The synthesis and application of fluorous boronates without perfluorinated solvents

Article abstract of DOI:10.1016/j.jfluchem.2004.12.014

The synthesis of a fluorous diol 4 bearing a perfluorodecyl chain was described. A series of boronic acid were attached to 4 by esterification. The purification of the products was fulfilled by facile filtration instead of expensive and environmental troublesome fluorous liquid-liquid extraction. The Suzuki cross-coupling reactions of the formed fluorous boronates 5 underwent smoothly and the fluorous diol 4 was recycled in good yields.

Full text of DOI:10.1016/j.jfluchem.2004.12.014

Journal of Fluorine Chemistry 126 (2005) 996–1001
www.elsevier.com/locate/fluor
The synthesis and application of fluorous boronates
without perfluorinated solvents
Chun-Yan Wang a, Wei-Dong Meng a, Yan-Gen Huang b, Feng-Ling Qing a,b,
*
a Institute of Biological Sciences and Biotechnology, Donghua University, 1882 West Yanan Road, Shanghai 200051, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, China
Received 8 November 2004; received in revised form 20 December 2004; accepted 21 December 2004
Available online 25 February 2005
Dedicated to Professor Herbert W. Roesky on the occasion of his 70th birthday.
Abstract
The synthesis of a fluorous diol 4 bearing a perfluorodecyl chain was described. A series of boronic acid were attached to 4 by
esterification. The purification of the products was fulfilled by facile filtration instead of expensive and environmental troublesome fluorous
liquid–liquid extraction. The Suzuki cross-coupling reactions of the formed fluorous boronates 5 underwent smoothly and the fluorous diol 4
was recycled in good yields.
# 2005 Elsevier B.V. All rights reserved.
Keywords: Fluorous biphase synthesis; Fluorous boronates; Suzuki coupling reaction
1. Introduction
usually isolable or recoverable by fluorous liquid–liquid
extraction, and a large amount of perfluorinated solvents are
needed. Compared with common organic solvents, the
fluorous solvents are expensive and may cause the
environmental persistence. Several groups reported that
the fluorous solid/organic liquid separation which could be
used to recycle the fluorous catalysts [5–7]. Several kinds of
polymer-bound diols [8] and fluorous diols [9] were used to
immobilize boronic acid and facilitate the intermediate
purification steps. According to the empirical rule [10]
‘‘longer fluorous chains cause an increase in partition
coefficient coupled with a decrease in absolute solubilities in
both phases’’, we designed and synthesized a fluorous diol 4
bearing a perfluorodecyl chain and then used it to attach the
boronic acid. The immobilization of the boronic acid via
fluorous diol 4 has two essential advantages compared with
the above methods. Firstly, the intermediates can be purified
through facile filtration, which omitted the expensive and
un-environmental perfluorinated solvent. Secondly, the
reaction can be conducted homogeneously and monitored
by TLC. We used the Suzuki coupling reaction of the
fluorous boronates as a de-tag strategy to recycle the fluorous
The solid-phase polymers and fluorous ponytails were
commonly used as ‘‘tags’’ in combinatorial and parallel
synthesis, which were usually designed to facilitate the
isolation of products, catalysts or reagents [1,2]. Solid-phase
synthesis has successfully simplified the separation to be an
easy wash and filtration, but the reactivity of the supported
substrates is slowed down because of unfavorable hetero-
geneous reaction kinetics. In addition, the inability to
monitor the reaction by NMR, mass spectroscopy and TLC
is another serious disadvantage for usual solid-phase
synthesis [3]. Therefore, fluorous synthesis has become
an excellent strategic alternative to solid-phase synthesis.
Fluorous synthesis that is similar to solid-phase synthesis in
concept is performed in homogeneous reactions. Many
applications of fluorous methodology have been extensively
developed in the last few years [4]. Fluorous compounds are
* Corresponding author. Fax: +86 21 54925187.
E-mail address: flq@mail.sioc.ac.cn (F.-L. Qing).
