Convenient syntheses of fluorous phenols of the formula triarylphosphites

Article abstract of DOI:10.1016/S0022-1139(02)00242-7

The aldehydic benzyl ethers PhCH₂OC₆H₄CHO (2; a/b = paralmeta series) are readily available from the corresponding phenols and react with Wittig reagents derived from [Ph₃PCH₂CH₂R_f8]^+- (R_f8 = (CF₂)₇CF₃) to give PhCH₂OC₆H₄CH=CHCH₂R_f8 (86-93%, Z major). Reactions with H₂ over Pd/C give the fluorous phenols HOC₆H₄(CH₂)₃R_f8 (4a,b; 87-91%). Condensations with PCl₃ and NEt₃ (3.0:1:0:3.3 mol ratio) give the flourous phosphites P[OC₆H₄(CH₂)₃R_f8] ₃ (5a,b; 92-94%), but traces of 4a,b are difficult to remove. The phthalate-based benzyl ethers PhCH₂OC₆H₃COOR ₂ (7; c/d = 3,5/3,4 -OC₆H₃-3,n-(R)₂ series) are easily accessed and reduced with LiAlH₄ to the diols PhCH₂OC₆H₃(CH₂OH)₂ (8c,d; 89-90%). Diol 8c and the Dess-Martin periodinane react to give the dialdehyde PhCH₂OC₆H₃(CHO)₂ (9C; 95%). This is elaborated by a sequence analogous to 2 → 4 → 5 to the flourous phenol HOC₆H₃((CH₂)₃R_f8) ₂ (11c; 97%/96%, two steps) and phosphite P[OC₆H₃((CH₂)₃R_f8) ₂]₃ (12C, 92%), from which traces of 11c are difficult to remove. Diol 8d can be similarly elaborated to 11d, but the dialdehyde 9d is labile and combined yield of the Dess-Martin/Wittig steps is 32%. The CF₃C₆F₁₁/ toluene partition coefficients of 11c,d, and 12c (two pony tails; 70:30,72:28, 92:8) are much higher than those of 4a and b (one pony tail; 12:88, 14:86).

Full text of DOI:10.1016/S0022-1139(02)00242-7

Journal of Fluorine Chemistry 119 (2003) 141±149
Convenient syntheses of ¯uorous phenols of the formula
HOC6H5Àn((CH2)3(CF2)7CF3)n (n ˆ 1, 2) and the
corresponding triarylphosphites
Sylvie Le Stang, Ralf Meier, Christian Rocaboy, J.A. Gladysz*
È È È
Institut fur Organische Chemie, Friedrich-Alexander-Universitat Erlangen-Nurnberg,
Henkestrasse 42, 91054 Erlangen, Germany
Received 28 August 2002; received in revised form 16 September 2002; accepted 16 September 2002
Abstract
The aldehydicbenzyl ethers PhCH 2OC6H4CHO (2; a/b ˆ para/meta series) are readily available from the corresponding phenols and react
‡ À
with Wittig reagents derived from [Ph3PCH2CH2Rf8] I (Rf8 ˆ ꢀCF2†7CF3) to give PhCH2OC6H4CH=CHCH2Rf8 (86±93%, Z major).
Reactions with H2 over Pd/C give the ¯uorous phenols HOC6H4(CH2)3Rf8 (4a,b; 87±91%). Condensations with PCl3 and NEt3
(3.0:1.0:3.3 mol ratio) give the ¯uorous phosphites P[OC6H4(CH2)3Rf8]3 (5a,b; 92±94%), but traces of 4a,b are dif®cult to remove. The
phthalate-based benzyl ethers PhCH2OC6H3(COOR)2 (7; c=d ˆ 3,5/3,4 ±OC6H3-3,n-(R)2 series) are easily accessed and reduced with
LiAlH4 to the diols PhCH2OC6H3(CH2OH)2 (8c,d; 89±90%). Diol 8c and the Dess-Martin periodinane react to give the dialdehyde
PhCH2OC6H3(CHO)2 (9c; 95%). This is elaborated by a sequence analogous to 2 ! 4 ! 5 to the ¯uorous phenol HOC6H3((CH2)3Rf8)2 (11c;
97%/96%, two steps) and phosphite P[OC6H3((CH2)3Rf8)2]3 (12c, 92%), from which traces of 11c are dif®cult to remove. Diol 8d can be
similarly elaborated to 11d, but the dialdehyde 9d is labile and the combined yield of the Dess-Martin/Wittig steps is 32%. The CF3C6F11/
toluene partition coef®cients of 11c,d, and 12c (two pony tails; 70:30, 72:28, 92:8) are much higher than those of 4a and b (one pony tail;
12:88, 14:86).
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Fluorous; Phenols; Phosphites; Wittig reaction; Partition coef®cients
1. Introduction
¯uorous catalyst under biphasic conditions at lower tem-
peratures. The recovered catalyst solution is then directly
reused.
The development of catalysts that have high af®nities for
``¯uorous'' phases has proceeded rapidly since the ®rst
report of ``¯uorous biphase catalysis'' in 1994 [1,2]. This
technique makes use of two phenomena: (1) the tempera-
ture-dependent miscibility of organic solvents with ¯uorous
solvents (saturated per¯uorocarbons, per¯uorodialkylethers,
or per¯uorotrialkylamines) [3], and (2) phase labels or
``pony tails'' of the formula (CH2)m(CF2)nÀ1CF3 (abbre-
viated (CH2)mRfn) [4], which when added to catalysts in
suf®cient numbers, provide exceptional ¯uorous solvent
af®nities. Reactions can be conducted in mixtures of organic
and ¯uorous solvents under monophasicconditions at higher
temperatures, and the products (which normally have much
greater af®nities for organicsolvents) separated from the
Approximately, half of the ¯uorous metal catalysts devel-
oped to date feature ¯uorous phosphines [1,5,6], and much
effort has been devoted to the synthesis of such ligands
[5d],[6a,f-h], [7±9]. However, less attention has been given
to the synthesis and application of ¯uorous trialkylphosphites
[8a,c]1, [10]1, or triarylphosphites [11].2 Phosphites consti-
tute an extremely useful and sometimes singularly successful
class of ligands for metal-catalyzed reactions, and Fig. 1
summarizes the ¯uorous triarylphosphites reported to date.
However, the most readily accessible (I, IV) contain only one
pony tail per ring [11a,b]. At least two pony tails are required
to impart high ¯uorous phase af®nities to benzenoid com-
pounds [12]. Also, a range of insulating (CH2)m segment
1 To date, only P(OCH2CH2Rf8)3, and P(OCH2CH2Rf6)3 have been
reported.
* Corresponding author. Tel.: ‡49-9131-8522540;
fax: ‡49-9131-8526865.
2 For phosphorus donor ligands with one or two O(CH2)mRfn
E-mail address: gladysz@organik.uni-erlangen.de (J.A. Gladysz).
substituents, see references [6d,8a].
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 2 ) 0 0 2 4 2 - 7

142
S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
Scheme 1. Synthesis of fluorous phosphites with one pony tail.
The simultaneous removal of the benzyl protecting group
and reduction of the C=C linkages in 3a,b was envisioned.
