CH2CH2-). 19F
3
3
NMR(CDCl3, 376 MHz, [ppm]):  -115.3 (m, 2F, JFF = 13.5 Hz ), -115.4 (m, 2F, JFF = 10.2
Hz), -129.7 (s, 2F), -157.0 to -157.2) (m, 1F). 29Si (CDCl3, 99 MH, [ppm]):  -45.2. MS (EI, 70
eV): m/z (% relative intensity) 520 (M+, 7), 329 (52), 163 (100), 119 (3), 109 (25), 81 (20).

4.8. General procedure for compounds 24 and 25
A 25 mL r.b. flask, equipped with a stir bar and reflux condenser, was charged with 9 (0.20
g, 0.40 mmol), 2 2-dimethoxy-2-phenylacetophenone (DMPA, 6 mg, 0.02 mmol), butanethiol
(0.08 mL, 0.75 mmol), and THF (0.50 mL). The flask was irradiated under two UV lamps (254
nm) for 2 hrs. A 1H NMR was taken to verify the conversion of reactants to products. All volatiles
were removed under reduced.
4.8.1. 4-(3-butylsulfanylpropyl)-1-[2-[4-(3-butylsulfanylpropyl)-2-methoxy-phenoxy]-
3,3,4,4,5,5-hexafluoro-cyclopenten-1-yl]oxy-2-methoxy-benzene (24)
Compound 24 was synthesized using 9 (0.20 g, 0.40 mmol), DMPA (6 mg, 0.02 mmol),
butanethiol (0.08 mL, 0.75 mmol), and THF (0.50 mL). The reaction was complete after stirring
at room temperature under the UV lamps for 2h. Compound 24 was obtained as a clear, yellow
liquid ( 0.26 g, 98 %). 1H NMR(CDCl3, 500 MHz, [ppm]):  6.71 (d, aromatic, 2H, 3JHH = 8.0
Hz), 6.55-6.52 (m, aromatic, 4H), 3.71 (s, -OCH3, 6H), 2.60 (t, -CCH2CH2CH2S-, 4H, 3JHH = 7.5
Hz), 2.51-2.45 (m, -CCH2CH2CH2S-, -SCH2CH2CH2CH3, 8H), 1.82 (p, -CCH2CH2CH2S-, 4H,
3JHH = 7.5 Hz), 1.54 (p, -SCH2CH2CH2CH3, 4H, 3JHH = 7.3 Hz), 1.39, (sext., -SCH2CH2CH2CH3,
4H, 3JHH = 7.3 Hz), 0.90 (t, -SCH2CH2CH2CH3, 6H, 3JHH = 7.3 Hz). 13C NMR(CDCl3, 125 MHz,
DEPT, [ppm]):  149.5 (aromatic C), 141.7 (aromatic C), 139.4 (aromatic C), 120.0 (aromatic
CH), 118.3 (aromatic CH), 112.6 (aromatic CH), 55.8 (-OCH3), 34.6 (-CCH2CH2CH2S-), 31.9
(alkyl -CH2- ), 31.8 (alkyl -CH2- ), 31.4(alkyl -CH2- ), 31.2 (alkyl -CH2- ), 22.1 (-
19
SCH2CH2CH2CH3), 13.8 (-SCH2CH2CH2CH3). F NMR(CDCl3, 470 MHz, [ppm]):  -114.1
(bs, 4F), -130.2 (s, 2F).
4.8.2. 2-[3-[4-[3,3,4,4,5,5-hexafluoro-2-[4-[3-(2-hydroxyethylsulfanyl)propyl]-2-methoxy-
phenoxy]cyclopenten-1-yl]oxy-3-methoxy-phenyl]propylsulfanyl]ethanol (25)