0022-1139/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.12.014

C.-Y. Wang et al. / Journal of Fluorine Chemistry 126 (2005) 996–1001
997
diol 4. The intermediates and final products can be purified
by simple wash and filtration.
carbon bond formation. As shown in Scheme 2, the Suzuki
coupling reaction of fluorous boronates 5 with aryl halides 6
underwent smoothly under standard Suzuki reaction
conditions [12]. Although fluorous boronates were used in
this case, we did not find any retarding effect for the Suzuki
coupling reaction by the perfluoroalkyl chains. Biaryl 7 was
obtained by filtration followed by chromatography (silica
gel) in good yield. The fluorous diol 4 was recovered at high
yield and purified by simple filtration which could be reused
for the reaction sequence. The results were summarized in
Table 1.
2. Results and discussion
The fluorous diol 4 and fluorous boronates 5 were
prepared as shown in Scheme 1. Dibenzoyl peroxide (DBP)
initiated addition of perfluorodecyl iodide to allyl acetate
afforded the adduct 2 in good yield [11]. Then reduction of 2
with zinc and acetic acid gave the fluorous alkene 3.
Dihydroxylation of 3 with N-methylmorpholine-N-oxide in
the presence of osmium tetraoxide and small quantity of
pyridine in aqueous acetone at 50 8C provided the desired
fluorous diol 4 in 87% yield. Subsequently, the fluorous diol
4 was used to immobilize boronic acid in trifluoromethyl-
benzene (BTF) at 50–80 8C. Diol 4 was completely
converted into fluorous boronate 5 by treatment with
1.0 equiv. or slightly excess of arylboronic acid. The
immobilization reaction usually took more than 15 h to
be finished. Higher reaction temperature can accelerate the
reaction. The reaction could be monitored by TLC. After
complete disappearance of fluorous diol 4, the reaction
mixture was concentrated in vacuo. A little ethanol was
added, and the excess organic boronic acid was removed by
shaking and filtration. The filtration cake was dissolved in
dichloromethane at elevated temperature. After cooling at
ꢀ10 8C, the white solid was re-crystallized from the
solution. Then the fluorous boronates 5a–j were obtained
through rapid filtration in high purity and good yields which
were fully characterized by 1H NMR, 19F NMR, IR, MS and
elemental analysis. Fluorous boronates 5 are mostly white or
pale yellow solids. Since prolonged exposure of moisture
might cause the hydrolysis of fluorous boronates, they were
kept in dry vessels and showed adequate storage stability for
long periods of time.
In conclusion, we have designed and synthesized a new
fluorous diol 4. A series of boronic acids were attached to
fluorous diol 4 by esterification. The key aspect of our
strategy was the application of fluorous solid/organic liquid
extraction without perfluorinated solvent. The formed
fluorous boronates could be purified by facile filtration.
The Suzuki coupling reaction was adopted as the de-tagging
strategy in synthesis, which also demonstrated the useful-
ness of fluorous solid/organic liquid extraction without
perfluorinated solvent. In addition, the fluorous diol could be
recovered in high yields and high purities.
3. Experimental
3.1. General
CF3C6H5 (BTF) was distilled over P2O5. Other purchased
chemicals and reagents were used as received. All reactions
were carried out under a dry nitrogen atmosphere in pre-
dried glasswares. Melting points were determined on a Pai-
ke melting point apparatus and were uncorrected. The
1
structures of all products were characterized by H NMR
and 19F NMR spectroscopy (Bruker AM 300, 300 MHz for
1
1H, 282 MHz for 19F or Bruker AM 400, 400 MHz for H,
The fluorous boronates 5a–j were then applied in Suzuki
coupling reaction, which is an important tool for carbon–
376 MHz for 19F) using TMS and CFCl3 as internal
standard. All chemical shifts (d) are expressed in ppm, and
Scheme 1. Synthesis of fluorous diol and its application in immobilizing organic boronic acids.