Accordingly, 3a,b and H2 (1 atm) were reacted in the
presence of 10% Pd/C (10 mol.%). Workups gave the cor-
responding phenols HOC6H4(CH2)3Rf8 (4a,b) as low-melt-
ing white solids in 87±91% yields. When reactions were
conducted above room temperature, reduction to substituted
cyclohexanols HOC6H11(CH2)3Rf8 was observed, as evi-
Fig. 1. Some previously reported fluorous phosphites (Rf8 ˆ ꢀCF2†CF3).
lengths are desirable, such that the phosphorus donor/accep-
tor properties can be ®ne-tuned [13].
In this paper, we report convenient and general metho-
dology for the synthesis of ¯uorous phenols and triarylpho-
sphites bearing one and two pony tails per ring. Our
approach uses easily accessed ethers of phenol aldehydes,
and readily available ¯uorous Wittig reagents [12a]. The
¯uorous phase af®nities of selected compounds are also
quanti®ed.
1
denced by characteristic H and 13C NMR signal patterns.
Phenols 4a,b were characterized by microanalysis, IR and
NMR (1H, 13C, 19F) spectroscopy, and mass spectrometry.
Other new compounds that were not mixtures of isomers
were generally characterized similarly. All structures fol-
lowed readily from the spectroscopic properties.
Phenols 4a,b were next condensed with PCl3 and NEt3
(3.0:1.0:3.3 mol ratio) under standard conditions for the
synthesis of triarylphosphites. Workups gave the ¯uorous
phosphites P[OC6H4(CH2)3Rf8]3 (5a,b) in 92±94% yields as
low-melting white powders. Although 5a,b afforded satis-
factory microanalyses, NMR spectra consistently showed 5±
8% of the phenol precursors, as assayed from well-separated
2. Results
We recently described facile syntheses of the ¯uorous
‡ À
phosphonium salts [Ph3PCH2CH2Rfn] I (n ˆ 6, 8 (1), 10),
and high-yield Wittig reactions with benzaldehyde, phtha-
laldehydes, and related compounds [12]. The resulting
alkenes were easily hydrogenated to the corresponding
¯uorous arenes. As shown in Scheme 1, a similar sequence
was used to prepare protected ¯uorous phenols. Commer-
cially available 4- and 3-hydroxybenzaldehyde were
®rst converted to previously characterized benzyl ethers
PhCH2OC6H4CHO (2a,b) [14,15] under standard conditions
(Na2CO3, PhCH2Br). Then the phosphonium salt 1, K2CO3,
and 2a or b were heated in 1,4-dioxane. Workups gave the
¯uorous alkenes PhCH2OC6H4CH=CHCH2Rf8 (3a,b) in
88±92% yields as 95:5 mixtures of Z/E isomers. The stereo-
chemistry was assigned from the 3JHH values of the CH=CH
1H NMR signals, and was consistent with much literature
precedent for Wittig reactions of unstabilized ylides.
1
aryl H NMR signals. Extensive efforts to remove these
traces, either by selective extraction, chromatography (alu-
mina, carefully dried silica gel), or species capable of
scavenging hydroxylic impurities (e.g. Na, or the Sicapent1
formulation of P2O5) were unsuccessful. Phenols 4a,b were
soluble in a broad spectrum of organic and ¯uorous solvents
(toluene, ether, THF, CHCl3, CH2Cl2, CH3CN, DMF, NEt3,
CF3C6H5, CF3C6F5, CF3C6F11). Phosphites 5a,b were also
soluble in many organicsolvents (toluene, ether, THF,
CHCl3, CH2Cl2), moderately soluble in CF3C6F11, and
insoluble in hexane.
We sought to extend the preceding sequences to phenols
and triarylphosphites with two pony tails per ring. Hence,

S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
143
Scheme 3. Synthesis of a second fluorous phenol with two pony tails.
ging to isolate. Accordingly, the crude material from the
Dess-Martin oxidation was immediately subjected to the
Wittig conditions (1, K2CO3). Workup gave the ¯uorous
diene 10d in 32% yield as a mixture of isomers. Hydro-
genation and hydrogenolysis as above gave the target phenol
11d in 90% yield.
The ¯uorous phenols 11c,d were low-melting white solids
(ca. 70 and 47 8C) with solubility characteristics similar to
Scheme 2. Synthesis of a fluorous phosphite with two pony tails.
Table 1
Partition coefficients (24 8C)
dialdehyde building blocks were required. As shown in
Scheme 2, commercial 5-hydroxyisophthalic acid dimethyl
ester (6c) was converted to the benzyl ether (7c) (K2CO3,
PhCH2Br; 86%). Since ethanol was used as the solvent,
transesteri®cation occurred simultaneously. Reduction with
LiAlH4 gave the corresponding diol 8c in 89% yield after
workup. Oxidation with the Dess-Martin periodinane
afforded the dialdehyde 9c (95%), which was treated with
the phosphonium salt 1 and K2CO3 according to the pro-
cedure in Scheme 1. Workup gave the ¯uorous diene 10c in
97% yield as a mixture of ZZ, ZE, and EE isomers. Hydro-
genation and hydrogenolysis were effected as in Scheme 1 to
give the target 3,5-substituted phenol 11c in 96% yield.
The 3,4-substituted analog of 11c was sought. Commer-
cial 4-hydroxyphthalic acid was ®rst converted to its known
dimethyl ester 6d (MeOH, H2SO4; 82%) [16]. As shown in
Scheme 3, 6d was then transformed to the corresponding
benzyl ether 7d (K2CO3, PhCH2Br; 95%). Acetone solvent
was used to avoid the transesteri®cation encountered in
Scheme 2. Reduction with LiAlH4 gave the corresponding
diol 8d in 90% yield after workup. Reaction with the Dess-
Martin periodinane afforded the dialdehyde 9d. However, it
was much more labile than isomer 9c, and proved challen-
Analyte
CF3C6F11/toluene
HOC6H4-4-(CH2)3Rf8 (4a)
HOC6H4-3-(CH2)3Rf8 (4b)
HOC6H3-3,5-((CH2)3Rf8)2 (11c)
HOC6H3-3,4-((CH2)3Rf8)2 (11d)
HOC6H4-4-(CH2)2Rf8 (13)
P[OC6H3-3,5-((CH2)3Rf8)2]3 (12c)
C6H5(CH2)3Rf8 (14)
12:88a
14:86a
70:30a
72:28a
20:80a
92:8a
49.5:50.5b,c
91.2:8.8b,c
90.7:9.3b,c
69.5:30.5b,d
74.7:25.3b,d
73.9:26.1b,d
66.6:33.4b,e
1,2-C6H4((CH2)3Rf8)2 (15)
1,3-C6H4((CH2)3Rf8)2 (16)
IC6H3-3,4-((CH2)3Rf8)2 (17)
IC6H3-2,4-((CH2)3Rf8)2 (18)
IC6H3-2,5-((CH2)3Rf8)2 (19)
P[C6H4-4-(CH2)3Rf8]3 (20)
C8F17H/1-decene
P[OC6H4-4-(CH2)2Rf8]3 (IVb)
P[OC6H4-2-(CH2)2Rf8]3 (IVc)
P[OC6H3-2,4-((CH2)2Rf8)2]3 (V)
95:5b,f
95:5b,f
99:1b,f
a Determined by 1H and/or 19F NMR, this work.
b Determined by GC.
c Reference [12a].
d Reference [12b].
e Reference [5d], 27 8C.
f Reference [11c].

