Sodium iodide/tert-butyl(dimethyl)silyl chloride-induced isomerization of 2,3-allenols to 2(E)-enals

Article abstract of DOI:10.1002/adsc.201300835

Through an unexpected C=C bond migration, 2(E)-enals were efficiently prepared highly stereoselectively in moderate to good yields via the sodium iodide/tert-butyl(dimethyl)silyl chloride (NaI/TBSCl)-mediated reaction of the easily available 2,3-allenols. Based on a careful mechanistic study, including control experiments and deuterium-labeling experiments, an electron-withdrawing substituent group in the 4 position has been proven to be crucial and a possible mechanism has been proposed.

Full text of DOI:10.1002/adsc.201300835

FULL PAPERS
DOI: 10.1002/adsc.201300835
Sodium Iodide/tert-Butyl(dimethyl)silyl Chloride-Induced
G
Isomerization of 2,3-Allenols to 2(E)-Enals
Rong Zeng,a Zhichao Ma,a Chunling Fu,a,* and Shengming Maa,*
a
Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027,
Zhejiang, Peopleꢀs Republic of China
Fax : (+86)-21-6260-9305; e-mail: fucl@zju.edu.cn or masm@sioc.ac.cn
Received: September 13, 2013; Revised: December 30, 2013; Published online: March 17, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300835.
Abstract: Through an unexpected C=C bond migra- experiments, an electron-withdrawing substituent
tion, 2(E)-enals were efficiently prepared highly ste- group in the 4 position has been proven to be crucial
reoselectively in moderate to good yields via the and a possible mechanism has been proposed.
sodium iodide/tert-butylACTHNURGTNE(NUG dimethyl)silyl chloride (NaI/
TBSCl)-mediated reaction of the easily available 2,3-
allenols. Based on a careful mechanistic study, in- Keywords: allenols; electrophilic addition; migra-
cluding control experiments and deuterium-labeling tion; oxidation; a,b-unsaturated aldehydes
Introduction
2(E)-enals substituted with an electron-withdrawing
group at the 4 position were unexpectedly formed
a,b-Unsaturated aldehydes are an important class of upon the treatment with NaI and TBSCl (Scheme 1).
chemical compounds because of the wide existence of Herein, we wish to report the details of this transfor-
this unit in nature, the extensive use in food, cosmetic mation.
and pharmaceutical industries,[1] and for being valua-
ble intermediates in organic synthesis.[2] Therefore,
there have been many practical methods for the syn- Results and Discussion
thesis of the this type of compounds.[3–9] On the other
hand, as an equivalent to TMSI, TMSCl/NaI reagent At the beginning of our work, the reaction of per-
has been widely used in synthetic organic chemis- fluoroalkyl-containing 2,3-allenol 1a, prepared follow-
try.[10,11] In 1989, Y. Ishii et al. reported a facile iodina- ing the known procedure,[14] with NaI and TMSCl was
tion of allylic alcohols with the NaI/TMSCl/H2O carried out in MeCN at room temperature with the
forming allylic iodides (Scheme 1).[11b] However, when purpose of preparing the corresponding allenyl
we applied this set of reagents to 2,3-allenols with an iodide. Surprisingly, instead of forming the expected
electron-withdrawing group on the allene unit,[12,13] allenyl iodide product Z-3a, a new product was
1
formed unexpectedly. Interestingly, the H/13C NMR
and IR analysis of this product indicated the presence
of an aldehyde functionality. Further study of the
mass spectra led us to the conclusion that this product
should be 4-butyl-6,7,7,8,8,9,9,9-octafluoro-2-phenyl-
2(E),5(Z)-nonadienal 2a (Table 1). The configuration
of the double bond in the 2-position was determined
by a NOESY analysis.[15] Having established the iden-
tity of 2a, the solvent effect was then examined with
2.0 equiv. each of NaI and TMSCl at room tempera-
ture to optimize the reaction yield (entries 1–6,
Table 1): toluene gave a similar result with benzene
(entries 1 and 4, Table 1); using THF as solvent, the
Scheme 1.
reaction was messy (entry 3, Table 1); MeCN re-
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1343

FULL PAPERS
Rong Zeng et al.
Table 1. Optimization of reaction conditions for the reaction of 1a with NaI and chlorosilanes.[a]
Entry
Solvent
R
Time [h]
Yield [%][b] of (E,Z)-2a
ACHUTGTNREN(NUG E,Z)/ACHTUNGTRENNUNG(Z,Z)
1
2
3
4
5
6
7
toluene
CH2Cl2
THF
benzene
DCE
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
Me
Me
Me
Me
Me
Me
–
Me
Me
13
2
2
2
2
2
2
2
1.5
2
44
38
98/2
99/1
–
98/2
98/2
98/2
–
complicated
48
53
61
0[d]
[c]
8[e]
9[f]
10
11
12[g,i]
13[g,j]
complicated
58
66
62
59
72 (70)
–
98/2
98/2
98/2
98/2
98/2
t-Bu[g]
t-Bu[h]
t-Bu
t-Bu
2
2
2
[a]
The reaction was carried out using 0.1 mmol or 0.15 mmol of 1a, 2.0 equiv. of NaI, and 2.0 equiv. of RMe2SiCl in 2 mL of
solvent.
[b]
[c]
[d]
[e]
[f]
1
Determined by H NMR analysis using mesitylene as the internal standard.
RMe2SiCl was not used.
97% of 1a was recovered.
NaI was not used.
2.0 equiv. of KI were used.
[g]
[h]
[i]
1.5 equiv. of t-BuMe2SiCl were used.
1.2 equiv of t-BuMe2SiCl were used.
1.5 equiv. of NaI were used.
The concentration of 1a in MeCN was 0.1M.
[j]
mained the best with a 61% yield (entry 6, Table 1). group may be phenyl (entries 1, 9 and 11, Table 2),
In addition, this reaction did not proceed in the ab- substituted phenyl (entries 2–6, 10, 12 and 13,
sence of either NaI or TMSCl (entries 7 and 8, Table 2) or a thienyl group (entry 7, Table 2). The re-
Table 1). The yield of 2a could be improved to 66% action of substrates with R2 being an electron-donat-
when 1.5 equiv. of TBSCl were used, and further in- ing phenyl group (entries 2–4 and 12, Table 2) gave
creased to 72% yield when the concentration of 1a in better results than that of the phenyl (entries 1, 9, 10
MeCN was adjusted to 0.1M (entry 13, Table 1). and 14, Table 2) or those with an electron-withdraw-
Thus, we defined the experimental protocol for the ing group on the phenyl ring (entries 5, 6, 10 and 13,
migrative oxidation of 4-electron-withdrawing group- Table 2). Alkyl groups may also be introduced as the
substituted 2,3-allenols with 2.0 equiv. NaI and R2 group (entry 8, Table 2), although the yield was
1.5 equiv. TBSCl in MeCN at room temperature as lower. In order to further clarify the structure of this
the standard reaction conditions for further study.
compound, we attempted the condensation reaction
With the optimized conditions in hand, the scope of of 2n with 2,4-dinitrophenylhydrazine to afford a solid
this reaction was studied, and the typical results are product (E,Z)-4a, whose X-ray single crystal diffrac-
summarized in Table 2. Differently substituted 6- tion study definitely showed that the product 2n is
fluoro-6-perfluoroalkyl-2,3,5(Z)-trien-1-ols
1a–1n 6,6,6,7-tetrafluoro-4-butyl-2-phenyl-2-heptenal in the
were successfully applied in this reaction to afford 6- E,Z-configuration (Figure 1).[16]
fluoro-6-perfluoroalkyl-2(E),5(Z)-dienals 2a–2n in
In order to further extend the scope, 4-methyl-2-
moderate to good yields with high stereoselectivity. phenyl-2,3-pentadienol 1p and 5,5,5-trifluoro-4-
The substituent R1 could be alkyl groups, such as n- methyl-2-phenyl-2,3-pentadienol 1q were prepared[17]
butyl (entries 1–10, Table 2) or n-hexyl group (en- and submitted to the standard conditions, respectively.
tries 11–13, Table 2); the Rf group could be n-C3F7 Interestingly, the reaction of 4-trifluoromethyl-substi-
(entries 1–8 and 11–13, Table 2), n-C5F11 (entries 9 tuted substrate 1q led to the similar aldehyde product
and 10, Table 2), or CF3 (entry 14, Table 2); the R2 E-2q in 55% yield while the reaction of 1p was com-
1344
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
Table 2. Highly stereoselective synthesis of a,b-unsaturated aldehydes by isomerization of fluorine-containing allenols.
Entry
R1/R2/Rf
Isolated yield [%] of (E,Z)-2
ACHUTGTNRNEUG(N E,Z)/ACHTUNGTRENNUNG
(Z,Z)[a]
1
2
3
4
5
6
7
8
n-C4H9/Ph/n-C3F7 [(Z)-1a]
70 [(E,Z)-2a]
80 [(E,Z)-2b]
78 [(E,Z)-2c]
68 [(E,Z)-2d]
68 [(E,Z)-2e]
53 [(E,Z)-2f]
60 [(E,Z)-2g]
32 [(E,Z)-2h]
60 [(E,Z)-2i]
66 [(E,Z)-2j]
68 [(E,Z)-2k]
80 [(E,Z)-2l]
69 [(E,Z)-2m]
62 [(E,Z)-2n]
98/2
98/2
98/2
98/2
98/2
98/2
95/5
99/1
98/2
98/2
98/2
98/2
98/2
98/2
n-C4H9/4-MeOC6H4/n-C3F7 [(Z)-1b]
n-C4H9/4-MeC6H4/n-C3F7 [(Z)-1c]
n-C4H9/3-MeC6H4/n-C3F7 [(Z)-1d]
n-C4H9/4-FC6H4/n-C3F7 [(Z)-1e]
n-C4H9/4-BrC6H4/n-C3F7 [(Z)-1f]
n-C4H9/2-thienyl/n-C3F7 [(Z)-1g]
n-C4H9/n-C4H9/n-C3F7 [(Z)-1h]
n-C4H9/Ph/n-C5F11 [(Z)-1i]
n-C4H9/4-FC6H4/n-C5F11 [(Z)-1j]
n-C6H13/Ph/n-C3F7 [(Z)-1k]
n-C6H13/4-MeC6H4/n-C3F7 [(Z)-1l]
n-C6H13/4-FC6H4/n-C3F7 [(Z)-1m]
n-C4H9/Ph/CF3 [(Z)-1n]
9
10
11
12
13
14
[a]
1
The (E,Z)/
N
Figure 1. Formation and ORTEP representation of (E,Z)-4a.
plicated, which indicated that an electron-withdrawing tion of 5a with the electron-withdrawing methoxycar-
group at the 4-position of allenols is essential for this bonyl group also afforded the expected a,b-unsaturat-
reaction (upper vs. middle parts, Scheme 2). The con- ed aldehyde 8a in 27% yield, although the major
densation reaction of E-2q with 2,4-dinitrophenylhy- product is the lactonization product 7a involving the
drazine afforded a solid product E-4b, whose X-ray ester functionality as expected (47% yield).[13k] In ad-
single crystal diffraction study definitely clarified the dition to these two products, only 6% of cyclization
structure of E-2q (lower part, Scheme 2).[18]
This electronic effect of the electron-withdrawing served in this reaction based on the H NMR analysis
group was further confirmed by the fact that the reac- of the crude reaction mixture (Scheme 3). These ex-
product involving the hydroxy group,[13k] 6a, was ob-
1
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1345

FULL PAPERS
Rong Zeng et al.
perimental results indicate the presence of cationic in-
termediates Int-A[13k] and Int-B[13k] forming from elec-
trophilic addition of 5a with H+. Due to the destabili-
zation effect of the electron-withdrawing methoxycar-
bonyl group, Int-A was prefered over Int-B, affording
8a and 7a as the major products.