Compound 25 was synthesized using 9 (0.11 g, 0.22 mmol), DMPA (5 mg, 0.02 mmol),
2-mercaptoethanol (0.03 mL, 0.45 mmol), and THF (0.50 mL). The reaction was complete after
stirring at room temperature under the UV lamps for 2h. Compound 25 was obtained as a clear
and light yellow viscous liquid (0.14 g, 93 %). 1H NMR(CDCl3, 500 MHz, [ppm]):  6.73 (d,
aromatic, 2H, 3JHH = 8.0 Hz), 6.56-6.52 (m, aromatic, 4H), 3.73 (s, -OCH3, 6H), 3.70 (t, -
SCH2CH2OH, 4H, 3JHH = 6.0 Hz), 2.64 (t, -SCH2CH2OH, 4H, 3JHH = 7.5 Hz), 2.56 (t, -
CCH2CH2CH2S-, 4H, 3JHH = 7.5 Hz), 2.43 (t, --CCH2CH2CH2S-, 4H, 3JHH = 7.5 Hz, ), 1.77 (p, -
CCH2CH2CH2S-, 4H, 3JHH = 7.5 Hz). 13C NMR(CDCl3, 125 MHz, DEPT, [ppm]):  149.5
(aromatic C), 141.7 (aromatic C), 139.2 (aromatic C), 120.0 (aromatic CH), 118.4 (aromatic
CH), 112.6 (aromatic CH), 60.7 (-SCH2CH2OH), 55.8 (-OCH3), 35.1 (-SCH2CH2OH), 34.4 (-
CCH2CH2CH2S-), 31.2 (-CCH2CH2CH2S- ), 31.1 (-CCH2CH2CH2S-). 19F NMR(CDCl3, 470
MHz, [ppm]):  -114.1 (s, 4F), -130.2 (s, 2F).
4.9. General procedures for compound 26 and 27
A 25 mL r.b. flask, equipped with a stir bar and reflux condenser, was charged with 14 or
15, TEA, and 15.0 mL of Et2O. To a 10 mL addition funnel was added methacryloyl chloride and
10 mL of Et2O. This solution was added slowly, dropwise to the r.b. flask. The solution was stirred
under N2, overnight. The suspension was vacuum filtered and the filtrate was concentrated using
rotary evaporation.
4.9.1. 2-[2-(4-allyl-6-methoxy-6,6,6,6,6,6-hexamethyl-2,4-dimethylene-cyclohexa-1,3-dien-
1-yl)oxy-3,3,4,4,5,5-hexafluoro-cyclopenten-1-yl]sulfanylethyl 2-methylprop-2-enoate (26)
Compound 26 was synthesized using 14 (0.60 g, 1.45 mmol), TEA (0.30 mL, 2.16 mmol),
and methacryloyl chloride (0.20 mL, 2.05 mmol). Compound 26 was obtained as a clear and
yellow liquid (0.49 g, 70.1 %). 1H NMR (CDCl3, 500 MHz, [ppm]): 7.05 (d, aromatic, 1H, 3JHH