144
S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
those of 4a,b. As shown in Scheme 2, 11c was condensed
with PCl3 and NEt3 under conditions analogous to those
used above. Workup gave the six pony-tailed ¯uorous
phosphite P[OC6H3-3-5-((CH2)3Rf8)2]3 (12c) in 92% yields.
NMR spectra usually showed 3±5% of the precursor phenol
11c, and the puri®cation techniques investigated with 5a,b
were again unsuccessful. Phosphite 12c was soluble in
toluene, ether, THF, CHCl3, CH2Cl2, CF3C6H5, CF3C6F5,
and C8F17Br, and moderately soluble in CF3C6F11.
Finally, the CF3C6F11/toluene partition coef®cients of
phenols 4a,b, 11c,d, and HOC6H4-4-(CH2)2Rf8 (13) [11c]
were measured. The last compound features one less methy-
lene group than 4a. However, GC analyses were not satis-
factory from the standpoint of tailing (11c,d) and/or mass
balance. Hence, 1H and/or 19F NMR spectroscopy was
utilized, as detailed in the experimental section. The parti-
tion coef®cient of a sample of 12c that contained no
detectable phenol was also determined. Data are summar-
ized in Table 1. Published values for selected reference
compounds are included for comparison, and trends are
analyzed in the Section 3.
results in catalysis, they were not included in our initial
study.
Although our target triarylphosphites were normally
obtained in purities of ca. 95%, this is a suf®cient level
for many catalyst screening studies, which were in fact
conducted under the auspices of an industrial cooperation.
It should be emphasized that there are no detectable phos-
phorus-containing impurities, only the precursor phenols. In
terms of electronic properties, the triply pony-tailed ¯uorous
triarylphosphine P(4-C6H4(CH2)3Rf8)3 remains less basic
than PPh3, as assayed by the IR nCO value of an iridium
adduct [5d]. Hence, the inductive effect of the per¯uoralkyl
segment can be transmitted through many connecting atoms
[13]. We suggest that the basicities of double pony tailed
11c,d are decreased by comparable amounts relative to
unsubstituted phenol, and that both are stronger Brùnsted
acids. The phosphites 4a,b and 12c should also be somewhat
weaker donors and stronger acceptors than triphenylpho-
sphite. However, these contain an extra insulating atom
(oxygen) between the donor atom and each per¯uoroalkyl
segment.
The partition coef®cients in Table 1 show the expected
general dependence upon the number of pony tails. In the
singly pony-tailed series, C6H5(CH2)3Rf8 (14) represents a
useful reference compound. Upon introducing a polar phe-
nolichydroxy group in the 4- or 3-position (4a,b), the
partition coef®cient drops from ca. 50:50 to (12±14):(88±
86). However, when a methylene group is removed from 4a
to give 13, the partition coef®cient increases slightly to
20:80. In the double pony-tailed series, the partition coef®-
cients of the reference compounds C6H4((CH2)3Rf8)2 (1,2-,
15; 1,3-, 16) decrease from ca. 91:9 to (70±72):(30±28) upon
introduction of a hydroxy group (11c,d). The latter values
are very close to those of several aryl iodides of the formula
IC6H3((CH2)3Rf8)2 (17±19), ca. (70±75):(30±25) [12b], one
of which can be viewed as a substitution product of 11d.
Interestingly, the partition coef®cient of the phosphite 12c
(92:8) is substantially higher than those of the phenols 11c,d,
and despite the polar functional group matches the ¯uor-
ohydrocarbons 15 and 16. It is sometimes found that assem-
bling a molecule or complex from several components or
ligands with modest ¯uorous phase af®nities gives a much
more ¯uorophilicspeices [5d,6g]. Finally, the C8F17H/1-
decene partition coef®cients of several of the phosphites in
Fig. 1 have been determined by GC (Table 1). Although
these data are not strictly comparable to ours due to the
different solvent system, higher values would be expected
due to the decreased numbers of methylene groups (see 13
versus 4a). Again, two pony tails per ring provides a
substantial ¯uorous phase af®nity (V, 99:1).
3. Discussion
Our syntheses of ¯uorous phenols in Schemes l±3 are
fundamentally different from those used as precursors to the
¯uorous triarylphosphites I±V in Fig. 1. For example, the
phenols needed for I±III are derived from high-temperature
copper-induced coupling reactions of bromophenols and the
per¯uoroalkyl iodide IRf8 [11a,b]. To our knowledge, it is
not possible to introduce pony tails with (CH2)m spacers
by this method. However, reactions of Grignard reagents
derived from monobrominated anisoles with ICH2CH2Rf8 in
the presence of copper catalysts give single pony-tailed
anisoles (45±65%) that can easily be converted to IV
[11c]. Unfortunately, yields drop dramatically when this
method is applied to double pony-tailed arenes, as needed
for phosphite V. Coupling reactions utilized for precursors to
II also proceed in low yields.
Our syntheses introduce pony tails via Wittig reactions
of the phosphonium salt 1. This is in turn derived from the
commercial ¯uorous iodide ICH2CH2Rf8 [12]. Analogous
Wittig reactions have been used to prepare a number of
¯uorous arenes [5d,12] and pyridines [17], including
examples with shorter (Rf6) and longer (Rf10) per¯uor-
oalkyl segments. Except for the labile dialdehyde 9d in
Scheme 3, yields are in all cases high. After the hydro-
genation step, pony tails with (CH2)3 insulating moieties
are generated. Since ¯uorous iodides with longer methy-
lene chains are readily available [7a,b], our methodology
can certainly be extended to longer insulating segments,
and likely shorter (CH2)2 segments as well [18]. We also
see no reason why similar methods cannot be applied to
triarylphosphites with pony tails in ortho positions. How-
ever, since ortho-substituted ligands often give anomalous
In summary, this paper has described simple and
general syntheses of two valuable types of ¯uorous ligands
and/or building blocks, phenols and triarylphosphites. These
exploit Wittig reactions of benzyl ethers of phenol alde-
hydes, can be adapted to different (CH2)m and Rfn segment
lengths, and constitute the ®rst ef®cient routes to such

S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
145
compounds with two pony tails per ring. Key physical
properties of these molecules have been characterized.
Applications, as well as syntheses of other types of useful
¯uorous molecules, will be described in future reports
[12b,19].
(25.03 g, 117.9 mmol, 72%). The 1H NMR spectrum
matched that in literature [15].
4.4. PhCH2OC6H4-4-CH=CHCH2Rf8 (3a)
A Schlenk ¯ask was charged with 2a (0.425 g, 2.00 mmol),
‡ À
[Ph3PCH2CH2Rf8] I (1 [12]; 2.000 g, 2.39 mmol), K2CO3
4. Experimental section
(0.694 g, 5.02 mmol), H2O (0.2 ml), and 1,4-dioxane (30 ml).
The solution was heated under N2 (95 8C, 12 h) and cooled.
The volatiles were removed by rotary evaporation. The
residue was taken up in CH2Cl2 (100 ml) and H2O (50 ml).