A similar cyclization was observed with the reac-
tion of Z-1o, in which there is an extra hydroxymethyl
group at the 4-position: 2,5-dihydrofuran 10a was
formed as the major product, while the expected
product 2o and the other cyclization product 9a were
not detected in the crude product. These experimen-
tal results may nicely explain that H+ is indeed the
active species under the current reaction conditions
affording the product 10a via highly efficient H+-
mediated electrophilic cyclic etherification of Z-1o
(Scheme 4).
Then the corresponding allenol TBS ether Z-11a
was synthesized and treated with NaI and TBSCl in
the presence of 5 equiv. of water. After 2 h, the ex-
pected aldehyde product 2a was formed in 70% iso-
lated yield [Eq. (1), Scheme 5]. Furthermore, a deute-
rium-labeling experiment was performed: the reaction
of 1a-D under the standard condition affording (E,Z)-
2a-D with 0% and less than 5% D at the C-3 and C-4
positions, respectively, while 63% D was observed at
C-1, indicating an isotopic effect [Eq. (2), Scheme 5].
The reaction of Z-1a was performed in the presence
of 10 equiv. of D2O affording the (E,Z)-2a-D’ with
62% and 84% D incorporated into the C-3 and C-4
positions, respectively [Eq. (3), Scheme 5].
Scheme 2.
With the evidence above, we proposed a mechanism
for this transformation (Scheme 6). The reaction of
fluorine-containing 2,3-allenol 1a-D with NaI and
TBSCl would form the allenol TBS ether 11a-D and
Scheme 3.
Scheme 4.
1346
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
Scheme 5.
Scheme 6.
generate HI in situ. The electrophilic addition of the Conclusions
allene unit intermediate 11a-D with H+ would form
p-allylic cation M1. Due to the destabilization effect In summary, we have observed a unique C=C migra-
of the electron-withdrawing fluorine-containing sub- tion of 4-electron-withdrawing group-substituted 2,3-
stituent at the 4-position of the substrate, the cation allenols, which provides an efficient synthesis of 4-
center was inclined to the C-2 position. H+- or D+- electron-withdrawing group-substituted 2(E)-enals.
elimination of M1 would form conjugated trienol silyl Due to the easy availability of the starting allenols,[14]
ether M2 or M2-D, respectively, which upon reaction and the highly functionalized nature of the products,
with H+ or D+ would afford the thermodynamically this method would be useful in organic synthesis.
more stable product (E,Z)-2a and (E,Z)-2a-D. The Based on a careful mechanistic study, a possible
rapid proton-exchange and kinetic isotopic effect mechanism has been proposed. Further studies in this
would lead to the low D-incorporation at the C-4 po- area are being carried out in our laboratory.
sition and 63% D-incorporation at the C-1 position of
the product.
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1347

FULL PAPERS
Rong Zeng et al.
266.9 Hz, J2 =28.2 Hz), 138.4, 133.3, 128.7, 128.6, 127.1,
123.5, 122.1–111.8 (m), 108.5, 103.4 (d, J=2.9 Hz), 61.8, 31.7
(d, J=2.8 Hz), 30.3, 22.2, 21.5, 13.8; 19F NMR (282 MHz,
CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.0 ~(À118.2) (m,
2F), À126.9 ~(À127.2) (m, 1F), À127.2 ~(À127.4) (m, 2F);
IR (neat): n=3374, 2960, 2932, 2864, 1933, 1681, 1604, 1490,
1467, 1360, 1267, 1231, 1187, 1152, 1119, 1058, 1033, 951,
919 cmÀ1; MS (EI, 70 eV): m/z (%)=428 (M+, 1.50), 368
(100); HR-MS: m/z=428.1391, calcd. for C20H20F8O (M+):
428.1386.
Experimental Section
Materials
THF and Et2O were distilled from Na/benzophenone before
use. MeCN and DCM were distilled from CaH2 before use.
PhMgCl (1.8M solution in THF) was purchased from Acros.
Other Grignard reagents were prepared from the corre-
sponding aryl halides and magnesium. Other commercially
available chemicals were purchased and used without addi-
1
tional purification unless noted otherwise. H NMR spectra
The following compounds were prepared according to
Procedure 1.
4-(n-Butyl)-6,7,7,8,8,9,9,9-octafluoro-2-(4-bromophenyl)-
nona-2,3,5(Z)-trienol (Z-1f): The reaction of 1aa (1.0684 g,
were recorded on a Bruker-300 MHz spectrometer and
13C NMR spectra were recorded at 75 MHz. All 1H NMR
experiments were measured with tetramethylsilane (0 ppm)
in CDCl3 as the internal reference and 13C NMR experi-
ments were measured in relative to the signal of CDCl3
(77.0 ppm) in CDCl3. Due to the coupling of multiple fluo-
rines, 13C NMR signals of perfluoroalkyl group are extreme-
ly weak, and 19F NMR experiments were undecoupled and
measured relative to the signal of residual CFCl3 (0 ppm) in
1
CDCl3. The coupling constant in the H NMR spectra larger
than 30 Hz is the H,F coupling.
Preparation of Starting Allenols
Compounds 1a–1c, 1e, 1h–1i, 1k–1m as well as new com-
pounds 1d, 1f, 1g, 1j, 1n and 1o were prepared according to
the literature procedures.[14]
3.0 mmol), Et2O (8 mL), and p-BrC6H4MgBr (1.6M in THF,
7.5 mL, 12 mmol) afforded Z-1f (eluent: petroleum ether/
DCM=3/1) as an oil; yield: 0.6448 g (44%); 1H NMR
(300 MHz, CDCl3): d=7.54–7.43 (m, 2H, Ar-H), 7.34–7.20
(m, 2H, Ar-H), 5.90 (d, J=34.2 Hz, 1H, CH=), 4.58 (d, J=
5.7 Hz, 2H, CH2O), 2.38 (t, J=7.2 Hz, 2H, CH2), 1.74–1.62
(m, 1H, OH), 1.56–1.28 (m, 4H, CH2 ꢂ2), 0.90 (t, J=7.2 Hz,
3H, CH3); 13C NMR (75 MHz, CDCl3): d=207.3 (d, J=
5.0 Hz), 145.2 (dt, J1 =267.5 Hz, J2 =28.1 Hz), 132.5, 131.8,
128.0, 121.6, 111.7–111.4 (m), 107.6, 103.5 (d, J=2.5 Hz),
61.7, 31.8 (d, J=2.9 Hz), 30.3, 22.2, 13.8; 19F NMR
(282 MHz, CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.0 ~
(À118.3) (m, 2F), À125.8 ~(À126.2) (m, 1F), À127.1 ~
(À127.4) (m, 2F); IR (neat); n=3357, 2961, 2933, 2875,
1934, 1682, 1489, 1467, 1361, 1229, 1185, 1153, 1120, 1076,
1038, 1009 cmÀ1; MS (EI, 70 eV): m/z (%)=494 (M+ (81Br),
1.90), 492 (M+ (79Br), 1.78), 341 (100); HR-MS: m/z=
492.0329, calcd. for C19H1779BrF8O (M+ (79Br)): 492.0335.
4-(n-Butyl)-6,7,7,8,8,9,9,9-octafluoro-2-(2-thiophenyl)no-
na-2,3,5(Z)-trienol (Z-1g): The reaction of 1aa (1.0655 g,
Typical Procedure 1: 4-(n-Butyl)-6,7,7,8,8,9,9,9-
octafluoro-2-(3-methylphenyl)nona-2,3,5(Z)-trienol
(Z-1d)
To a dry Schlenk tube containing 1aa (1.0689 g, 3.0 mmol)
and 7.5 mL of anhydrous Et2O was added m-MeC6H4MgBr
(2.0m in THF, 6.0 mL, 12.0 mmol) dropwise by syringe
under a nitrogen atmosphere at room temperature within
5 min. Then the resulting reaction mixture was stirred at
room temperature for 2 h. After quenching with an aqueous
solution of saturated ammonium chloride (5 mL) and water
(15 mL), the resulting mixture was extracted with diethyl
ether (30 mLꢂ3), washed with brine once, and dried over
anhydrous Na2SO4. Filtration, evaporation and column chro-
matography on silica gel (eluent: petroleum ether/ethyl ace-
tate=30/1 to 20/1) afforded Z-1d as an oil; yield: 0.9684 g
1
(75%); H NMR (300 MHz, CDCl3): d=7.30–7.22 (m, 1H,
Ar-H), 7.22–7.14 (m, 2H, Ar-H), 7.13–7.05 (m, 1H, Ar-H),
5.92 (d, J=34.2 Hz, 1H, CH=), 4.59 (s, 2H, CH2O), 2.45–
2.33 (m, 5H, CH2 and CH3), 1.69 (s, 1H, OH), 1.55–1.30 (m,
4H, CH2 ꢂ2), 0.91 (t, J=7.1 Hz, 3H, CH3); 13C NMR
(75 MHz, CDCl3):d=207.4 (d, J=5.2 Hz), 144.8 (dt, J1 =
1348
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
3.0 mmol), Et2O (7.5 mL), and 2-thiophenylMgBr (2.0M in
THF, 4.5 mL, 9.0 mmol) afforded Z-1g as an oil (eluent: pe-
troleum ether/ethyl acetate=40/1 to 20/1); yield 1.0191 g
1
(81%); H NMR (300 MHz, CDCl3): d=7.30–7.20 (m, 1H,
Ar-H), 7.10–6.96 (m, 2H, Ar-H), 5.90 (d, J=33.9 Hz, 1H,
CH=), 4.55 (d, J=5.4 Hz, 2H, CH2O), 2.38 (t, J=7.5 Hz,
2H, CH2), 1.76 (t, J=5.7 Hz, 1H, OH), 1.58–1.30 (m, 4H,
CH2 ꢂ2), 0.91 (t, J=7.2 Hz, 3H, CH3); 13C NMR (75 MHz,
CDCl3): d=206.6 (d, J=5.4 Hz), 145.1 (dt, J1 =267.3 Hz,
J2 =28.4 Hz), 137.3, 127.6, 125.4, 124.2, 111.8–111.4 (m),
104.3, 103.7 (d, J=2.9 Hz), 62.4, 32.0 (d, J=2.4 Hz), 30.2,
22.2, 13.8; 19F NMR (282 MHz, CDCl3): d=À80.8 ~(À80.9)
(m, 3F), À118.1 ~(À118.3) (m, 2F), À125.9 ~(À126.3) (m,
1F), À127.2 ~(À127.4) (m, 2F); IR (neat): n=3374, 2961,
2933, 2875, 1933, 1681, 1467, 1360, 1228, 1187, 1154, 1120,
1034, 957, 913 cmÀ1; MS (EI, 70 eV): m/z (%)=420 (M+,
2.35), 347 (100); HR-MS: m/z=420.0791, calcd. for
C17H16F8OS (M+): 420.0794.