998
C.-Y. Wang et al. / Journal of Fluorine Chemistry 126 (2005) 996–1001
Scheme 2. Suzuki coupling reaction of fluorous boronates.
coupling constants (J) are given in Hertz. Mass spectra were
determined on a Finnigan-MAT-8430 instrument using EI
ionization at 70 eV. IR spectra were recorded on a Shimadzu
IR-440 spectrometer.
iso-propanol (60 mL) and the gray solution was heated.
After the temperature raised to 85 8C, acetic acid (30 mL)
diluted in iso-propanol (50 mL) was added dropwise for 1 h.
Then the reaction mixture was warmed to reflux for 7 h.
After the reaction mixture was cooled to room temperature,
a white solid was precipitated. Poured out the upper solution
and the solid was dried under vacuum. The desired product 3
3.2. 2-Iodo-3-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,
13,13,13-henicosafluorodecyl)propyl acetate(2)
1
was obtained as a white solid (12.401 g, 75%). H NMR
(400 MHz, CDCl3) d 5.86–5.79 (m, 1H), 5.39–5.33 (m, 2H),
2.93–2.82 (m, 2H); 19F NMR (376 MHz, CDCl3) d ꢀ80.94
(s, 3F), ꢀ113.34 (s, 2F), ꢀ121.84 (s, 10F), ꢀ122.81 (s, 2F),
ꢀ123.17 (s, 2F), ꢀ126.24 (s, 2F).
1-Iodoperfluorodecane
1 (27.101 g, 42 mmol) and
dibenzoyl peroxide (0.166 g, 1 mmol) were added into
trifluoromethylbenzene (10 mL) under nitrogen with stir-
ring. After the temperature was raised to 70 8C, the
substrates were dissolved completely. Then allyl acetate
(6.302 g, 63 mmol) was added dropwise for 1 h. The
reaction mixture was stirred for 8 h at 95–100 8C. Then the
reaction mixture was cooled to room temperature, a violet
brown solid was obtained. Purification of the crude product
by column chromatography (silica gel, petroleum ether:-
ethyl acetate = 50:1) gave compound 2 as a white solid
3.4. 3-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-
Henicosafluorodecyl)-propane 1,2-diol (4)
In a three-necked flask, NMNO (2.889 g, 22 mmol) and 3
(6.969 g, 12.4 mmol) were dissolved in a mixture of acetone
(40 mL), H2O (4 mL) and pyridine (1 mL). The mixture was
cooled to 0–5 8C, and 4% aqueous solution of OsO4
(1.2 mL) was added by syringe. After stirred for 1 h at 0 8C,
the reaction mixture was warmed to 50 8C and stirred for
20 h. Aqueous sodium disulfite (20 mL) was slowly added
through a dropping funnel to quench the reaction. The
reaction mixture is filtered on Buchner funnel. The filtrate
was extracted twice with ethyl acetate (30 mL) and the filter
residue was dissolved in ethyl acetate. The combined
organic layers were dried over anhydrous magnesium
sulfate, filtered and concentrated to afford the crude product.
Purification of the crude product by column chromatography
on silica gel (petroleum ether: ethyl acetate = 4: 3) gave
compound 4 as a white solid in 87% yield, mp: 136–138 8C.
1H NMR (400 MHz, Methanol–d4) d 3.98–3.94 (m, 1H),
3.46–3.35 (m, 2H), 2.39–2.29 (m, 1H), 2.20–2.07 (m, 1H);
19F NMR (376 MHz, Methanol–d4) d ꢀ82.32 (s, 3F),
ꢀ113.40, ꢀ114.02 (m, 2F), ꢀ122.66 (s, 10F), ꢀ123.66 (s,
2F), ꢀ124.62 (s, 2F), ꢀ127.22 (s, 2F). IR(KBr) 3405, 2963,
1209, 1151, 802, 647 cmꢀ1; MS (EI, 70 ev, m/z) 595
(M+ + 1,1), 594 (M+, 1), 577 (1), 563 (100), 169 (20), 131
(39), 100 (10), 69 (59).