The CH2Cl2 layer was washed with H2O (10 ml) and dried
(MgSO4). The solution was concentrated by rotary evapora-
tion and ®ltered through a silica gel column, which was rinsed
with hexanes/CH2Cl2 (100 ml, 10:1 v/v). The solvents were
removed by rotary evaporation and oil pump vacuum to give
3a as a white solid (1.182 g, 1.84 mmol, 92%; 95:5 Z/E), mp
50.8±51 8C (capillary).
4.1. General
Chemicals were treated as follows: ether and toluene,
distilled from Na/benzophenone; hexanes, distilled from
LiAlH4; CH2Cl2, distilled from CaH2; CF3C6H5 (ABCR),
distilled from P2O5; CDC13 (Aldrich) and other solvents,
used as received; NEt3, distilled from KOH and deoxyge-
nated; PhCH2Br, 3- and 4-hydroxybenzaldehyde, 5-hydro-
xyisophthalicacid dimethyl ester ( 6c), 4-hydroxyphthalic
acid, LiAlH4 (6 Â Aldrich), 10% Pd/C (Acros), used as
received. NMR spectra were recorded on Bruker or Jeol
400 MHz spectrometers.3 IR spectra were measured on a
ASI React-IR spectrometer. DSC data were recorded with a
Mettler-Toledo DSC821 instrument and treated by standard
methods [20]. Gas chromatography was conducted on Ther-
moQuest Trace GC 2000 instrument. Elemental analyses
were conducted with a Carlo Erba EA1110 instrument.
1
NMR data, Z-3a (d, CDCl3) (see Footnote 3): H 7.51±
7.31 (m, C6H5), 7.18 (m, 2H of C6H4), 6.97 (m, 2H of C6H4),
6.74 (d, 3JHH ˆ 12 Hz, C6H4CH=), 5.66 (dt, 3JHH ˆ 12 Hz,
3JHH ˆ 7 Hz, =CHCH2), 5.08 (s, 2H, CH2O), 3.10 (td,
3
3JHF ˆ 18 Hz, JHH ˆ 7 Hz, CH2CF2); 13C {1H} 158.2 (s,
OCipso), 136.8, 136.6 (2s, 2CCipso), 134.8, 129.7, 128.7,
128.6, 127.5 (5s, other Caryl), 116.5, 114.9 (2s, C=C), 70.0 (s,
2
CH2O), 30.6 (t, JCF ˆ 22 Hz, CH2CF2); 19F À80.7 (t,
3JFF ˆ 10 Hz, 3F), À113.1 (pseudopentet, 2F), À121.7
(m, 2F), À121.9 (m, 4F), À122.7 (m, 2F), À123.5 (m,
2F), À126.1 (m, 2F).
4.2. PhCH2OC6H4-4-CHO (2a) [14]
A ¯ask was charged with 4-hydroxybenzaldehyde
(20.00 g, 163.8 mmol), PhCH2Br (33.61 g, 196.5 mmol),
Na2CO3, (19.09 g, 180.2 mmol), and ethanol (100 ml,
95%). The mixture was re¯uxed for 12 h. The solvent
was evaporated and Et2O (100 ml) and CH3C6H5
(100 ml) were added. The mixture was washed with H2O
(2 Â 20 ml) and dried (MgSO4). The solvents were removed
by rotary evaporation, and Et2O (100 ml) was added. A
white solid precipitated (20 8C), which was collected on a
glass frit and washed with Et2O. Two additional crops of
crystals were collected, combined and dried by oil pump
vacuum to give 2a (27.46 g, 129.4 mmol, 79%). The 1H and
13C NMR spectra matched those in literature [14].
4.5. PhCH2OC6H4-3-CH=CHCH2Rf8 (3b)
Compound 2b (0.425 g, 2.00 mmol),
1
(2.000 g,
2.39 mmol) [12], K2CO3 (0.694 g, 5.02 mmol), 1,4-dioxane
(30 ml) and H2O (0.2 ml) were combined in a procedure
analogous to that for 3a. An identical workup gave 3b as a
white solid (1.131 g, 1.76 mmo1, 88%; 95:5 Z/E).
1
NMR data, Z-3b (d, CDCl3) (see Footnote 3): H 7.44±
3
7.25 (m, 6ArH), 6.93±6.82 (m, 3ArH), 6.79 (d, JHH
3
ˆ
3
12 Hz, C6H4CH=), 5.74 (dt, JHH ˆ 12 Hz, JHH ˆ 7 Hz,
3
=CHCH2), 5.08 (s, CH2O), 3.08 (td, JHF ˆ 18 Hz,
3JHH ˆ 7 Hz, CH2CF2); 13C {1H} 158.8 (s, OCipso),
137.3, 136.8 (2s, 2CCipso), 135.3, 129.6, 128.6, 128.0,
127.4, 121.1, 118.5 (7s, other Caryl), 114.9, 114.1 (2s,
4.3. PhCH2OC6H4-3-CHO (2b) [15]
2
C=C), 70.0 (s, CH2O), 30.6 (t, JCF ˆ 22 Hz, CH2CF2);
19F À80.8 (t, 3JFF ˆ 10 Hz, 3F), À113.1 (pseudopentet, 2F),
À121.6 (m, 2F), À121.8 (m, 4F), À122.8 (m, 2F), À123.2
(m, 2F), À126.0 (m, 2F).
The reaction/workup given for 2a was repeated with
3-hydroxybenzaldehyde (20.00 g, 163.8 mmol), PhCH2Br
(33.61 g, 196.5 mmol), Na2CO3 (19.09 g, 180.2 mmol) and
ethanol (100 ml, 95%). This gave 2b as colorless crystals
4.6. HOC6H4-4-(CH2)3Rf8 (4a)
3 NMR spectra were recorded at ambient probe temperature in CDCl3
and referenced as follows unless noted: 1H, residual internal CHCl3
(d ˆ 7:24 ppm); 13C, internal CDCl3 (d ˆ 77:0); 31P external 85% H3PO4
(d ˆ 0:00); 19F, external CFCl3 (d ˆ 0:00). The 13C signals of the
fluorinated carbons are omitted. The hydroxyl 1H NMR signals of 8c and
11c,d were not observed.
A Schlenk ¯ask was charged with 3a (0.150 g,
0.23 mmol, 95:5 Z/E), 10% Pd/C (0.025 g, 0.023 mmol,
10 mol%), and ethanol (10 ml). The ¯ask was evacuated
and ®lled with H2 (3 Â) and then kept at 1 atm (balloon,
20 8C). The mixture was stirred until GC monitoring showed

146
S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
it to be complete (reduction of the arene was observed at
higher temperatures), and ®ltered through a syringe ®lter.
The solvent was removed by rotary evaporation. The residue
was taken up in a minimum of CH2Cl2 and loaded onto a
3 cm plug of silica gel. Trace by-products were eluted with
hexanes/CH2Cl2 (10 ml; 10:1 v/v). The plug was then
¯ushed with ethanol (30 ml). Solvent was removed from
the ®ltrate by rotary evaporation and oil pump vacuum to
give 4a as a white powder (0.116 g, 0.21 mmol, 91%), mp
90.7 8C (DSC), 92.8±93.0 8C (capillary). Anal. calcd. for
C17H11F17O: C, 36.84; H, 2.00. Found: C, 37.15; H, 2.06. IR
(cmÀl, solid ®lm) 3380 (broad, w), 1197 (vs), 1145 (vs),
text, 1H NMR spectra of all samples showed 5±8% of 4a. IR
(cmÀ1, solid ®lm) 1235 (s), 1198 (vs), 1164 (s), 1146 (vs),
‡
1134 (vs), 1113 (s). MS (FAB, m/z) 1691 (M , 50), 1137
‡
(M ±4a, 100).