34.8 Hz, 1H, CH=), 4.58 (d, J=3.9 Hz, 2H, CH2O), 2.37 (t,
J=7.4 Hz, 2H, CH2), 2.02–1.90 (m, 1H, OH), 1.60–1.28 (m,
4H, CH2 ꢂ2), 0.90 (t, J=7.1 Hz, 3H, CH3); 13C NMR
(75 MHz, CDCl3): d=207.2 (d, J=5.5 Hz), 144.8 (dq, J1 =
265.1 Hz, J2 =38.0 Hz), 133.4, 128.7, 127.6, 126.4, 118.6 (qd,
J1 =270.3 Hz, J2 =40.7 Hz), 109.5–109.1 (m), 108.3, 103.2 (d,
J=3.1 Hz), 61.6, 31.6 (d, J=3.2 Hz), 30.3, 22.2, 13.7;
19F NMR (282 MHz, CDCl3): d=À72.5 (d, J=12.7 Hz, 3F),
À131.5 (dq, J1 =33.7 Hz, J2 =12.0 Hz, 1F); IR (neat): n=
3359, 2960, 2932, 2874, 1934, 1689, 1598, 1496, 1467, 1359,
1307, 1288, 1188, 1141, 1047, 1026 cmÀ1; MS (EI, 70 eV): m/z
(%)=314 (M+, 1.38), 254 (100); HR-MS: m/z=314.1307,
calcd. for C17H18F4O (M+): 314.1294.
4-(n-Butyl)-6,7,7,8,8,9,9,9-octafluoro-2-(2-thiophenyl)no-
na-2,3,5(Z)-trienol (Z-1j): The reaction of 1ab (1.1093 g,
2-[2,3,3,4,4,5,5,5-(Z)-Octafluoropentenyl]-4-phenylpenta-
2,3-diene-1,5-diol (Z-1o): The reaction of 1ad (64.9 mg,
2.5 mmol), Et2O (6.5 mL), and p-FC6H4MgBr (2.0M in
THF, 5.0 mL, 10 mmol) afforded Z-1j as an oil (eluent: pe-
troleum ether/ethyl acetate=100/1 to 60/1 to 40/1 to 30/1);
yield: 1.0700 g (81%); 1H NMR (300 MHz, CDCl3): d=
7.42–7.32 (m, 2H, Ar-H), 7.11–6.98 (m, 2H, Ar-H), 5.91 (d,
J=34.2 Hz, 1H, CH=), 4.58 (d, J=6.0 Hz, 2H, CH2O), 2.38
(t, J=7.4 Hz, 2H, CH2), 1.71 (t, J=6.2 Hz, 1H, OH), 1.60–
1.30 (m, 4H, CH2 ꢂ2), 0.90 (t, J=7.1 Hz, 3H, CH3);
13C NMR (75 MHz, CDCl3): d=207.2 (d, J=3.3 Hz), 163.9,
160.6, 145.2 (dt, J1 =267.2 Hz, J2 =28.3 Hz), 129.4 (d, J=
2.9 Hz), 128.1 (d, J=7.7 Hz), 115.8 (d, J=21.7 Hz), 112.0–
111.7 (m), 107.5, 103.4 (d, J=2.9 Hz), 61.9, 31.8 (d, J=
3.0 Hz), 30.3, 22.2, 13.8; 19F NMR (282 MHz, CDCl3): d=
À80.7 ~(À80.9) (m, 3F), À114.1 ~(À114.3) (m, 1F), À117.0
~(À117.3) (m, 2F), À122.7 ~(À123.2) (m, 4F), À126.1 ~
(À126.5) (m, 3F); IR (neat): n=3342, 2961, 2933, 2875,
1933, 1682, 1603, 1510, 1468, 1364, 1237, 1203, 1143, 1110,
1047 cmÀ1; MS (EI, 70 eV): m/z (%)=532 (M+, 1.62), 109
(100); HR-MS: m/z=532.1068, calcd. for C21H17F13O (M+):
532.1072.
0.2 mmol), Et2O (0.5 mL), and PhMgCl (1.8M in THF,
0.56 mL, 1.0 mmol) afforded Z-1o as an oil (eluent: petrole-
um ether/ethyl acetate=3/1 for the first round and DCM/
ethyl acetate=5/1 to 4/1 for the second round); yield:
53.3 mg (70%); 1H NMR (300 MHz, CDCl3): d=7.40–7.22
(m, 5H, Ar-H), 5.97 (d, J=36.0 Hz, 1H, CH=), 5.59 (d, J=
13.2 Hz, 1H, CH2O), 5.50 (d, J=13.2 Hz, 1H, CH2O), 4.36
(s, 2H, CH2O), 3.90 (bs, 2H, OH ꢂ 2); 13C NMR (75 MHz,
CDCl3): d=206.6 (d, J=5.6 Hz), 145.2 (dt, J1 =266.3 Hz,
J2 =28.4 Hz), 132.8, 128.8, 128.1, 126.4, 111.3, 109.8–109.4
(m), 104.5 (d, J=4.1 Hz), 61.5 (d, J=5.0 Hz), 61.1; 19F NMR
(282 MHz, CDCl3): d=À80.9 (t, J=8.3 Hz, 3F), À118.0 ~
(À118.2) (m, 2F), À125.3 ~(À125.7) (m, 1F), À127.2 (d, J=
2.5 Hz, 2 F); IR (neat): n=3332, 2935, 2880, 1939, 1683,
4-(n-Butyl)-2-phenyl-6,7,7,7-tetrafluorohepta-2,3,5(Z)-tri-
enol (Z-1n): The reaction of 1ac (440.4 mg, 1.72 mmol),
Et2O (6 mL), and PhMgCl (2.0M in THF, 3.6 mL, 7.2 mmol)
afforded Z-1n as an oil (eluent: petroleum ether/ethyl ace-
tate=20/1 to 10/1); yield: 469.0 mg (87%); 1H NMR
(300 MHz, CDCl3): d=7.46–7.18 (m, 5H, Ar-H), 5.90 (d, J=
1496, 1453, 1360, 1228, 1187, 1155, 1120, 1053, 1029 cmÀ1
;
MS (ESI): m/z (%)=411 (M+ +Na, 100); HR-MS: m/z=
411.0617, calcd. for C16H12F8NaO2 (M+): 411.0602.
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1349

FULL PAPERS
Rong Zeng et al.
4-(n-Butyl)-1-deuterio-6,7,7,8,8,9,9,9-octafluoro-2-
phenylnona-2,3,5(Z)-trienol (Z-1a-D)
4-Methyl-2-phenyl-5,5,5-trifluoro-2,3-pentadienol (1q)
Compound 1q was prepared according to the literature
procedure.[20] To
a dried Schlenk tube equipped with
a Teflon-coated magnetic stirring bar were added LiBr
(52.0 mg, 0.6 mmol), CuBr.Me2S (124.3 mg, 0.6 mmol), THF
(2 mL), 1q-THP-OMs (133.3 mg, 0.4 mmol), and THF
(2 mL) sequentially at À508C under a nitrogen atmosphere.
Then PhMgCl (1.8M in THF, 0.33 mL, 0.6 mmol) was added
dropwise using the syringe in 2 min at À508C. After 1.5 h,
the reaction was quenched with a saturated aqueous solu-
tion of NH4Cl (2 mL) at À508C, and the aqueous layer was
extracted with Et2O (15 mLꢂ3). The combined organic
layer was dried over anhydrous Na2SO4. Filtration, evapora-
tion, and silica gel flash column chromatography (eluent:
petroleum ether/ethyl acetate=100/1 to 30/1) afforded the
product 1q-THP, which was used in the next step directly.
To a dried Schlenk tube equipped with a Teflon-coated
magnetic stirring bar were added 1q-THP, MeOH (3 mL),
and TsOH·H2O (7.8 mg, 0.04 mmol) sequentially at room
temperature. After 8.0 h, the reaction mixture was evaporat-
ed, and silica gel flash column chromatography (eluent: pe-
troleum ether/ethyl acetate=10/1) afforded the product 1q
as a liquid; yield: 74.9 mg (81% for 2 steps); 1H NMR
(300 MHz, CDCl3): d=7.44–7.25 (m, 5H, Ar-H), 4.58 (d, J=
4.8 Hz, 2H, CH2O), 2.14–2.05 (m, 1H, OH), 1.97 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): d=201.7 (q, J=4.2 Hz),
132.3, 128.8, 128.3, 126.6, 123.5 (q, J=272.3 Hz), 112.6, 98.7
(q, J=34.4 Hz), 61.2, 13.1; 19F NMR (282 MHz, CDCl3): d=
À65.3; IR (neat): n=3346, 2933, 1969, 1600, 1497, 1463,
1379, 1298, 1169, 1119, 1090, 1034 cmÀ1; MS (EI, 70 eV): m/z
(%)=228 (M+, 39.3), 178 (100); HR-MS: m/z=228.0763,
calcd. for C12H11F3O (M+): 228.0762.
Compound Z-1a-D was prepared by oxidation and reduc-
tion of Z-1a.[19] To a dried Schlenk tube equipped with
a Teflon-coated magnetic stirring bar were added FeCl3
(24.6 mg, 0.15 mmol), TEMPO (23.8 mg, 0.15 mmol),
NaNO2 (10.2 mg, 0.15 mmol), phenol (29.2 mg, 0.3 mmol),
and DCM (2 mL) sequentially at room temperature under
an oxygen atmosphere (1 atm). After stirring for 10 min, Z-
1a (621.6 mg, 1.5 mmol) and DCM (4 mL) were added. The
resulting mixture was stirred for 13 h, filtrated through
a short column of silica gel (eluent: Et2O), purified by flash
column chromatography on silica gel (eluent: petroleum
ether/ethyl ether=80/1) to afford Z-1a-O, which was used
for the reduction reaction directly.