1
(26.893 g, 86%). H NMR (400 MHz, CDCl3) d 4.39–4.19
(m, 3H), 2.90–2.77 (m, 2H), 2.05 (s, 3H); 19F NMR
(376 MHz, CDCl3) d ꢀ81.07 (s, 3F), ꢀ113.40, ꢀ114.02 (2s,
2F), ꢀ122.02 (s, 10F), ꢀ122.96 (s, 2F), ꢀ123.76 (s, 2F),
ꢀ126.38 (s, 2F).
3.3. 3-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-
Henicosafluorodecyl)-propene (3)
Zinc powder (2.493 g, 38 mmol) was added to a
vigorously stirred solution of 2 (22.124 g, 29 mmol) in
Table 1
Suzuki coupling reaction of fluorous boronates 5 and the recovery of diol 4a
Entry
Fluorous
R0X
RR0
Yield
(%)
Recovery of
diol 4 (%)b
boronates 5
1
2
3
4
5
6
7
8
a
5a
5b
5e
5f
5g
5h
5i
6a
6a
6a
6a
6a
6a
6a
6b
7aa
7ab
7ae
7af
7ag
7ah
7ai
84
87
76
92
89
86
82
84
91
92
89
94
89
76
81
90
5a
7ba
3.5. General procedure for the preparation of fluorous
boronates (5)
All reactions were carried out in the presence of aryl halides
(0.16 mmol), fluorous boronates (0.15 mmol), Pd(PPh3)4 (6 mg,
5
0.0052 mmol) and aqueous potassium phosphate (2 M, 15 mL, 0.3 mmol)
To a mixture of organic boronic acid (0.300 mmol) and
fluorous diol 4 (178 mg, 0.299 mmol) was added BTF
in dioxane (3 mL).
b
Yields were based on the fluorous boronates 5.

C.-Y. Wang et al. / Journal of Fluorine Chemistry 126 (2005) 996–1001
999
(6 mL) under nitrogen atmosphere. Then the mixture was
3.5.4. 2-Styryl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,
stirred at 70 8C for about 15 h. The solvent was removed
under vacuum to afford a white solid, then ethanol (1.5 mL)
was added. The mixture was shaken vigorously and filtered.
Then the filtration cake was dissolved in dichloromethane
at elevated temperature, cooled to ꢀ10 8C and fluorous
boronates 5 were obtained by rapid filtration.
11,11-henicosaflu-orodecyl)-[1,3,2] dioxaborolane(5d)
Yield: 196 mg (94%) 1H NMR (300 MHz, CDCl3) d 7.5–
7.50 (m, 2H), 7.44 (d, J = 18.3 Hz, 1H), 7.40–7.33 (m, 3H),
6.18 (d, J = 18.3 Hz, 1H), 4.95–4.86 (m, 1H), 4.54–4.48 (t,
J = 9.0 Hz, 1H), 4.04–3.98 (t, J = 9.0 Hz, 1H), 2.70–2.57
(m, 1H), 2.48–2.34 (m, 1H); 19F NMR (282 MHz, CDCl3) d
ꢀ80.97 (s, 3F), ꢀ112.81 (s, 2F), ꢀ122.07 (s, 10F), ꢀ122.98
(s, 2F), ꢀ123.80 (s, 2F), ꢀ126.40 (s, 2F); IR(KBr) 2965,
2923, 1625, 1577, 1450, 1351, 1212, 1151, 1113, 1025, 881,
752, 695, 649, 558, 529 cmꢀ1; MS (EI, 70 ev, m/z) 707 (M+,
20), 706 (M+ ꢀ 1,100), 173 (71), 143 (15), 117 (25), 116
(55), 69 (16); Anal. Calcd. for C21H12F21BO2: C 35.69,
H 1.71; Found: C 35.55, H 2.01.