NMR (d, CDCl3) (see Footnote 3): H 7.10 (m, 6H of
1
3
3C6H4), 7.04 (m, 6H of 3C6H4), 2.66 (t, JHH ˆ 8 Hz,
3C6H4CH2), 2.15±1.86 (m, 3CH2CH2CF2); 13C {1H}
150.0 (d, JCP ˆ 3 Hz, OCipso) [21],4 136.5 (s, CCipso),
2
3
129.5 (s, OCipso CC), 120.8 (d, JCP ˆ 7 Hz, OCipsoC)
[21] (see Footnote 4), 34.3 (s, C6H4CH2), 30.2 (t,
2JCF ˆ 22 Hz, CH2CF2), 21.9 (s, CH2CH2CF2); 19F À80.8
3
(t, JFF ˆ 10 Hz, 9F), À114.1 (pseudopentet, 6F), À121.7
‡
1134 (vs), 1115 (vs). MS (FAB, m/z) 554 (M , 100).
(m, 6F), À121.9 (m, 12F), À122.7 (m, 6F), À123.4 (m, 6F),
À126.1 (m, 6F); 31P {1H} 128.5 (s).
NMR (d, CDCl3) (see Footnote 3): 1H 7.14±6.97 (m, 2H
of C6H4), 6.79±6.76 (m, 2H of C6H4), 4.59 (br, s, OH), 2.64
3
(t, JHH ˆ 8 Hz, C6H4CH2), 2.13±2.00, 1.93±1.86 (2 m,
4.9. P[OC6H4-3-(CH2)3Rf8]3 (5b)
CH2H2CF2); 13C {1H} 153.9 (s, OCipso), 132.9 (s, CCipso),
129.5, 115.4 (2s, other Caryl), 34.1 (s, C6H4CH2), 30.3 (t,
2JCF ˆ 22 Hz, CH2CF2), 22.0 (s, CH2CH2CF2); 19F À80.7
Compound 4b (0.1001 g, 0.181 mmol), NEt3 (0.028 ml,
0.201 mmol), Et2O (1.0 ml), and PCl3 (0.005 ml, 0.057
mmol) were combined in a procedure analogous to that for
5a. An identical workup gave 5b as a white powder (0.0947 g,
0.054 mmol, 94%), mp 58.0±58.5 8C (capillary). Anal. calcd.
forC51H30F51O3P: C, 36.23;H, 1.79. Found C, 36.05;H, 1.81.
3
(t, JFF ˆ 10 Hz, 3F), À114.1 (pseudopentet, 2F), À121.7
(m, 2F), À121.9 (m, 4F), À122.7 (m, 2F), À123.4 (m, 2F),
À126.0 (m, 2F).
1
4.7. HOC6H4-3-(CH2)3Rf8 (4b)
As described in the text, HÀN1 MR spectra of all samples
showed 5±12% of 4b. IR (c m , solid ®lm) 1198 (vs), 1145
(vs), 1133 (vs), 1115 (vs), 1108 (vs). MS (FAB, m/z) 1691
Compound 3b (0.400 g, 0.62 mmol), 10% Pd/C (0.066 g,
0.062 mmol, 10 mol%), ethanol (20 ml) and H2 were com-
bined in a procedure analogous to that for 4a. An identical
work up gave 4b as a white powder (0.299 g, 0.54 mmol,
87%), mp 51.5 8C (DSC), 52.5±52.6 8C (capillary). Anal.
calcd. for C17H11F17O: C, 36.84; H, 2.00. Found: C, 36.78;
H, 2.17. IR (cmÀ1, solid ®lm) 3340 (broad, w), 1199 (vs),
‡
‡
(M , 92), 1137 (M ±4b, 100).
NMR(d, CDCl3) (seeFootnote3): 1H 7.26(t, 3JHH ˆ 4 Hz,
3H of 3C6H4), 7.00±6.91 (m, 9H of 3C6H4), 2.65 (t,
3JHH ˆ 8 Hz, 3C6H4CH2), 2.11±2.00, 1.98±1.85 (2 m,
2
3CH2CH2CF2); 13C {1H} 151.7 (d, JCP ˆ 3 Hz, OCipso),
142.7 (s, CCipso), 129.8, 124.3, 120.6, 118.5 (4s, other Caryl),
34.8 (s, C6H4CH2), 30.2 (t, 2JCF ˆ 22 Hz, CH2CF2), 21.7 (s,
‡
1144 (vs). MS (FAB, m/z) 554 (M , 100).
NMR(d, CDCl3)(seeFootnote3):1H 7.18(t, 3JHH ˆ 8 Hz,
CH2CH2CF2); 19F À80.8 (t, JFF ˆ 10 Hz, 9F), À114.2
3
1H of C6H4), 6.76 (d, 3JHH ˆ 8 Hz, 1H of C6H4), 6.70±6.67
(pseudopentet, 6F), À121.8 (m, 6F), À122.0 (m, 12F),
À122.8 (m, 6F), À123.4 (m, 6F), À126.1 (m, 6F); 31P
{1H} 128.2 (s).
3
(m, 2H of C6H4), 4.69 (br, s, OH), 2.66 (t, JHH ˆ 8 Hz,
C6H4CH2), 2.14±2.01, 1.97±1.89 (2m, CH2CH2CF2); 13C
{1H} 155.7 (s, OCipso), 142.6 (s, CCipso), 129.8, 120.9,
115.3, 113.3 (4s, other Caryl), 34.9 (s, C6H4CH2), 30.3 (t,
2JCF ˆ 22 Hz, CH2CF2), 21.7 (s, CH2CH2CF2); 19F À80.8 (t,
3JFF ˆ 10 Hz, 3F), À114.1 (pseudopentet, 2F), À121.7 (m,
2F), À121.9(m,4F), À122.7(m, 2F), À123.4(m, 2F), À126.1
(m, 2F).
4.10. PhCH2OC6H3-3,5-(COOCH2CH3)2 (7c)
The reaction/workup given for 2a was repeated with
5-hydroxyisophtalicaicd dimethyl ester ( 6c) (27.33 g,
130.0 mmol), PhCH2Br (26.68 g, 156.0 mol), K2CO3
(19.76 g, 143.0 mmol), and ethanol (100 ml, 95%). This
gave 7c as colorless crystals (36.71 g, 111.8 mmol, 86%),
mp 50.8±51.4 8C (capillary). Anal. calcd. for C19H20O5: C,
69.50; H, 6.14. Found: C, 69.37; H, 6.11. MS (EI, m/z) 328
4.8. P[OC6H4-4-(CH2)3Rf8]3 (5a)
A Schlenk ¯ask was charged with 4a (0.800 g,
1.443 mmol), NEt3 (0.221 ml, 1.588 mmol), and Et2O
(10.0 ml). Then PCl3 (0.042 ml, 0.482 mmol) was added
slowly by syringe with stirring (20 8C). Awhite solid started
to precipitate. After 2 h, the mixture was ®ltered through a
silica gel column, which was rinsed with Et2O (20 ml). The
solvent was removed from the ®ltrate by oil pump vacuum to
give 5a as a white powder (0.766 g, 0.433 mmol, 92%), mp
68.2±68.4 8C (capillary). Anal. calcd. for C51H30F51O3P: C,
36.23; H, 1.79. Found: C, 36.14; H, 1.82. As described in the
‡
‡
(M , 20), 91 (C7H7 , 100).