To a dried Schlenk tube equipped with a Teflon-coated
magnetic stirring bar were added Z-1a-O and THF (4 mL)
at room temperature under a nitrogen atmosphere. The
tube was then submerged in a cooling bath at À788C. After
stirring for 5 min, LiAlD4 (19.0 mg, 0.45 mmol) and THF
(2 mL) were added. After 3.5 h, the reaction was quenched
with a saturated aqueous solution of NH4Cl (1 mL) at
À788C, and the aqueous layer was extracted with Et2O
(25 mLꢂ3). The combined organic layer was washed with
brine, dried over anhydrous Na2SO4. Filtration, evaporation,
and silica gel flash column chromatography (eluent: petrole-
um ether/ethyl acetate=20/1 to 10/1) afforded the product
Z-1a-D as an oil; yield: 375.8 mg (60%); 1H NMR
(300 MHz, CDCl3); d=7.46–7.24 (m, 5H, Ar-H), 5.92 (d,
J=34.2 Hz, 1H, CH=), 4.65–4.55 (m, 1H, CHO), 2.39 (t, J=
7.4 Hz, 2H, CH2), 1.62 (s, 1H, OH), 1.57–1.30 (m, 4H,
CH2 ꢂ2), 0.90 (t, J=7.1 Hz, 3H, CH3); 13C NMR (75 MHz,
CDCl3): d=207.4 (d, J=4.9 Hz), 144.9 (dt, J1 =268.7 Hz,
J2 =28.6 Hz), 133.4, 128.8, 127.7, 126.4, 112.0–111.7 (m),
108.4, 103.5 (d, J=2.7 Hz), 61.4 (t, J=22.6 Hz), 31.8 (d, J=
3.8 Hz), 30.4, 22.3, 13.8; 19F NMR (282 MHz, CDCl3): d=
À80.8 (t, J=9.4 Hz, 3F), À118.0 ~(À118.2) (m, 2F), À126.6
~(À127.0) (m, 1F), À127.2 ~(À127.4) (m, 2F); IR (neat):
n=3340, 2961, 2933, 1933, 1682, 1599, 1496, 1453, 1361,
1230, 1188, 1153, 1120, 1059, 1032 cmÀ1; MS (EI, 70 eV): m/z
(%)=415 (M+, 1.45), 355 (100); HR-MS: m/z=415.1283,
calcd. for C19H17DF8O (M+): 415.1293.
Methyl 2-Butyl-4-phenyl-5-hydroxypenta-2,3-dienoate
(5a)
Compound 5a was prepared according to the literature
procedure.[21] To a flask was added 5aa (401.1 mg, 2 mmol),
MeOH (10 mL), and PdACHTNUGTRNEUGN(PPh3)4 (46.6 mg, 0.04 mmol) se-
quentially. The resulting mixture was degassed with CO for
three times, and then stirred at room temperature under
1350
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
200 psi of CO in an autoclave for 5.5 h. After removal of the
solvent under vacuum, the residue was purified by flash
chromatography on silica gel (petroleum ether/diethyl
ether=5/1 to 4/1) to afford 5a as a liquid; yield: 0.5211 g
1
(100%); H NMR (300 MHz, CDCl3): d=7.45–7.23 (m, 5H,
Ar-H), 4.63 (s, 2H, CH2O), 3.74 (s, 3H, CH3), 2.44–2.32 (m,
2H, CH2), 2.14 (bs, 1H, OH), 1.52–1.28 (m, 4H, CH2 ꢂ2),
0.88 (t, J=7.2 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d=210.1, 167.3, 132.8, 128.7, 127.8, 126.4, 110.6, 104.9, 61.5,
52.3, 30.2, 28.7, 22.3, 13.8; IR (neat): n=3417, 2955, 2919,
ing with water (10 mL), the resulting mixture was extracted
with diethyl ether (15 mL ꢂ 3), washed with brine, and dried
over anhydrous Na2SO4. Filtration, evaporation and column
chromatography on silica gel (eluent: 30–608C petroleum
ether/ethyl acetate=80/1 to 40/1) afforded (E,Z)-2a as an
2872, 1944, 1716, 1496, 1453, 1436, 1267, 1133, 1087 cmÀ1
;
MS (EI, 70 eV): m/z (%)=260 (M+, 2.2), 141 (100); HR-
MS: m/z=260.1413, calcd. for C16H20O3 (M+): 260.1412.
oil; yield: 58.0 mg (70%); (E,Z)/ACTHUNTGRNEUNG(Z,Z)=98/2 determined by
1
1H NMR analysis of the crude product; H NMR (300 MHz,
CDCl3): d=9.65 (s, 1H, CHO), 7.48–7.33 (m, 3H, Ar-H),
7.16–7.05 (m, 2H, Ar-H), 6.48 (dd, J1 =10.4 Hz, J2 =0.8 Hz,
1H, CH=), 5.58 (dd, J1 =32.7 Hz, J2 =9.9 Hz, 1H, CH=),
3.79–3.61 (m, 1H, CH), 1.65–1.45 (m, 2H, CH2), 1.35–1.09
(m, 4H, CH2 ꢂ2), 0.90–0.76 (m, 3H, CH3); 13C NMR
(75 MHz, CDCl3): d=193.0, 152.5, 146.1 (dt, J1 =260.0 Hz,
J2 =29.1 Hz), 144.7, 131.9, 129.1, 128.5, 128.4, 116.4–116.0
(m), 35.1 (d, J=2.4 Hz), 34.3, 28.8, 22.2, 13.7; 19F NMR
(282 MHz, CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.5 ~
(À118.8) (m, 2F), À127.4 ~(À127.5) (m, 2F), À128.5 ~
(À128.8) (m, 1F); IR (neat): n=2933, 2862, 2715, 1698,
1633, 1495, 1444, 1350, 1224, 1187, 1120, 1079, 949 cmÀ1; MS
(EI, 70 eV): m/z (%)=414 (M+, 100); HR-MS: m/z=
414.1214, calcd. for C19H18F8O (M+): 414.1230.
4-(n-Butyl)-6,7,7,8,8,9,9,9-octafluoro-2-phenylnona-
2,3,5(Z)-trienyl tert-Butyl(dimethylsilyl) Ether (Z-
11a)
To a dry Schlenk tube were added Z-1a (415.6 mg,
1.0 mmol), DCM (10 mL), Et3N (0.28 mL, d=0.726 gmLÀ1,
203.3 mg, 2 mmol), TBSCl (188.1 mg, 1.2 mmol), and
DMAP (6.2 mg, 0.05 mmol) sequentially at 08C under a ni-
trogen atmosphere. After 17 h, the reaction mixture was
treated with TBSCl (45.5 mg, 0.3 mmol) and stirred for 5 h.
After quenching with water (5 mL), the resulting mixture
was extracted with diethyl ether (20 mLꢂ3) and dried over
anhydrous Na2SO4. Filtration, evaporation and column chro-
matography on silica gel (eluent: petroleum ether) afforded
The following compounds were prepared according to
Procedure 2.
4-Butyl-6,7,7,8,8,9,9,9-octafluoro-2-(4-methoxyl-phenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2b]: The reaction of Z-1b
(91.7 mg, 0.21 mmol), NaI (60.8 mg, 0.41 mmol), and TBSCl
1
Z-11a as an oil; yield: 492.7 mg (93%); H NMR (300 MHz,
CDCl3): d=7.44–7.29 (m, 4H, Ar-H), 7.28–7.20 (m, 1H, Ar-
H), 5.92 (d, J=35.7 Hz, 1H, CH=), 4.60 (s, 2H, CH2O), 2.38
(t, J=7.7 Hz, 2H, CH2), 1.58–1.30 (m, 4H, CH2 ꢂ2), 0.94–
0.80 (m, 12H, CH3 ꢂ4), 0.07 (s, 6H, CH3 ꢂ2); 13C NMR
(75 MHz, CDCl3): d=208.7–208.5 (m), 134.1, 128.5, 128.4
(d, J=1.3 Hz), 126.6, 112.5–112.2 (m), 108.2 (d, J=2.0 Hz),
103.0 (t, J=4.2 Hz), 62.2, 31.5 (d, J=4.2 Hz), 30.4 (d, J=
1.3 Hz), 25.7, 22.3 (d, J=2.0 Hz), 18.1, 13.9, 13.8, À5.4;
19F NMR (282 MHz, CDCl3): d=À80.8 (t, J=8.7 Hz, 3 F),
À117.9 ~(À118.2) (m, 2 F), À127.2 ~(À127.4) (m, 2 F),
À128.2 ~(À127.6) (m, 1 F); IR (neat): n=2958, 2932, 2860,
1935, 1681, 1496, 1472, 1361, 1256, 1231, 1187, 1120,
1051 cmÀ1; MS (ESI): m/z (%)=529 (M+ +H), 551 (M+ +
Na, 100); HR-MS: m/z=551.1990, calcd. for C25H32F8NaOSi
(M+): 551.1987.
(46.1 mg, 0.31 mmol) in MeCN (2.0 mL) at room tempera-
ture for 2 h afforded (E,Z)-2b (eluent: 30–608C petroleum
ether/ethyl acetate=80/1 to 60/1 to 40/1) as an oil; yield:
1
73.0 mg (80%); (E,Z)/
G
1
analysis of the crude product; H NMR (300 MHz, CDCl3):
d=9.62 (s, 1H, CHO), 7.09–7.01 (m, 2H, Ar-H), 6.99–6.91
(m, 2H, Ar-H), 6.43 (d, J=10.2 Hz, 1H, CH=), 5.57 (dd,
J1 =32.9 Hz, J2 =10.1 Hz, 1H, CH=), 3.93–3.66 (m, 4H,
CH3O and CH), 1.62–1.46 (m, 2H, CH2), 1.34–1.10 (m, 4H,
CH2 ꢂ2), 0.84 (t, J=6.8 Hz, 3H, CH3); 13C NMR (75 MHz,
CDCl3): d=193.5, 159.6, 152.4, 145.9 (dt, J1 =259.7 Hz, J2 =
28.9 Hz), 144.1, 130.3, 123.9, 116.5–116.2 (m), 113.9, 55.2,
35.1 (d, J=2.4 Hz), 34.3, 28.8, 22.2, 13.7; 19F NMR
(282 MHz, CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.5 ~
(À118.7) (m, 2F), À127.4 ~(À127.5) (m, 2F), À128.6 ~
(À129.0) (m, 1F); IR (neat): n=2961, 2935, 2862, 2712,
1696, 1608, 1514, 1467, 1350, 1293, 1245, 1228, 1186, 1120,
1074, 1033 cmÀ1; MS (EI, 70 eV): m/z (%)=444 (M+, 100);
Typical Procedure 2: Synthesis of 6-Fluoro-6-
perfluoroalkyl-2(E),5(Z)-dienals 2
4-Butyl-6,7,7,8,8,9,9,9-octafluoro-2-phenyl-2(E),5(Z)-nona-
dienal [(E,Z)-2a]: To a dry Schlenk tube was added NaI
(60.7 mg, 0.40 mmol), Z-1a (83.0 mg, 0.20 mmol), MeCN
(2.0 mL), and TBSCl (46.2 mg, 0.31 mmol) at room tempera-
ture under a nitrogen atmosphere. Then the reaction mix-
ture was stirred at room temperature for 2 h. After quench-
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1351

FULL PAPERS
Rong Zeng et al.
HR-MS: m/z=444.1336, calcd. for C20H20F8O2 (M+):
444.1336.
4-Butyl-6,7,7,8,8,9,9,9-octafluoro-2-(4-methylphenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2c]: The reaction of Z-1c
(85.7 mg, 0.20 mmol), NaI (60.8 mg, 0.41 mmol), and TBSCl
34.3, 28.8, 22.1, 21.2, 13.7; 19F NMR (282 MHz, CDCl3): d=
À80.8 ~(À80.9) (m, 3F), À118.5 ~(À118.8) (m, 2F), À127.4
~(À127.5) (m, 2F), À128.8 ~(À129.1) (m, 1F); IR (neat):
n=2961, 2933, 2862, 1698, 1467, 1350, 1230, 1186, 1120,
1080, 1032 cmÀ1; MS (EI, 70 eV): m/z (%)=428 (M+, 27.48),
105 (100); HR-MS: m/z=428.1386, calcd. for C20H20F8O
(M+): 428.1386.