3.5.1. 2-Phenyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,
11,11,11-henicosafluorodecyl-[1,3,2] dioxaborolane (5a)
1
Yield: 191 mg (94%), H NMR (400 MHz, CDCl3) d
7.82–7.80 (m, 2H), 7.52–7.48 (m, 1H), 7.41–7.34 (m, 2H),
4.58 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.09 (dd,
J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.73–2.65 (m, 1H), 2.45–
2.38 (m, 1H); 19F NMR (376 MHz, CDCl3) d ꢀ80.67 (s, 3F),
ꢀ112.40 (s, 2F), ꢀ121.72 (s, 10F), ꢀ122.65 (s, 2F),
ꢀ123.47 (s, 2F), ꢀ126.06 (s, 2F); IR (KBr) 2963, 2921,
1603, 1500, 1485, 1441, 1406, 1386, 1355, 1218, 1151,
1095, 1027, 884, 802, 760, 700, 648, 556, 529 cmꢀ1; MS
(EI, 70 ev, m/z) 680 (M+, 29), 148 (10), 147 (100), 118 (28),
117 (12), 91 (32), 77 (5), 69 (9). Anal. Calcd. for
C19H10F21BO2: C 33.56, H 1.48; Found: C 33.86, H
1.70.
3.5.5. 2-Thienyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,
11,11-henicosafluorodecyl)-[1,3,2] dioxaborolane(5e)
Yield: 190 mg (94%) 1H NMR (400 MHz, CDCl3) d 7.69
(d, J = 4.0 Hz, 2H), 7.22(t, J = 4.0 Hz 1H), 5.02–4.95 (m,
1H), 4.60–4.56 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.12–4.08
(dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.76–2.71 (m, 1H), 2.45–
2.39 (m, 1H); 19F NMR (376 MHz) d ꢀ80.69 (s, 3F), ꢀ112.37
(s, 2F), ꢀ121.71 (s, 10F), ꢀ122.65 (s, 2F), ꢀ123.48 (s, 2F),
ꢀ126.06 (s, 2F); IR(KBr) 2997, 2926, 1524, 1438, 1428,
1360, 1303, 1208, 1151, 1062, 1020, 885, 657, 556,
529 cmꢀ1; MS (EI, 70 ev, m/z) 687 (M+ + 1, 12), 686
(M+, 54), 153 (100), 124 (24), 97 (35), 69 (20); Anal. Calcd.
for C17H8F21BO2S: C 29.76, H 1.17; Found: C 29.83,
H 1.13.
3.5.2. 2-p-Tolyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,
10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane(5b)
1
Yield: 195 mg (94%), H NMR (400 MHz, CDCl3) d
7.70(d, J = 8.0 Hz, 2H), 7.21(d, J = 8 Hz, 2H), 5.00–4.95
(m, 1H), 4.57 (dd, J1 = 7.2 Hz, J2 = 9.2 Hz, 1H), 4.08 (dd,
J1 = 7.2 Hz, J2 = 9.2 Hz, 1H), 2.73–2.69 (m, 1H), 2.44–2.38
(m, 1H), 2.38 (s, 3H); 19F NMR (376 MHz, CDCl3) d
ꢀ80.68 (s, 3F), ꢀ112.39 (s, 2F), ꢀ121.71 (s, 10F), ꢀ122.64
(s, 2F), ꢀ123.47 (s, 2F), ꢀ126.05 (s, 2F); IR(KBr) 2989,
2921, 1614, 1519, 1486, 1438, 1409, 1386, 1354, 1322,
1217, 1152, 1092, 1022, 884, 816, 647, 556, 529 cmꢀ1; MS
(EI, 70 ev, m/z) 695 (M+ + 1,17), 694 (M+, 80), 161 (100),
132 (44), 105 (48), 91 (28), 69 (15). Anal. Calcd for
C20H12F21BO2: C 34.60, H 1.74; Found: C 34.38, H
2.15.