NMR(d, CDCl3) (seeFootnote3): 1H 8.29(t, 4JHH ˆ 1 Hz,
1H of C6H3), 7.84 (d, 4JHH ˆ 1 Hz, 2H of C6H3), 7.46±7.26
(m, C6H5), 5.14 (s, CH2O), 4.39 (q, 3JHH ˆ 7 Hz, 2CH2CH3),
1.40 (t, 3JHH ˆ 7 Hz, 2CH3); 13C {1H} 165.6 (s, CO) 158.7 (s,
OCipso), 136.0, 132.2 (2s, 2CCipso), 128.6, 128.2, 127.6,
4 These assignments follow from the chemical shift and coupling
constant trends found for triphenylphosphite [21].

S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
147
3
123.0, 119.9 (5s, other Caryl), 70.4 (s, CH2O), 61.3 (s,
CH2CH3), 14.2 (s, CH3).
=CHCH2) 5.07 (s, CH2O), 3.04 (td, JHF ˆ 18 Hz,
3JHH ˆ 7 Hz, 2CH2CF2); 13C {1H) 159.0 (s OCipso), 137.5,
136.6 (2s, 2Cipso), 135.0, 128.7, 128.1, 127.4, 120.9 (5s, other
4.11. PhCH2OC6H3-3,5-(CH2OH)2 (8c)
Caryl), 118.7, 114.2 (2s, C=C), 70.1 (s, CH2O), 30.6 (t,
2JCF ˆ 22 Hz, CH2CF2); 19F À81.1 (t, JFF ˆ 9 Hz, 6F),
À113.1 (pseudopentet, 4F), À121.9 (m, 4F), À122.1 (m,
8F), À122.9 (m, 4F), À123.2 (m, 4F), À126.3 (m, 4F).
3
A three necked ¯ask was charged with LiAlH4 (5.313 g,
140.0 mmol) and dry Et2O (10 ml) and cooled to 0 8C. Then
a solution of 7c (16.418 g, 50.00 mol) in Et2O (130 ml) was
slowly added. The mixture was re¯uxed for 3 h and cooled to
0 8C. Then H2SO4 (10%; 1 ml) and H2O (1 ml) were added.
The mixture was ®ltered, and H2O (20 ml) was added. The
4.14. HOC6H3-3,5-((CH2)3Rf8)2 (11c)
A Fisher Porter bottle was charged with 10c (3.000 g,
2.73 mmol), 10% Pd/C (0.287 g, 0.27 mmol, 10 mol.%),
ethanol (30 ml), and CF3C6H5 (30 ml). The bottle was
evacuated and ¯ushed with H2 (3Â) and pressurized to
5 atm (20 8C). The mixture was stirred and periodically
repressurized to 5 atm (72 h), and then further stirred until
H2 uptake ceased (ca. 24 h). The mixture was ®ltered
through a syringe ®lter, concentrated by rotary evaporation,
and loaded onto a 3 cm plug of a silica gel. The plug was
eluted with ethanol (100 ml). The solvent was removed from
the ®ltrate by rotary evaporation and oil pump vacuum to
give 11c as a white powder (2.693 g, 2.62 mmol, 96%), mp
67.7 8C (DSC), 69.5±70.2 8C (capillary). Anal. calcd. for
C28H16F34O: C, 33.15; H, 1.59. Found: C, 33.24; H, 1.70. IR
(cmÀ1, solid ®lm) 3502 (broad, w), 1196 (vs), 1145 (vs),
organiclayer was washed with H O (2 Â 10 ml) and dried
2
(MgSO4). The solvents were removed by rotary evaporation
and oil pump vacuum to give 8c as a white solid (10.832 g,
44.34 mmol, 89%), mp 64.8±65.2 8C (capillary). Anal.
calcd. for C15H16O3: C, 73.74; H, 6.61. Found: C, 73.70;
‡
‡
H, 6.69. MS (EI, m/z) 244 (M , 30), 91 (C7H7 , 100).
NMR (d, CDCl3) (see Footnote 3): 1H 7.42±7.29 (m,
C6H5), 6.88 (s, 1H of C6H3), 6.86 (s, 2H of C6H3), 5.10 (s,
CH2OC), 4.55 (s, CH2OH); 13C {1H} 159.1 (s, OCipso),
142.8, 136.8 (2s, 2CCipso), 128.6, 128.0, 127.5, 117.8, 112.4
(5s, other Caryl), 70.0 (s, CH2O), 64.9 (s, CH2OH).
4.12. PhCH2OC6H3-3,5-(CHO)2 (9c)
‡
A
Schlenk ¯ask was charged with 8c (2.579 g,
1134 (vs). MS (FAB, m/z) 1014 (M , 100).
1
10.56 mmol), the Dess-Martin periodinane (11.185 g,
26.37 mmol), [22] and CH2Cl2 (100 ml). The mixture was
stirred for 12 h (20 8C) and ®ltered through a plug of silica
gel (6 cm  2 cm), which was rinsed with CH2Cl2 (100 ml).
The solvent was removed from the ®ltrate by rotary eva-
poration and oil pump vacuum to give 9c as a white solid
(2.404 g, 10.01 mmol, 95%), mp 68.3±68.7 8C (capillary).
Anal. calcd. for C15H12O3: C, 74.99; H, 5.03. Found: C,
74.54; H, 5.09. IR (cmÀ1, solid ®lm) 3028 (m), 2841 (m),
2744 (m), 2728 (m), 1687 (vs), 1296 (vs). MS (EI, m/z) 240
NMR (d, CDCl3) (see Footnote 3): H 6.56 (s, 1H of
3
C6H3), 6.50 (d, JHH ˆ 1 Hz, 2H of C6H3), 2.62 (t,
3JHH ˆ 7 Hz, 2C6H3CH2), 2.09±1.86 (m, 2CH2CH2CF2);
13C {1H) 156.0 (s, OCipso), 142.8 (s, CCipso), 121.1, 113.4
(2s, 1C and 2C of C6H3), 34.8 (s, C6H3CH2), 30.2 (t,
2JCF ˆ 23 Hz, CH2CF2), 21.7 (s, CH2CH2CF2); 19F À81.1
(t, 3JFF ˆ 9 Hz, 6F), À114.4 (pseudopentet, 4F), À122.0 (m,
4F), À122.2 (m, 8F), À123.0 (m, 4F), À123.6 (m, 4F),
À126.4 (m, 4F).
‡
‡
(M , 30), 91 (C7H7 , 100).
4.15. P[OC6H3-3,5-((CH2)3Rf8)2]3 (12c)
1
NMR (d, CDCl3) (see Footnote 3): H 10.04 (s, 2CHO),
7.97 (t, 4JHH ˆ 1 Hz, 1H of C6H3), 7.73 (d, 4JHH ˆ 1 Hz, 2H
of C6H3), 7.47±7.34 (m, C6H5), 5.19 (s, CH2); 13C {1H}
190.7 (s, CHO), 159.9 (s, OCipso), 138.4, 135.6 (2s, 2CCipso),
128.8, 128.4, 127.6, 124.3, 120.2 (5s, other Caryl), 70.7 (s,
CH2).