4-Butyl-6,7,7,8,8,9,9,9-octafluoro-2-(4-fluoro-phenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2e]: The reaction of Z-1e
(87.2 mg, 0.20 mmol), NaI (60.8 mg, 0.41 mmol), and TBSCl
(45.8 mg, 0.30 mmol) in MeCN (2.0 mL) at room tempera-
ture for 2 h afforded (E,Z)-2c (eluent: 30–608C petroleum
ether/ethyl acetate=80/1 to 40/1) as an oil; yield: 67.0 mg
1
(78%); (E,Z)/
G
1
of the crude product; H NMR (300 MHz, CDCl3): d=9.63
(s, 1H, CHO), 7.23 (d, J=7.8 Hz, 2H, Ar-H), 6.99 (d, J=
8.1 Hz, 2H, Ar-H), 6.45 (d, J=10.5 Hz, 1H, CH=), 5.56
(dd, J1 =32.7 Hz, J2 =9.9 Hz, 1H, CH=), 3.82–3.64 (m, 1H,
CH), 2.38 (s, 3H, CH3), 1.65–1.45 (m, 2H, CH2), 1.32–1.10
(m, 4H, CH2 ꢂ2), 0.84 (t, J=6.8 Hz, 3H, CH3); 13C NMR
(75 MHz, CDCl3): d=193.4, 152.4 (d, J=1.4 Hz), 145.9 (dt,
J1 =260.0 Hz, J2 =29.5 Hz), 144.6, 138.2, 129.2, 128.9, 128.8,
116.5–116.1 (m), 35.1 (d, J=1.0 Hz), 34.3, 28.8, 22.2, 21.2,
13.7; 19F NMR (282 MHz, CDCl3): d=À80.8 ~(À80.9) (m,
3F), À118.5 ~(À118.8) (m, 2F), À127.4 ~(À127.5) (m, 2F),
À128.6 ~(À128.9) (m, 1F); IR (neat): n=2961, 2931, 2862,
2711, 1698, 1636, 1515, 1467, 1350, 1311, 1221, 1187, 1156,
1120, 1073, 1032 cmÀ1; MS (EI, 70 eV): m/z (%)=428 (M+,
100); HR-MS: m/z=428.1401, calcd. for C20H20F8O (M+):
428.1386.
(46.1 mg, 0.31 mmol) in MeCN (2.0 mL) at room tempera-
ture for 2 h afforded (E,Z)-2e (eluent: 30–608C petroleum
ether/ethyl acetate=100/1 to 80/1) as an oil; yield: 58.9 mg
1
(68%); (E,Z)/
G
1
of the crude product; H NMR (300 MHz, CDCl3): d=9.63
(s, 1H, CHO), 7.18–7.03 (m, 4H, Ar-H), 6.49 (d, J=10.2 Hz,
1H, CH=), 5.57 (dd, J1 =32.7 Hz, J2 =9.9 Hz, 1H, CH=),
3.78–3.60 (m, 1H, CH), 1.70–1.48 (m, 2H, CH2), 1.32–1.10
(m, 4H, CH2 ꢂ2), 0.84 (t, J=6.8 Hz, 3H, CH3); 13C NMR
(75 MHz, CDCl3): d=192.9, 164.4, 161.1, 153.1, 146.2 (dt,
J1 =259.9 Hz, J2 =29.3 Hz), 143.8, 130.9 (d, J=8.1 Hz), 127.7
(d, J=3.5 Hz), 116.2–115.9 (m), 115.6 (d, J=21.2 Hz), 35.1
(d, J=1.7 Hz), 34.3, 28.8, 22.2, 13.7; 19F NMR (282 MHz,
CDCl3): d=À80.8 ~(À80.9) (m, 3F), À113.1 ~(À113.2) (m,
1F), À118.6 ~(À118.8) (m, 2F), À127.4 ~(À127.5) (m, 2F),
À128.4 ~(À128.75) (m, 1F); IR (neat): n=2962, 2934, 2863,
2715, 1697, 1604, 1512, 1350, 1225, 1187, 1159, 1120,
1071 cmÀ1; MS (EI, 70 eV): m/z (%)=432 (M+, 84.99), 178
(100); HR-MS: m/z=432.1122, calcd. for C19H17F9O (M+):
432.1136.
4-Butyl-6,7,7,8,8,9,9,9-octafluoro-2-(3-methylphenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2d]: The reaction of Z-1d
(85.8 mg, 0.20 mmol), NaI (61.0 mg, 0.41 mmol), and TBSCl
4-Butyl-6c,7,7,8,8,9,9,9-octafluoro-2-(4-bromophenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2f]: The reaction of Z-1f
(91.8 mg, 0.19 mmol) and NaI (56.7 mg, 0.37 mmol) and
(45.0 mg, 0.30 mmol) in MeCN (2.0 mL) at room tempera-
ture for 2 h afforded (E,Z)-2d (eluent: 30–608C petroleum
ether/ethyl acetate=100/1 to 60/1) as an oil; yield: 58.5 mg
1
(68%); (E,Z)/
G
1
of the crude product; H NMR (300 MHz, CDCl3): d=9.63
(s, 1H, CHO), 7.35–7.27 (m, 1H, Ar-H), 7.23–7.14 (m, 1H,
Ar-H), 6.95–6.85 (m, 2H, Ar-H), 6.46 (d, J=9.9 Hz, 1H,
CH=), 5.56 (dd, J1 =32.7 Hz, J2 =10.2 Hz, 1H, CH=), 3.80–
3.62 (m, 1H, CH), 2.36 (s, 3H, CH3), 1.70–1.46 (m, 2H,
CH2), 1.35–1.10 (m, 4H, CH2 ꢂ2), 0.84 (t, J=6.6 Hz, 3H,
CH3); 13C NMR (75 MHz, CDCl3): d=193.2, 152.5, 145.9
(dt, J1 =260.1 Hz, J2 =29.3 Hz), 144.8, 138.1, 131.8, 129.7,
129.1, 128.3, 126.1, 116.5–116.1 (m), 35.1 (d, J=2.0 Hz),
TBSCl (42.0 mg, 0.28 mmol) in MeCN (2.0 mL) at room
temperature for 2 h afforded (E,Z)-2f (eluent: 30–608C pe-
troleum ether/ethyl acetate=80/1 to 60/1) as an oil; yield:
1
48.4 mg (53%); (E,Z)/
(Z,Z)=98/2 determined by H NMR
1
analysis of the crude product; H NMR (300 MHz, CDCl3):
d=9.62 (s, 1H, CHO), 7.60–7.53 (m, 2H, Ar-H), 7.03–6.94
(m, 2H, Ar-H), 6.50 (dd, J1 =10.4 Hz, J2 =0.5 Hz, 1H, CH=
1352
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
), 5.56 (dd, J1 =32.7 Hz, J2 =9.9 Hz, 1H, CH=), 3.75–3.57
(m, 1H, CH), 1.60–1.47 (m, 2H, CH2), 1.32–1.11 (m, 4H,
CH2 ꢂ2), 0.85 (t, J=6.8 Hz, 3H, CH3); 13C NMR (75 MHz,
CDCl3): d=192.6, 153.1, 143.6, 131.8, 130.8, 130.7, 122.8,
116.1–115.8 (m), 35.2 (d, J=1.4 Hz), 34.3, 28.8, 22.2, 13.7;
19F NMR (282 MHz, CDCl3): d=À80.8 ~(À80.9) (m, 3F),
À118.6 ~(À118.8) (m, 2F), À127.4 ~(À127.5) (m, 2F),
À128.1 ~(À128.4) (m, 1F); IR (neat): n=2955, 2925, 2854,
2712, 1699, 1638, 1590, 1489, 1465, 1349, 1220, 1187, 1156,
1121, 1066, 1012 cmÀ1; MS (EI, 70 eV): m/z (%)=495 (M+-
CH3 ꢂ2); 13C NMR (75 MHz, CDCl3): d=194.8, 151.8–151.7
(m), 144.5, 116.7–116.3 (m), 34.4–34.2 (m), 30.1, 29.0, 24.1,
22.8, 22.3, 13.8, 13.7; 19F NMR (282 MHz, CDCl3): d=À80.8
~(À80.9) (m, 3F), À118.6 ~(À118.8) (m, 2F), À127.4 ~
(À127.5) (m, 2F), À129.7 ~(À130.0) (m, 1F); IR (neat): n=
2961, 2934, 2864, 1694, 1642, 1468, 1351, 1229, 1187, 1155,
1122 cmÀ1; MS (EI, 70 eV): m/z (%)=394 (M+, 12.83), 111
(100); HR-MS: m/z= calcd. for C17H22F8O (M+): 394.1543.
4-Butyl-6,7,7,8,8,9,9,10,10,11,11,11-dodecafluoro-2-phenyl-
2(E),5(Z)-undecadienal [(E,Z)-2i]: The reaction of Z-1i
A
+A(81Br), 45.03), 493 (M+A(79Br)+1,
CHUTGTNRENNUG HCTUNGTRENNUGN
CHTUNGTRENNUNG
CTHUNGTRENNUNG
(102.8 mg, 0.20 mmol), NaI (60.9 mg, 0.40 mmol), and
TBSCl (45.7 mg, 0.30 mmol) in MeCN (2.0 mL) at room
temperature for 2 h afforded (E,Z)-2i (eluent: 30–608C pe-
troleum ether/ethyl acetate=100/1 to 80/1) as an oil; yield:
1
62.1 mg (60%); (E,Z)/
G
1
analysis of the crude product; H NMR (300 MHz, CDCl3):
d=9.65 (s, 1H, CHO), 7.48–7.34 (m, 3H, Ar-H), 7.14–7.06
(m, 2H, Ar-H), 6.49 (d, J=10.2 Hz, 1H, CH=), 5.57 (dd,
J1 =32.7 Hz, J2 =9.9 Hz, 1H, CH=), 3.78–3.63 (m, 1H, CH),
1.64–1.45 (m, 2H, CH2), 1.30–1.08 (m, 4H, CH2 ꢂ2), 0.83 (t,
J=6.8 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): d=193.2,
152.7, 146.2 (dt, J1 =259.4 Hz, J2 =29.0 Hz), 144.7, 131.8,
129.0, 128.44, 128.37, 116.4–116.1 (m), 35.1 (d, J=1.7 Hz),
34.3, 28.8, 22.2, 13.7; 19F NMR (282 MHz, CDCl3): d=À80.8
~(À81.0) (m, 3F), À117.5 ~(À117.8) (m, 2F), À122.9 ~
(À123.2) (m, 2F), À123.2 ~(À123.4) (m, 2F), À126.2 ~
(À126.5) (m, 2F), À128.3 ~(À128.7) (m, 1F); IR (neat): n=
2962, 2934, 2863, 2710, 1698, 1636, 1601, 1497, 1468, 1445,
1353, 1317, 1239, 1203, 1143, 1108, 1081, 1028 cmÀ1; MS (EI,
70 eV): m/z (%)=514 (M+, 71.56), 160 (100); HR-MS:
m/z=514.1163, calcd. for C21H18F12O (M+): 514.1166.