= 8.5 Hz), 6.75-6.73 (m, aromatic, 2H), 6.09 (s, vinyl H, 1H), 5.97-5.90 (m, vinyl, 1H), 5.58 (s,
vinyl , 1H), 5.10-5.06 (m, vinyl, 2H), 4.20 (t, -SCH2CH2O-, 2H, 3JHH = 6.8 Hz), 3.81 (s, -OCH3,
3H), 3.38 (d, CH2=CHCH2C-, 2H, 3JHH = 7.0 Hz), 3.11 (t, -SCH2CH2O-, 2H, 3JHH = 6.5 Hz), 1.92
(s, -CH(CH3)OC=CH2, 3H). 13C NMR (CDCl3, 100 MHz, DEPT, [ppm]): 167.0 (C=O), 150.7
(aromatic C), 140.6 (aromatic C), 139.7 (aromatic C), 136.8 (CH2=CHCH2-), 135.9 (-
CH(CH3)C=CH2), 126.2 (-CH(CH3)C=CH2), 121.0 (aromatic CH), 120.8 (aromatic CH), 116.5
(CH2=CHCH2-), 112.7 (aromatic CH), 63.1 (-OCH2CH2S-), 55.8 (-PhOCH3), 40.0 (CH2=CHCH2-
), 30.8 (-OCH2CH2S-), 18.3 (-CH(CH3)C=CH2). 19F NMR (CDCl3, 470 MHz, [ppm]):  -106.5
(s, 2F), -115.2 (s, 2F, 3JFF = 2.6 Hz), -129.9 (s, 2F, 3JFF = 5.0 Hz). MS (EI, 70 eV): m/z (% relative
intensity) 482 (M+, 16), 396 (11), 368 (13), 174 (57), 161 (90), 146 (56), 113 (100), 103 (100), 91
(21), 69 (52), 41 (64).
4.9.2. 6-[2-(4-allyl-6-methoxy-6,6,6,6,6,6-hexamethyl-2,4-dimethylene-cyclohexa-1,3-dien-
1-yl)oxy-3,3,4,4,5,5-hexafluoro-cyclopenten-1-yl]sulfanylhexyl 2-methylprop-2-enoate (27)
Compound 27 was synthesized using 15 (0.19 g, 0.40 mmol), TEA (61 L, 0.44 mmol),
and methylacryloyl chloride (39 L, 0.40 mmol). Compound 27 was obtained as a light yellow
wax (0.22 g, 79%). 1H NMR (CDCl3, 500 MHz, [ppm]): 7.01 (d, aromatic, 1H, 3JHH = 8.0 Hz),
6.74-6.72 (m, aromatic, 2H), 6.07 (s, vinyl, 1H), 5.98-5.89 (m, vinyl, 1H), 5.53 (s, vinyl, 1H), 5.09-
3
5.05 (m, vinyl, 2H), 4.10 (t, -OCH2CH2CH2-, 2H, JHH = 7 Hz), 3.81 (s, -OCH3, 3H), 3.37 (d,
3
3
CH2=CHCH2C-, 2H, JHH = 6.5 Hz), 2.81 (t, -CH2CH2CH2S-, 2H, JHH = 7 Hz), 1.92 (s,
CH2=C(CH3)-, 3H), 1.68-1.59 (m, -OCH2CH2CH2-, 2H), 1.52-1.48 (m, -SCH2CH2CH2-, 2H),
1.35-1.30 (m, -SCH2CH2CH2-, -OCH2CH2CH2-, 4H). 13C NMR (CDCl3, 125 MHz, DEPT,
[ppm]): 167.6 (C=O), 150.7 (aromatic C), 140.9 (aromatic C), 139.3 (aromatic C), 136.9
(CH2=CHCH2-), 136.5 (-CH(CH3)C=CH2), 125.4 (-CH(CH3)C=CH2), 120.7 (aromatic CH), 120.6

(aromatic CH), 116.4 (CH2=CHCH2-), 112.8 (aromatic CH), 64.6 (-OCH2CH2CH2-), 55.8 (-
OCH3), 40.0 (CH2=CHCH2-), 32.2 (-OCH2CH2CH2-), 29.5 (-CH2CH2CH2S-), 28.5 (-
CH2CH2CH2S-), 28.1 (-CH2CH2CH2S-), 25.5 (-OCH2CH2CH2-), 18.4 (-CH(CH3)C=CH2). 19F
3
NMR (CDCl3, 376 MHz, [ppm]):  -106.4 (s, 2F), -115.0 (s, 2F, JFF = 2.6 Hz), -130.0 (s, 2F).
MS (EI, 70 eV): m/z (% relative intensity) 538 (M+, 53), 452 (3), 370 (22), 337 (12), 328 (9), 161
(11), 147 (100), 131 (9), 115 (12), 91 (11), 69 (39), 55 (19).
Conflicts of interest
There are no conflicts to declare.
Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This paper was supported by the Air Force Office of Scientific Research. Additional
support was provided by the Air Force Research Laboratory, Aerospace Systems
Directorate, Edwards Air Force Base, CA.

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