A Schlenk ¯ask was charged with 11c (0.500 g,
0.493 mmol), NEt3 (0.076 ml, 0.547 mmol), and Et2O
(3.0 ml). Then PCl3 (0.015 ml, 0.172 mmol) was slowly
added by syringe with stirring (20 8C). A white solid started
to precipitate. After 2 h, the mixture was ®ltered through a
silica gel column, which was rinsed with Et2O/hexanes
(30 ml, 50:50 v/v). The solvent was removed from the
®ltrate by oil pump vacuum to give 12c as a white powder
(0.469 g, 0.151 mmol, 92%), mp 54.6 8C (DSC). Anal.
calcd. for C84H45F102O3P: C, 32.85; H, 1.47. Found: C,
33.23; H, 1.65. The 1H NMR spectrum showed up to 2.7% of
11c (see text).
4.13. PhCH2OC6H3-3,5-(CH=CHCH2Rf8)2 (10c)
The reaction/workup given for 3a was repeated with
9c (1.250 g, 5.20 mmol), 1 (10.002 g, 11.96 mmol), [12]
K2CO3 (3.306 g, 23.92 mmol), H2O (0.6 ml), and 1,4-diox-
ane (85 ml). An identical workup gave 10c as a white solid
(5.522 g, 5.02 mmol, 97%, mixture of ZZ/ZE/EE isomers).
IR (cmÀl, solid ®lm) 3502 (broad, w), 1584 (m), 1198 (vs),
1145 (vs).
NMR (d, CDCl3/CF3C6F5) (see Footnote 3): 1H 6.86 (s, 3H
3
of 3C6H3), 6.78 (s, 6H of 3C6H3), 2.64 (t, JHH ˆ 7 Hz,
3C6H3(CH2)2), 2.07±1.83 (2m, 6CH2CH2CF2); 15C {1H}
152.3 (s, OCipso), 143.9 (s, 2CCipso), 124.7, 118.7 (2s, other
NMR data, ZZ-10c (d, CDCl3) (see Footnote 3): 1H 7.43±
7.29 (m, 6 of 8Haryl), 6.79±6.68 (m, 2 of 8Haryl and
C
aryl), 35.1 (s, 2C6H3CH2), 30.5 (t, 2JCF ˆ 23 Hz, 2CH2CF2),
3
3
2C6H3CH=), 5.76 (dt, JHH ˆ 12 Hz, JHH ˆ 7 Hz, 2
22.0 (s, 2CH2CH2CF2); 31P {1H) 128.5 (s).

148
S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
3
4.16. HOC6H3-3,4-(COOCH3)2 (6d) [16]
4JHH ˆ 2 Hz, 1H of C6H3), 6.86 (dd, JHH ˆ 8 Hz,
4JHH ˆ 2 Hz, 1H of C6H3), 5.05 (s, 2H, C6H5CH2), 4.66,
4.64 (2s, 2CH2OH), 2.72 (br, s, 2OH); 13C {1H} 169.2 (s,
OCipso), 158.8, 141.2, 136.7 (3s, 3CCipso), 131.2, 128.6,
128.0, 127.4, 116.5, 113.8 (6s, other Caryl), 70.0 (s,
C6H5CH2), 64.3, 63.7 (2s, 2CH2OH).
A round bottom ¯ask was charged with 4-hydroxyphthalic
acid (2.000 g, 10.98 mmol), MeOH (30 ml), and a few drops
of concentrated H2SO4. The mixture was re¯uxed for 12 h.
The solvent was removed by rotary evaporation and Et2O
(20 ml) and H2O (10 ml) were added. The organiclayer was
washed with H2O (2 Â 10 ml) and dried (MgSO4). The
sample was concentrated and hexanes (30 ml) was added.
The white powder was collected by ®ltration and dried under
oil pump vacuum to give 6d (1.893 g, 9.01 mmol, 82%). The
1H NMR spectrum matched that in the literature [16].
4.19. PhCH2OC6H3-3,4-(CH=CHCH2Rf8)2 (10d)
A Schlenk ¯ask was charged with 8d (1.000 g, 4.09 mmol),
the Dess-Martin periodinane (4.167 g, 9.82 mmol) [22] and
CH2Cl2 (20 ml). The mixturewas stirred for 4 h (20 8C) in the
dark. Then Et2O (20 ml) was added to precipitate a white
solid. The mixture was ®ltered and washed with a solution of
Na2S2O3 (17.059 g, 68.74 mmol) in NaHCO3-saturated H2O
(50 ml), and then saturated aqueous NaHCO3 (50 ml). The
combined aqueous phases were extracted with CH2Cl2
(20 ml). The CH2Cl2 phases were combined, dried (MgSO4)
and concentrated to give a solution of crude PhCH2OC6H3-
3,4-(CHO)2 (9d). The reaction/workup given for 3a was
repeated under nitrogen with 1 (7.532 g, 9.01 mmol), [12]
K2CO3 (1.358 g, 9.82 mmol), H2O (0.6 ml), and 1,4-dioxane
(20 ml). This gave 10d as a yellowish solid (1.458 g,
1.32 mmol, 32%, mixture of ZZ/ZE/EE isomers). Anal. calcd.
for C35H18OF34: C, 38.20; H, 1.65. Found: C, 37.60; H, 1.57.
4.17. PhCH2OC6H3-3,4-(COOCH3)2 (7d)
A round bottom ¯ask was charged with 6d (1.873 g,
8.91 mmol), K2CO3 (1.478 g, 10.69 mmol), PhCH2Br
(1.082 ml, 8.91 mmol) and acetone (40 ml). The mixture
was re¯uxed (3 h) and cooled. The solvent was removed by
rotary evaporation, and CH2Cl2 (20 ml) and H2O (20 ml)
were added. The organicphase was washed with H 2O
(2 Â 20 ml) and dried (MgSO4). The solvent was removed
by rotary evaporation and the oily residue triturated with
hexanes (20 ml). The powder was collected by ®ltration,
washed with hexanes (10 ml), and dried by oil pump vacuum
to give 7d (2.530 g, 8.43 mmol, 95%) as a white powder, mp
56.8 8C (DSC), 53.4±54.1 8C (capillary). Anal. calcd. for
C17H16O5: C, 67.99; H, 5.37. Found: C, 67.47; H, 5.02. IR
(cmÀ1, solid ®lm) 2957 (w), 1733 (s), 1717 (s), 1602 (m),
1571 (m), 1498 (w), 1432 (m), 1390 (m), 1332 (m), 1262
(vs), 1227 (vs), 1189 (s), 1119 (vs), 1069 (s), 1038 (m), 965
‡
MS (FAB, m/z) 1100 (M , 100).