0.20 mmol), NaI (60.8 mg, 0.41 mmol), and TBSCl (45.6 mg,
0.30 mmol) in MeCN (2.0 mL) at room temperature for 2 h
afforded (E,Z)-2g (eluent: 30–608C petroleum ether/ethyl
acetate=150/1) as an oil; yield: 50.1 mg (60%); (E,Z)/ACHTUNG-
1
TRENNUNG(Z,Z)=95/5 determined by H NMR analysis of the crude
product; 1H NMR (300 MHz, CDCl3): d=9.60 (s, 1H,
CHO), 7.47 (dd, J1 =3.6 Hz, J2 =2.4 Hz, 1H, Ar-H), 7.15–
7.08 (m, 2H, Ar-H), 6.47 (d, J=10.2 Hz, 1H, CH=), 5.60
(dd, J1 =32.9 Hz, J2 =9.8 Hz, 1H, CH=), 4.16–4.00 (m, 1H,
CH), 1.70–1.53 (m, 2H, CH2), 1.38–1.15 (m, 4H, CH2 ꢂ2),
0.87 (t, J=6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
d=192.3, 153.0, 136.9, 131.2, 128.6, 127.5, 127.0, 116.2–115.8
(m), 35.2 (d, J=3.9 Hz), 34.5, 28.8, 22.3, 13.8; 19F NMR
(282 MHz, CDCl3): d=À80.7 ~(À80.9) (m, 3F), À118.5 ~
(À118.7) (m, 2F), À127.3 ~(À127.5) (m, 2F), À127.8 ~
(À128.1) (m, 1F); IR (neat): n=2961, 2933, 2862, 2718,
4-Butyl-6,7,7,8,8,9,9,10,10,11,11,11-dodecafluoro-2-(4-
fluoro-phenyl)-2(E),5(Z)- undecadienal [(E,Z)-2j]: The re-
action of Z-1j (106.8 mg, 0.20 mmol), NaI (61.0 mg,
0.41 mmol), and TBSCl (45.2 mg, 0.30 mmol) in MeCN
1700, 1440, 1351, 1228, 1187, 1155, 1122, 1083, 1029 cmÀ1
;
MS (EI, 70 eV): m/z (%)=420 (M+, 76.52), 109 (100); HR-
MS: m/z=420.0786, calcd. for C17H16F8OS (M+): 420.0794.
2,4-Dibutyl-6,7,7,8,8,9,9,9-octafluoro-2(E),5(Z)-nonadienal
[(E,Z)-2h]: The reaction of Z-1h (78.0 mg, 0.20 mmol), NaI
(60.4 mg, 0.40 mmol), and TBSCl (45.1 mg, 0.30 mmol) in
MeCN (2.0 mL) at room temperature for 2 h afforded
(E,Z)-2h (eluent: 30–608C petroleum ether/ethyl ether=
100/1 to petroleum ether/ethyl acetate=60/1) as an oil;
(2.0 mL) at room temperature for 2 h afforded (E,Z)-2j
(eluent: 30–608C petroleum ether/ethyl acetate=100/1 to
60/1 to 40/1) as an oil; yield: 70.3 mg (66%); (E,Z)/ACHTUNGTRENNUNG(Z,Z)=
1
yield: 25.1 mg (32%); (E,Z)/ACTHNUGRTNEUNG(Z,Z)=99/1 determined by
98/2 determined by H NMR analysis of the crude product;
1H NMR (300 MHz, CDCl3): d=9.63 (s, 1H, CHO), 7.17–
7.04 (m, 4H, Ar-H), 6.49 (d, J=10.2 Hz, 1H, CH=), 5.57
(dd, J1 =32.7 Hz, J2 =9.9 Hz, 1H, CH=), 3.76–3.61 (m, 1H,
CH), 1.65–1.48 (m, 2H, CH2), 1.36–1.09 (m, 4H, CH2 ꢂ2),
0.84 (t, J=6.8 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3):
1
1H NMR analysis of the crude product; H NMR (300 MHz,
CDCl3): d=9.39 (s, 1H, CHO), 6.19 (d, J=10.2 Hz, 1H,
CH=), 5.52 (dd, J1 =32.4 Hz, J2 =10.2 Hz, 1H, CH=), 3.89–
3.73 (m, 1H, CH), 2.38–2.16 (m, 2H, CH2), 1.68–1.50 (m,
2H, CH2), 1.42–1.18 (m, 8H, CH2 ꢂ4), 0.97–0.84 (m, 6H,
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1353

FULL PAPERS
Rong Zeng et al.
d=193.0, 162.7 (d, J=246.3 Hz), 153.2, 146.3 (dt, J1 =
259.2 Hz, J2 =28.3 Hz), 143.7, 130.9 (d, J=8.0 Hz), 127.6 (d,
J=3.5 Hz), 116.3–115.9 (m), 115.7 (d, J=21.6 Hz), 35.1 (d,
J=2.0 Hz), 34.3, 28.8, 22.2, 13.7; 19F NMR (282 MHz,
CDCl3): d=À80.8 ~(À80.9) (m, 3F), À113.1 ~(À113.2) (m,
1F), À117.6 ~(À117.8) (m, 2F), À122.9 ~(À123.4) (m, 4F),
À126.2 ~(À126.5) (m, 2F), À128.2 ~(À128.5) (m, 1F); IR
(neat): n=2963, 2934, 2863, 1698, 1604, 1512, 1456, 1353,
1317, 1238, 1200, 1155, 1143, 1108, 1074 cmÀ1; MS (EI,
70 eV): m/z (%)=532 (M+, 100); HR-MS: m/z=532.1073,
calcd. for C21H17F13O (M+): 532.1072.
(m, 8H, CH2 ꢂ4), 0.85 (t, J=6.8 Hz, 3H, CH3);13C NMR
(75 MHz, CDCl3): d=193.4, 152.5, 146.0 (dt, J1 =260.2 Hz,
J2 =28.9 Hz), 144.5, 138.2, 129.1, 128.9, 128.8, 116.6–116.2
(m), 35.1 (d, J=1.5 Hz), 34.6, 31.4, 28.7, 26.6, 22.4, 21.2,
13.9; 19F NMR (282 MHz, CDCl3): d=À80.9 ~(À81.0) (m,
3F), À118.6 ~(À118.8) (m, 2F), À127.5 ~(À127.6) (m, 2F),
À128.6 ~(À129.0) (m, 1F); IR (neat): n=2961, 2930, 2859,
2710, 1696, 1634, 1515, 1460, 1351, 1309, 1228, 1187, 1120,
1074, 1032 cmÀ1; MS (EI, 70 eV): m/z (%)=456 (M+, 12.94),
43 (100); HR-MS: m/z=456.1698, calcd. for C22H24F8O
(M+): 456.1699.
4-Hexyl-6,7,7,8,8,9,9,9-octafluoro-2-phenyl-2(E),5(Z)-non-
4-Hexyl-6,7,7,8,8,9,9,9-octafluoro-2-(4-fluorophenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2m]: The reaction of Z-1m
(93.1 mg, 0.20 mmol), NaI (59.9 mg, 0.40 mmol), and TBSCl
adienal [(E,Z)-2k]:
The reaction of Z-1k (89.0 mg,
0.20 mmol), NaI (60.7 mg, 0.41 mmol), and TBSCl (45.8 mg,
0.30 mmol) in MeCN (2.0 mL) at room temperature for 2 h
afforded (E,Z)-2k (eluent: 30–608C petroleum ether/ethyl
acetate=80/1 to 60/1) as an oil; yield: 60.2 mg (68%);
(E,Z)/ACHTUNGTRENNUNG
(Z,Z)=98/2 determined by 1H NMR analysis of the
1
crude product; H NMR (300 MHz, CDCl3): d=9.65 (s, 1H,
CHO), 7.47–7.34 (m, 3H, Ar-H), 7.15–7.06 (m, 2H, Ar-H),
6.48 (d, J=10.2 Hz, 1H, CH=), 5.56 (dd, J1 =33.0 Hz, J2 =
9.9 Hz, 1H, CH=), 3.79–3.62 (m, 1H, CH), 1.59–1.44 (m,
2H, CH2), 1.32–1.08 (m, 8H, CH2 ꢂ4), 0.85 (t, J=6.6 Hz,
3H, CH3); 13C NMR (75 MHz, CDCl3, a signal at 29 ppm
belongs to residual petroleum ether): d=193.2, 152.7, 144.6,
131.8, 129.0, 128.45, 128.38, 116.4–116.0 (m), 35.1 (d, J=
1.1 Hz), 34.5, 31.4, 28.7, 26.6, 22.5, 14.0; 19F NMR (282 MHz,
CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.6 ~(À118.8) (m,
2F), À127.4 ~(À127.5) (m, 2F), À128.5 ~(À128.8) (m, 1F);
IR (neat): n=3060, 2930, 2859, 2710, 1694, 1635, 1601, 1497,
1467, 1445, 1350, 1231, 1156, 1120, 1078, 1028 cmÀ1; MS (EI,
70 eV): m/z (%)=442 (M+, 100); HR-MS: m/z=442.1541,
calcd. for C21H22F8O (M+): 442.1543.
(45.7 mg, 0.30 mmol) in MeCN (2.0 mL) at room tempera-
ture for 2 h afforded (E,Z)-2m (eluent: 30–608C petroleum
ether/ethyl acetate=100/1 to 80/1 to 60/1) as an oil; yield:
1
64.2 mg (69%); (E,Z)/
G
1
analysis of the crude product; H NMR (300 MHz, CDCl3):
d=9.63 (s, 1H, CHO), 7.17–7.04 (m, 4H, Ar-H), 6.49 (d, J=
10.2 Hz, 1H, CH=), 5.57 (dd, J1 =33.0 Hz, J2 =9.9 Hz, 1H,
CH=), 3.77–3.60 (m, 1H, CH), 1.63–1.47 (m, 2H, CH2),
1.32–1.11 (m, 8H, CH2 ꢂ4), 0.85 (t, J=6.6 Hz, 3H, CH3);
13C NMR (75 MHz, CDCl3): d=193.0, 162.7 (d, J=
246.5 Hz), 153.2, 146.1 (dt, J1 =259.1 Hz, J2 =28.6 Hz), 143.7,
130.9 (d, J=7.5 Hz), 127.6 (d, J=3.4 Hz), 116.2–115.9 (m),
115.6 (d, J=21.2 Hz), 35.1 (d, J=1.7 Hz), 34.5, 31.4, 28.7,
26.6, 22.5, 13.9; 19F NMR (282 MHz, CDCl3): d=À80.8 ~
(À80.9) (m, 3F), À113.1 ~(À113.3) (m, 1F), À118.6 ~
(À118.8) (m, 2F), À127.4 ~(À127.6) (m, 2F), À128.4 ~
(À128.8) (m, 1F); IR (neat): n=2932, 2860, 2712, 1697,
1604, 1512, 1468, 1351, 1228, 1187, 1159, 1121, 1096,
1072 cmÀ1; MS (EI, 70 eV): m/z (%)=460 (M+, 100); HR-
MS: m/z=460.1428, calcd. for C21H21F9O (M+): 460.1449.