3.5.6. 2-(4-Methylthiophenyl)-4-(2,2,3,3,4,4,5,5,6,6,
7,7,8,8,9,9,10,10,11,11,11-henicosafluorodecyl)-
[1,3,2]dioxaborolane(5f)
Yield: 206 mg (94%) 1H NMR (400 MHz, CDCl3) d
7.68(s, 1H), 7.56(d, J = 8.0 Hz 1H), 7.48–7.38 (m, 1H), 7.32
(d, J = 8.0 Hz 1H), 5.00–4.97 (m, 1H), 4.58 (dd, J1 = 8.0 Hz,
J2 = 8.0 Hz, 1H), 4.09 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H),
2.79–2.64 (m, 1H), 2.50 (s, 3H), 2.53–2.30 (m, 1H); 19F
NMR (376 MHz) d ꢀ80.67 (s, 3F), ꢀ112.34 (s, 2F),
ꢀ121.68 (s, 10F), ꢀ122.62 (s, 2F), ꢀ123.44 (s, 2F),
ꢀ126.03 (s, 2F); IR(KBr) 2983, 2920, 1631, 1592, 1440,
1353, 1209, 1152, 1017, 998, 881, 791, 701, 650, 556,
530 cmꢀ1; MS (EI, 70 ev, m/z) 728 (M+ + 2, 7), 727 (M+ + 1,
23), 726 (M+, 100), 193 (23), 164 (7), 137 (27), 69 (14);
Anal. Calcd. for C20H12F21BO2S: C 33.08, H 1.67; Found: C
33.05, H 2.15.
3.5.3. 2-(4-Methoxyphenyl)-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane (5c)
Yield: 195 mg (94%) 1H NMR (400 MHz, CDCl3) d 7.75
(d, J = 8.0 Hz, 2H), 6.92 (d, J = 8.0 Hz, 2H), 4.99–4.93 (m,
1H), 4.56 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.06 (dd,
J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 3.84 (s, 3 H), 2.72–2.68 (m,
1H), 2.43–2.36 (m, 1H); 19F NMR (376 MHz, CDCl3) d
ꢀ80.68 (s, 3 F), ꢀ112.37 (s, 2F), ꢀ121.70 (s, 10F), ꢀ122.63
(s, 2F), ꢀ123.46 (s, 2F), ꢀ126.04 (s, 2F); IR (KBr) 2962,
2934, 2839, 1608, 1569, 1486, 1454, 1439, 1413, 1386,
1355, 1296, 1215, 1151, 1095, 1031, 885, 831, 797, 646,
556, 529 cmꢀ1; MS (EI, 70 ev, m/z) 711 (M+ + 1, 23), 710
(M+, 100), 177 (41), 148 (26), 121 (39), 69 (16); Anal. Calcd.
for C20H12F21BO3: C 33.83, H 1.70; Found: C 33.79, H 1.70.
3.5.7. 2-(4-Chlorophenyl)-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane (5g)
Yield: 196 mg (94%) 1H NMR (400 MHz, CDCl3) d 7.73
(d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 5.02–4.95 (m,
1H), 4.58 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.09 (dd,
J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.74–2.67 (m, 1H), 2.45–2.38
(m, 1H); 19F NMR (376 MHz, CDCl3) d ꢀ80.67 (s, 3F),
ꢀ112.37 (s, 2F), ꢀ121.69 (s, 10F), ꢀ122.62 (s, 2F),

1000
C.-Y. Wang et al. / Journal of Fluorine Chemistry 126 (2005) 996–1001
ꢀ123.43 (s, 2F), ꢀ126.03 (s, 2F); IR(KBr) 2963, 2924,
1599, 1522, 1485, 1438, 1406, 1394, 1353, 1216, 1152,
1097, 1017, 884, 794, 644, 555, 529 cmꢀ1; MS (EI, 70 ev, m/
z) 716 (M+ + 2, 18), 714 (M+, 52), 183 (33), 181 (100), 154
(10), 152 (32), 127 (14), 125 (42), 69 (23); Anal. Calcd.
for C19H9F21BO2Cl: C 31.93, H 1.26; Found: C 31.62,
H 1.25.