NMR data, ZZ-10d (d, CDCl3) (see Footnote 3): 1H 7.42±
3
7.31 (m, C6H5), 7.11 (d, JHH ˆ 8 Hz, 1H of C6H3), 6.92
3
4
(dd, JHH ˆ 8 Hz, JHH ˆ 3 Hz, 1H of C6H3), 6.77 (d,
4JHH ˆ 3 Hz, 1H of C6H3), 6.71, 6.66 (2d, JHH ˆ 11 Hz,
3
C6H3(CH=)2), 5.77, 5.72 (2dt, 3JHH ˆ 11 Hz, 3JHH ˆ 7 Hz,
2 =CHCH2), 5.07 (s, CH2O), 2.91, 2.83 (2td, 3JHF ˆ 18 Hz,
3JHH ˆ 7 Hz, 2CH2CF2); 13C {1H} 158.1 (s, OCipso), 136.7,
136.4, 127.6 (3s, 3CCipso), 134.3, 133.8, 130.0, 128.6, 128.1,
127.3 (other Caryl), 119.4, 118.3, 115.2, 114.2 (4s, 2C=C),
70.2 (s, CH2O), 30.7 (m, CH2CF2).
‡
(m), 741 (vs), 695 (vs). MS (EI, m/z) 300 (M , 50), 269
‡
‡
(M ±OCH3), 91 (C7H7 , 100).
NMR (d, CDCl3) (see Footnote 3): 1H 7.78 (d,
3JHH ˆ 8 Hz, 1H of C6H3), 7.39±7.32 (m, C6H5), 7.15 (d,
4JHH ˆ 3 Hz, 1H of C6H3), 7.03 (dd, JHH ˆ 8 Hz,
3
4JHH ˆ 3 Hz, 1H of C6H3), 5.10 (s, CH2), 3.89, 3.85 (2s,
2CH3); 13C {1H} 168.5 (s, CO), 166.6 (s, CO), 161.0 (s,
OCipso), 135.6, 135.5, 122.4 (3s, 3CCipso), 131.5, 128.6,
128.2, 127.4, 116.4, 114.4 (6s, other Caryl), 70.4 (s, CH2),
52.8, 52.4 (2s, 2CH3).
4.20. HOC6H3-3,4-((CH2)3Rf8)2 (11d)
Compound 10d (1.400 g, 1.27 mmol), 10% Pd/C
(0.135 g, 0.13 mmol, 10 mol%), ethanol (20 ml), CF3C6H5
(20 ml) and H2 were combined in a procedure analogous to
that for 4a. The mixture was stirred at room temperature
until H2 uptake had ceased (ca. 48 h), and ®ltered through a
Celite pad. The pad was rinsed with CH2Cl2 (50 ml). The
solvents were removed by rotary evaporation and oil pump
vacuum to give 11d as a white powder (1.160 g, 1.14 mmol,
90%), mp 45.7 8C (DSC). Anal. calcd. for C28H16F34O: C,
33.15; H, 1.59. Found: C, 33.05; H, 1.64. IR (cmÀ1, solid
®lm) 3377 (broad, w), 1197 (vs), 1146 (vs), 1134 (vs), 957
4.18. PhCH2OC6H3-3,4-(CH2OH)2 (8d)
LiAlH4 (0.209 g, 5.49 mmol), Et2O (10 ml), and 7a
(1.500 g, 5.00 mmol) in Et2O (20 ml) were combined in a
procedure analogous to that for 8c. An identical workup
gave 8d as a white solid (1.095 g, 4.48 mmol, 90%), mp
68.9±69.4 8C (capillary), 69.9 8C (DSC). Anal. calcd. for
C15H16O3: C, 73.75; H, 6.60. Found: C, 73.33; H, 6.79. IR
(cmÀl, solid ®lm) 3204 (w), 2964 (w), 1606 (w), 1502 (w),
1455 (w), 1258 (s), 1100 (s), 1138 (s), 1000 (s), 1038 (m),
‡
(w), 703 (w), 656 (m). MS (FAB, m/z) 1014 (M , 97) 567
‡
(M ±CH2CH2Rf8, 100%).
NMR (d, CDCl3) (see Footnote 3): H 7.00 (m, 1H of
‡
1
765 (s), 730 (s), 691 (s). MS (EI, m/z) 244 (M , 55), 226
‡
‡
(M ±H2O, 25), 91 (C7H7 , 100).
C6H3), 6.64 (m, 2H of C6H3), 2.63 (m, C6H3(CH2)2) 2.15±
2.08, 1.90±1.84 (2m, 2CH2CH2CF2); 13C {1H} 154.5 (s,
OCipso), 140.5, 131.2 (2s, 2CCipso), 130.9, 116.4, 114.0 (3s,
NMR (d, CDCl3) (see Footnote 3): 1H 7.42±7.30 (m,
3
C6H5), 7.23 (d, JHH ˆ 8 Hz, 1H of C6H3), 6.99 (d,

S. Le Stang et al. / Journal of Fluorine Chemistry 119 (2003) 141±149
149
(h) S. Schneider, W. Bannwarth, Angew. Chem. Int. Ed. 39 (2000)
4142;
other Caryl), 32.2, 31.5 (2s, 2C6H3(CH2)2), 31.0, 30.9 (2t,
2JCF ˆ 23 Hz, 2CH2CF2), 22.3, 22.0 (2s, 2CH2CH2CF2).
S. Schneider, W. Bannwarth, Angew. Chem. 112 (2000) 4293;
(i) R. Grigg, M. York, Tetrahedron Lett. 41 (2000) 7255;
(j) Q. Zhang, Z. Luo, D.P. Curran, J. Org. Chem. 65 (2000) 8866;
(k) S. Darses, M. Pucheault, J.P. Genet, Eur. J. Org. Chem. (2001)
1121;
4.21. Partition coefficients
The following is representative. A 10 ml vial was charged
with 4a (0.0122 g, 0.0220 mmol), CF3C6F11 (2.000 ml), and
toluene (2.000 ml), ®tted with a mininert valve, vigorously
shaken (2 min), and allowed to stand at 24 8C. After 2 h, a
0.800 ml aliquot of each layer was added to 0.100 ml of a
standard 0.1063 M solution of CH3C6F5 in CDCl3. The
samples were diluted with CDCl3 to ca. 1.50 ml and ana-
lyzed by 1H and 19F NMR. Integration of the CF3 19F signal
of 4a (d À80.7) versus a CF signal of CH3C6F5 (d 158.3)
indicated 0.0076 mmol of 4a in the ¯uorous phase, and
0.0010 mmol in the organicphase (88:12; a 2.000/0.800
scale factor gives a total mass recovery of 0.0119 g, 98%).
Integration of the benzylic 1H signal of 4a (d 2.64) versus the
CH3 signal of CH3C6F5, (d 2.25) gave identical values.
(l) S. Saito, Y. Chounan, T. Nogami, O. Ohmori, Y. Yamamoto,
Chem. Lett. (2001) 444;
(m) S. Schneider, W. Bannwarth, Helv. Chim. Acta. 84 (2001) 735;
(n) S. Saito, Y. Chounan, T. Nogami, O. Ohmori, Y. Yamamoto,
Chem. Lett. (2001) 444;
(o) W. Chen, L. Xu, Y. Hu, A.M.B. Osuna, J. Xiao, Tetrahedron 58
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Â
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Acknowledgements
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We thank the Deutsche Forschungsgemeinschaft (DFG;
GL 301/3-l) for support.
(b) E. de Wolf, B. Richter, B.-J. Deelman, G. van Koten, J. Org.
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