4-Butyl-6,7,7,7-tetrafluoro-2-phenyl-2(E),5(Z)-heptadienal
[(E,Z)-2n]: The reaction of Z-1n (314.0 mg, 1.0 mmol), NaI
(303.1 mg, 2.0 mmol), and TBSCl (228.1 mg, 1.5 mmol) in
MeCN (10 mL) at room temperature for 2 h afforded (E,Z)-
4-Hexyl-6,7,7,8,8,9,9,9-octafluoro-2-(4-methylphenyl)-
2(E),5(Z)-nonadienal [(E,Z)-2l]:
The reaction of Z-1l
(90.8 mg, 0.20 mmol), NaI (60.8 mg, 0.41 mmol), and TBSCl
(46.1 mg, 0.31 mmol) in MeCN (2.0 mL) at room tempera-
ture for 2 h afforded (E,Z)-2l (eluent: 30–608C petroleum
ether/ethyl acetate=80/1 to 60/1) as an oil; yield: 72.8 mg
1
(80%); (E,Z)/
G
1
2n (eluent: 30–608C petroleum ether/ethyl ether=100/1 to
of the crude product; H NMR (300 MHz, CDCl3): d=9.63
(s, 1H, CHO), 7.23 (d, J=7.8 Hz, 2H, Ar-H), 7.00 (d, J=
8.1 Hz, 2H, Ar-H), 6.45 (d, J=9.9 Hz, 1H, CH), 5.57 (dd,
J1 =32.7 Hz, J2 =10.2 Hz, 1H, CH=), 3.82–3.65 (m, 1H,
CH), 2.37 (s, 3H, CH3), 1.66–1.45 (m, 2H, CH2), 1.32–1.10
60/1 to petroleum ether/ethyl acetate=30/1) as an oil; yield:
1
194.1 mg (62%); (E,Z)/
(Z,Z)=98/2 determined by H NMR
1
analysis of the crude product; H NMR (300 MHz, CDCl3):
d=9.63 (s, 1H, CHO), 7.48–7.31 (m, 3H, Ar-H), 7.18–7.06
1354
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
(m, 2H, Ar-H), 6.47 (d, J=9.9 Hz, 1H, CH=), 5.51 (dd, J1 =
33.3 Hz, J2 =9.9 Hz, 1H, CH=), 3.74–3.57 (m, 1H, CH),
1.62–1.45 (m, 2H, CH2), 1.30–1.06 (m, 4H, CH2 ꢂ2), 0.83 (t,
J=6.6 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): d=193.1,
152.9, 146.0 (dq, J1 =258.9 Hz, J2 =38.4 Hz), 144.5, 131.9,
129.0, 128.4, 128.3, 118.2 (qd, J1 =269.7 Hz, J2 =42.0 Hz),
113.4–113.1 (m), 34.7 (d, J=1.7 Hz), 34.2, 28.8, 22.2, 13.6;
19F NMR (282 MHz, CDCl3): d=À72.9 (d, J=10.7 Hz, 3F),
À133.6 (dq, J1 =33.3 Hz, J2 =11.6 Hz, 1F); IR (neat): n=
2960, 2933, 2861, 2709, 1696, 1636, 1497, 1467, 1444, 1362,
1342, 1199, 1145, 1080 cmÀ1; MS (EI, 70 eV): m/z (%)=314
(M+, 31.64), 105 (100); HR-MS: m/z=314.1297, calcd. for
C17H18F4O (M+): 314.1294.
7a: oil; 1H NMR (300 MHz, CDCl3): d=7.45–7.31 (m,
5H, Ar-H), 7.27 (t, J=1.4 Hz, 1H, CH=), 4.10–3.83 (m, 2H,
CH2O), 2.62 (brs, 1H, OH), 2.41–2.21 (m, 2H, CH2), 1.64–
1.48 (m, 2H, CH2), 1.45–1.28 (m, 2H, CH2), 0.91 (t, J=
7.4 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): d=173.2,
148.2, 136.7, 135.0, 128.8, 128.5, 125.3, 89.7, 67.3, 29.4, 25.0,
22.2, 13.7; IR (neat): n=3419, 2967, 2930, 2871, 1754, 1493,
1449, 1077, 1037 cmÀ1; MS (EI, 70 eV): m/z (%)=215
([MÀCH2OH]+, 100); MS (ESI): m/z (%)=247 (M+ +H,
100); HR-MS: m/z=247.1332, calcd. for C15H19O3 (M+ +H):
247.1329.
1
(E)-8a: oil; H NMR (300 MHz, CDCl3): d=9.68 (s, 1H,
CHO), 7.47–7.33 (m, 3H, Ar-H), 7.18–7.11 (m, 2H, Ar-H),
6.71 (d, J=10.5 Hz, 1H, CH=), 3.74 (s, 3H, CH3O), 3.55–
3.43 (m, 1H, CH), 1.92–1.75 (m, 1H, CH2), 1.71–1.54 (m,
1H, CH2), 1.31–1.07 (m, 4H, CH2 ꢂ2), 0.83 (t, J=6.9 Hz,
3H, CH3); 13C NMR (75 MHz, CDCl3): d=193.2, 172.9,
151.3, 145.0, 131.8, 129.3, 128.4, 128.3, 52.3, 45.6, 32.4, 28.9,
22.2, 13.7; IR (neat): n=2956, 2860, 1737, 1696, 1636, 1497,
1444, 1197, 1168, 1080 cmÀ1; MS (EI, 70 eV): m/z (%) 260
(M+, 21.4), 115 (100); HR-MS: m/z=260.1414, calcd. for
C16H20O3 (M+): 260.1412.
4-Methyl-2-phenyl-5,5,5-trifluoro-2(E)-pentenal [(E)-2q]:
The reaction of 1q (411.1 mg, 1.8 mmol), NaI (541.8 mg,
2-Hydroxymethyl-2-phenyl-4-[2,3,3,4,4,5,5,5-octafluoro-
1(Z)-pentenyl]-2,5-dihydrofuran [(Z)-10a]: The reaction of
Z-1o (140.5 mg, 0.36 mmol), NaI (210.8 mg, 1.4 mmol), and
3.6 mmol), and TBSCl (410.4 mg, 2.7 mmol) in MeCN
(15 mL) at room temperature for 2 h afforded E-2q as
a liquid (eluent: 30–608C petroleum ether/ethyl acetate=
100/1 to 60/1); yield: 226.4 mg (55%) (there is an unidenti-
fied product but is not the stereoisomer in the crude prod-
uct); 1H NMR (300 MHz, CDCl3): d=9.67 (s, 1H, CHO),
7.54–7.27 (m, 3H, Ar-H), 7.24–7.04 (m, 2H, Ar-H), 6.57 (d,
J=10.5 Hz, 1H, CH=), 3.44–3.22 (m, 1H, CH), 1.25 (d, J=
6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): d=192.7,
146.7, 146.5–146.2 (m), 131.4, 128.9, 128.6, 126.4 (q, J=
277.9 Hz), 38.8 (q, J=28.3 Hz), 13.8–13.5 (m); 19F NMR
(282 MHz, CDCl3): d=À71.4 (d, J=8.5 Hz); IR (neat): n=
2713, 1701, 1497, 1461, 1445, 1386, 1369, 1350, 1259, 1226,
1176, 1132, 1086, 1055, 1019 cmÀ1; MS (EI, 70 eV): m/z
(%)=228 (M+, 100); HR-MS: m/z=228.0762, calcd. for
C12H11F3O (M+): 228.0762.
TBSCl (162.5 mg, 1.08 mmol) in MeCN (4 mL) at room
temperature for 2 h afforded Z-10a (eluent: petroleum
ether/ethyl acetate=10/1 to 5/1 for first round; DCM to
DCM/ethyl acetate=5/1 for second round)as an oil; yield:
95.1 mg (68%); 1H NMR (300 MHz, CDCl3): d=7.42–7.25
(m, 5H, Ar-H), 6.36 (s, 1H, CH=), 6.26 (d, J=36.9 Hz, 1H,
CH=), 5.08 (d, J=12.6 Hz, 1H, CH2), 4.97 (d, J=12.9 Hz,
1H, CH2), 3.91–3.73 (m, 2H, CH2), 2.41 (dd, J1 =8.7 Hz, J2 =
4.5 Hz, 1H, OH); 13C NMR (75 MHz, CDCl3): d=141.0,
134.9 (d, J=4.8 Hz), 131.7 (d, J=4.1 Hz), 128.6, 127.7, 124.9,
107.5–107.1 (m), 94.2, 75.0 (d, J=7.7 Hz), 68.5; 19F NMR
(282 MHz, CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.4 ~
(À118.6) (m, 2F), À125.5 ~(À125.8) (m, 1F), À127.2 ~
(À127.3) (m, 2F); IR (neat): n=3426, 3072, 2921, 2868,
1687, 1491, 1449, 1364, 1230, 1155, 1120, 1043 cmÀ1; MS (EI,
70 eV): m/z (%)=357 ([MÀCH2OH]+, 100); elemental anal-
ysis calcd. for C16H12F8O2 (MW=388): C 49.50, H 3.12;
found: C 49.49, H 3.25.
Control Experiments
3-Butyl-5-(hydroxymethyl)-5-phenyl-2(5H)-furanone
(7a)
and methyl 2-butyl-5-oxo-4-phenyl-3(Z)-pentenoate [(E)-
8a]:
The reaction of 5a (51.5 mg, 0.20 mmol), NaI (60.1 mg,
0.4 mmol), and TBSCl (46.1 mg, 0.3 mmol) in MeCN
(2.0 mL) at room temperature for 100 min afforded (eluent:
petroleum ether/ethyl acetate=40/1 to 12/1 to 10/1 to 3/1)
7a; yield: 17.4 mg (36%) and (E)-8a;yield: 11.5 mg (22%)
1
[yields determined by H NMR analysis of crude product:
7a (47%)+8a (27%)+9a (6%)].
Reaction of (Z)-11a to Afford (E,Z)-2a: The reaction of
Z-11a (79.8 mg, 0.15 mmol), NaI (45.8 mg, 0.3 mmol), H2O
(13.5 mL, 0.75 mmol), and TBSCl (34.1 mg, 0.225 mmol) in
MeCN (1.5 mL) at room temperature for 2 h afforded
(E,Z)-2a (eluent: petroleum ether/ethyl ether=60/1) as an
1
oil; yield: 43.7 mg (70%); H NMR (300 MHz, CDCl3): d=
9.64 (s, 1H, CHO), 7.48–7.32 (m, 3H, Ar-H), 7.16–7.04 (m,
2H, Ar-H), 6.48 (d, J=9.9 Hz, 1H, CH=), 5.58 (dd, J1 =
32.9 Hz, J2 =10.1 Hz, 1H, CH=), 3.80–3.62 (m, 1H, CH),
1.64–1.45 (m, 2H, CH2), 1.35–1.03 (m, 4H, CH2 ꢂ2), 0.94–
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1355

FULL PAPERS
Rong Zeng et al.