3.6. Experimental procedures for the fluorous Suzuki-
coupling reaction
To a solution of aryl halide (0.16 mmol) in dioxane
(3 mL) was added fluorous boronate 5 (0.15 mmol), Pd
(PPh3)4 (6 mg, 0.0052 mmol) and aqueous potassium
phosphate (2 M, 15 mL, 0.3 mmol). The reaction mixture
was heated to reflux for 20 h and then extracted with ethyl
acetate (3 mL) twice. The combined organic layers were
filtered through a short plug of kieselguhr which was washed
with ethyl acetate (2 mL). The filtrate was concentrated on a
rotary evaporator, then filtered again and washed with
dichloromethane (1 mL). The fluorous diol 4 was recovered
as the filtration cake and dried in vacuum and characterized
by 1H and 19F NMR. The purity of the fluorous diol attained
was above 95%. Then the filtrate was concentrated by rotary
evaporation. The crude product was purified by chromato-
graphy on silica gel to give the biaryl product 7.
3.5.8. 2-(3-Aminophenyl)-4-(2,2,3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane (5h)
1
Yield: 189 mg (94%), H NMR (400 MHz, CDCl3) d
7.21–7.12 (m, 3 H), 6.84–6.81 (m, 1H), 5.00–4.93 (m, 1H),
4.56 (t, J = 8.0 Hz, 1H), 4.07 (t, J = 8.0 Hz, 1H), 3.75 (br,
2H), 2.72–2.68 (m, 1H), 2.45–2.34 (m, 1H); 19F NMR
(376 MHz, CDCl3) d ꢀ80.68 (s, 3F), ꢀ112.38 (s, 2F),
ꢀ121.69 (s, 10F), ꢀ122.63 (s, 2F), ꢀ123.46 (s, 2F),
ꢀ126.04 (s, 2F); IR(KBr) 3431, 3374, 2922, 1620, 1582,
1447, 1357, 1216, 1151, 1090, 1016, 887, 706, 665, 644,
557, 529 cmꢀ1; MS (EI, 70 ev, m/z) 696 (M+ + 1, 21),
695 (M+, 100), 694 (M+ ꢀ 1,35), 162 (35), 131 (11), 119
(49), 106 (36), 69 (20); Anal. Calcd. for C19H11F21BO2N:
C 32.83, H 1.59, N 2.01; Found: C 32.62, H 1.68,
N 1.70.
3.6.1. Biphenyl (7aa)
1H NMR (400 MHz, CDCl3) d 7.56 (d, J = 8.0 Hz, 4H),
7.44 (t, J = 8.0 Hz, 4H), 7.34 (t, J = 8.0 Hz, 2H).
3.6.2. 4-Phenyltoluene (7ab)
1H NMR (400 MHz, CDCl3) d 7.57 (d, J = 8.0 Hz, 2H),
7.49 (d, J = 8.0 Hz, 2H), 7.42 (t, J = 7.6, 2H), 7.32 (t,
J = 7.6 Hz, 1H), 7.24 (d, J = 8.0 Hz, 2H).
3.5.9. 2-(4-Formylphenyl)-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane (5i)
1
3.6.3. 2-Phenylthiophene (7ae)
1H NMR (400 MHz, CDCl3) d 7.63–7.61 (m, 2H), 7.40–
7.36 (m, 2H), 7.32–7.26 (m, 3H), 7.09–7.07 (m, 1H).
Yield: 194 mg (94%), H NMR (400 MHz, CDCl3) d
10.07 (s, 1H), 7.97 (d, J = 8.0 Hz, 2H), 7.89 (d, J = 8.0 Hz
2H), 5.06–4.99 (m, 1H), 4.63 (t, J = 8.0 Hz, 1H), 4.14 (t,
J = 8.0 Hz, 1H), 2.75–2.67 (m, 1H), 2.51–2.39 (m, 1H); 19
F
3.6.4. 3-Methylsulfanylbiphenyl (7af)
1H NMR (400 MHz, CDCl3) d 7.57–7.54 (m, 2H), 7.47–
7.40 (m, 3H), 7.36–7.31 (m, 3H), 7.25–7.20 (m, 1H), 2.50 (s,
3H).
NMR (376 MHz, CDCl3) d ꢀ80.70 (s, 3F), ꢀ112.35 (s, 2F),
ꢀ121.69 (s, 10F), ꢀ122.63 (s, 2F), ꢀ123.43 (s, 2F),
ꢀ126.04 (s, 2F); IR(KBr) 2963, 2925, 2849, 1707, 1677,
1563, 1511, 1438, 1406, 1384, 1352, 1219, 1151, 1090,
1018, 885, 828, 791, 645, 556, 529 cmꢀ1; MS (EI, 70 ev, m/
z) 708 (M+, 36), 707 (M+ ꢀ 1,100), 706 (M+ ꢀ 2,28), 175
(76), 146 (23), 119 (35), 91 (18), 69 (18); Anal. Calcd. for
C20H10F21BO3: C 33.93, H 1.42; Found: C 33.83,
H 1.68.
3.6.5. 4-Chlorobiphenyl (7ag)
1H NMR (400 MHz, CDCl3) d 7.58–7.50 (m, 4H), 7.46–
7.33 (m, 5H).
3.6.6. 3-Aminobiphenyl (7ah)
1H NMR (400 MHz, CDCl3) d 7.57–7.55 (m, 2H), 7.44–
7.33 (m, 3H), 7.26–7.24 (m, 1H), 7.02–6.72 (m, 3H), 3.89–
3.55 (br, 2H).
3.5.10. 2-Propyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,
11,11,11-henicosa-fluorodecyl)-[1,3,2] dioxaborolane (5j)
1
Yield: 175 mg (94%), H NMR (400 MHz, CDCl3) d
4.80–4.76 (m, 1H), 4.38 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H),
3.89 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.61–2.56 (m, 1H),
2.29–2.17 (m, 1H), 1.50–1.42 (m, 2H), 0.94 (t, J = 7.6 Hz,
3H), 0.85 (t, J = 7.6Hz, 3H); 19F NMR(376 MHz, CDCl3) d
ꢀ80.70 (s, 3F), ꢀ112.46 (s, 2F), ꢀ121.71 (s, 10F), ꢀ122.63
(s, 2F), ꢀ123.51 (s, 2F), ꢀ126.04 (s, 2F); IR(KBr) 2931,
1631, 1374, 1344, 1209, 1151, 1063, 892, 648, 557,
529 cmꢀ1; MS (EI, 70 ev, m/z) 645 (M+ ꢀ 1,2), 113 (88), 69
(82), 61 (100); Anal. Calcd. for C10H12F21BO2: C 29.74, H
1.87; Found: C 29.53, H 1.79.
3.6.7. 4-Formylbiphenyl (7ai)
1H NMR (400 MHz, CDCl3) d 10.06 (s, 1H), 7.97–7.95
(m, 2H), 7.77–7.75(m, 2H), 7.65–7.63 (m, 2H), 7.51–7.47
(m, 3H).
3.6.8. 2,4-Difluorobiphenyl (7ba)
1H NMR (400 MHz, CDCl3) d 7.70–7.68 (m, 2H), 7.60–
7.41 (m, 5H), 7.05–6.95 (m, 1H); 19F NMR (376 MHz,
CDCl3) d ꢀ111.68 (s, 1F), ꢀ113.70 (s, 1F).

C.-Y. Wang et al. / Journal of Fluorine Chemistry 126 (2005) 996–1001
1001
(h) B. Betzemeier, P. Knochel, Top. Curr. Chem. 206 (1999)
61–78;
Acknowledgement
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China and Shanghai Municipal Scientific Committee for
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