0.75 (m, 3H, CH3); 13C NMR (75 MHz, CDCl3): d=193.1,
152.6, 144.7, 131.9, 129.0, 128.44, 128.37, 116.4–116.0 (m),
35.1 (d, J=2.4 Hz), 34.3, 28.8, 22.2, 13.7; 19F NMR
(282 MHz, CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.5 ~
(À118.8) (m, 2F), À127.3 ~(À127.6) (m, 2F), À128.5 ~
(À128.8) (m, 1F); IR (neat): n=2961, 2933, 2862, 2710,
1698, 1497, 1361, 1221, 1187, 1120, 1079 cmÀ1; MS (EI,
70 eV): m/z (%)=414 (M+, 100); HR-MS: m/z=414.1236,
calcd. for C19H18F8O: 414.1230.
ether/ethyl acetate=80/1) as an oil; yield: 227.6 mg (69%);
1H NMR (300 MHz, CDCl3): d=9.62 (s, 1H, CHO), 7.47–
7.31 (m, 3H, Ar-H), 7.18–7.06 (m, 2H, Ar-H), 5.67–5.46 (m,
1H, CH=), 1.63–1.42 (m, 2H, CH2), 1.31–1.07 (m, 4H,
1
CH2 ꢂ2), 0.82 (t, J=6.8 Hz, 3H, CH3); H NMR [300 MHz,
CDCl3, the following signals are discernible for (E,Z)-2a]
d=6.52–6.42 (m, 0.38H, CH=), 3.79–3.62 (m, 0.16H, CH);
due to the presence of two D-incorporation, the 13C NMR
(75 MHz, CDCl3) spectra are very complicated. These spec-
tra are attached in the Supporting Information; 19F NMR
(282 MHz, CDCl3): d=À81.0 ~(À81.1) (m, 3F), À118.6 ~
(À118.9) (m, 2F), À127.5 ~(À127.7) (m, 2F), À128.8 ~
(À129.2) (m, 1F); IR (neat): n=2961, 2933, 2862, 2715,
1698, 1496, 1361, 1230, 1187, 1121 cmÀ1; MS (EI, 70 eV): m/z
(%)=417 ([M(D2)+ +1], 20.7), 416 ([M(D2)]+ or [M(D1)+ +
1], 100), 415 ([M(D1)]+ or [M+ +1], 66.5); HR-MS: m/z=
416.1354, calcd. for C19H16D2F8O: 416.1355.
Reaction of (Z)-1a-D to Afford (E,Z)-2a-D: The reaction
of Z-1a-D (83.8 mg, 0.2 mmol), NaI (60.8 mg, 0.4 mmol),
and TBSCl (45.1 mg, 0.3 mmol) in MeCN (2 mL) at room
Condensation Reaction of (E,Z)-4a, (E)-4b
4-Butyl-2-phenyl-6,7,7,7-tetrafluoro-hepta-2(E),5(Z)-dienal
(2,4-Dinitrophenyl)hydrazone [(E,Z)-4a] To a dried flask
equipped with an addition funnel were added (2,4-dinitro-
phenyl)hydrazine (91.8 mg, 0.46 mmol), concentrated H2SO4
temperature for 2 h afforded (E,Z)-2a-D (eluent: petroleum
ether to petroleum ether/ethyl ether=60/1) as an oil; yield:
52.8 mg (63%); 1H NMR (300 MHz, CDCl3): d=7.47–7.33
(m, 3H, Ar-H), 7.15–7.06 (m, 2H, Ar-H), 6.48 (d, J=
10.2 Hz, 1H, CH=), 5.56 (dd, J1 =32.9 Hz, J2 =9.8 Hz, 1H,
CH=), 3.79–3.62 (m, 0.97H, CH), 1.65–1.45 (m, 2H, CH2),
1.35–1.10 (m, 4H, CH2 ꢂ2), 0.83 (t, J=6.9 Hz, 3H, CH3);
1H NMR [300 MHz, CDCl3, the following signal is discerni-
ble for (E,Z)-2a]: d=9.64 (s, 0.37H, CHO); 13C NMR
(75 MHz, CDCl3): d=193.0, 152.5, 146.1 (dt, J1 =259.4 Hz,
J2 =29.1 Hz), 144.7, 131.9, 129.1, 128.5, 128.4, 116.4–116.0
(m), 35.1 (d, J=1.7 Hz), 34.3, 28.8, 22.2, 13.7; 13C NMR
[75 MHz, CDCl3, the following signal is discernible for
(E,Z)-2a-D]: d=192.7 (t, J=26.5 Hz); 19F NMR (282 MHz,
CDCl3): d=À80.8 ~(À80.9) (m, 3F), À118.5 ~(À118.8) (m,
2F), À127.4 ~(À127.5) (m, 2F), À128.5 ~(À128.8) (m, 1F);
IR (neat): n=2964, 2932, 2860, 1691, 1629, 1495, 1471, 1447,
1352, 1227, 1182, 1156, 1117, 1069, 1034 cmÀ1; MS (EI,
70 eV): m/z (%)=415 ([M+1]+, 100), 414 (M+, 62.7); HR-
MS: m/z=415.1294, calcd. for C19H17DF8O: 415.1293.
(0.75 mL), EtOH (7 mL), and H2O (16 mL) sequentially.
Then (E,Z)-2n (155.2 mg, 0.5 mmol) in EtOH (8 mL) was
added dropwise within 8 min at room temperature. The re-
sulting mixture was stirred at room temperature for 1.5 h,
extracted with ethyl acetate (50 mLꢂ3), washed with brine
(30 mLꢂ2), and dried over anhydrous Na2SO4. Evaporation
and column chromatography on silica gel (eluent: petroleum
ether/ethyl acetate/dichloromethane=10/1/10) afforded
(E,Z)-4a as an orange solid; yield: 222.9 mg (97%); mp
Reaction of (Z)-1a with 10 equiv. D2O to Afford (E,Z)-
2a-D’: The reaction of (Z)-1a (331.3 mg, 0.8 mmol), NaI
(241.5 mg, 1.6 mmol), D2O (145 mL, 8 mmol), and TBSCl
(181.7 mg, 1.2 mmol) in MeCN (8 mL) at room temperature
for 2 h afforded (E,Z)-2a-D’ (eluent: 30–608C petroleum
1
183.4–184.98C (DCM/hexane); H NMR (300 MHz, CDCl3):
d=11.19 (s, 1H), 9.08 (d, J=2.4 Hz, 1H), 8.17 (dd, J1 =
1356
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358

FULL PAPERS
Sodium Iodide/tert-ButylACTHNUTRGNEUG(N dimethyl)silyl Chloride-Induced Isomerization
9.5 Hz, J2 =2.3 Hz, 1H, Ar-H), 7.96 (s, 1H, Ar-H), 7.56–7.36
(m, 4H, Ar-H), 7.21 (d, J=7.2 Hz, 2H, Ar-H), 5.99 (d, J=
10.5 Hz, 1H, CH=), 5.47 (dd, J1 =33.3 Hz, J2 =9.8 Hz, 1H,
CH=), 3.58–3.38 (m, 1H, CH), 1.64–1.36 (m, 2H, CH2),
1.34–1.06 (m, 4H, CH2 ꢂ2), 0.84 (t, J=6.5 Hz, 3H, CH3);
13C NMR (75 MHz, CDCl3): d=151.0, 145.5 (dq, J1 =
257.9 Hz, J2 =38.4 Hz), 144.8, 141.4, 139.8, 138.2, 134.5,
130.0, 129.2, 128.3, 128.0, 123.2, 118.3 (qd, J1 =270.1 Hz, J2 =
41.0 Hz), 114.3–113.8 (m), 34.6, 28.9, 22.2, 13.8; 19F NMR
(282 MHz, CDCl3): d=À72.9 (d, J=11.8 Hz, 3F), À134.3 ~
À134.7 (m, 1F); IR (neat): n=3293, 1619, 1596, 1578, 1516,
1500, 1339, 1325, 1305, 1260, 1214, 1146, 1072 cmÀ1; MS (EI,
70 eV): m/z (%)=494 (M+, 30.04), 311 (100); elemental
analysis calcd. for C23H22F4N4O4: C 55.87, H 4.48, N 11.33;
found: C 55.88, H 4.70, N 11.22.
Acknowledgements
Financial supports from National Natural Science Founda-
tion (No. 21232006) and National Basic Research Program
of China (No. 2011CB808700). Shengming Ma is a Qiu Shi
Adjunct Professor at Zhejiang University. We thank Mr. Tao
Cao in this group for reproducing the results for synthesis of
compounds 2c, 2f, and 2j.
References
[1] a) P. Gallezot, D. Richard, Catal. Rev.-Sci. Eng. 1998,
40, 81; b) S. Burt, Int. J. Food Microbiol. 2004, 94, 223;
c) J. Cocchiara, C. S. Letizia, J. Lalko, A. Lapczynski,
A. M. Api, Food Chem. Toxicol. 2005, 43, 867.
[2] a) D. Almasi, D. A. Alonso, C. Najera, Tetrahedron:
Asymmetry 2007, 18, 299; b) S. B. Tsogoeva, Eur. J.
Org. Chem. 2007, 1701; c) J. L. Vicario, D. Badꢃa, L.
Carrillo, Synthesis 2007, 2065; d) D. Enders, C. Gron-
dal, M. R. M. Hꢄttl, Angew. Chem. 2007, 119, 1590;
Angew. Chem. Int. Ed. 2007, 46, 1570; e) X. Yu, W.
Wang, Org. Biomol. Chem. 2008, 6, 2037.
4-Methyl-2-phenyl-5,5,5-trifluoropent-2(E)-enal (2,4-dini-
trophenyl)hydrazone [(E)-4b]: To a dried flask equipped
with an addition funnel were added (2,4-dinitrophenyl)hy-
drazine (180.1 mg, 0.92 mmol), concentrated H2SO4
[3] For the oxidation of allylic alcohol, see: G. Tojo, M.
Fernꢅndez, in: Oxidation of Alcohols to Aldehydes and
Ketones: A Guide to Current Common Practice, (Ed.:
G. Tojo), Springer, Berlin, 2006, pp 1–375.
[4] For the Peterson olefinations, see: D. J. Ager, Synthesis
1984, 384.
[5] For the formylation reaction, see: a) B. Breit, Acc.
Chem. Res. 2003, 36, 264; b) H. Neumann, A. Sergeev,
M. Beller, Angew. Chem. 2008, 120, 4965; Angew.
Chem. Int. Ed. 2008, 47, 4887.
(1.5 mL), EtOH (20 mL), and H2O (35 mL) sequentially.
Then (E)-q (226.4 mg, 1.0 mmol) in EtOH (10 mL) was
added dropwise within 10 min at room temperature. The re-
sulting mixture was stirred at room temperature for 1.5 h,
extracted with ethyl acetate (50 mL ꢂ 3), washed with brine
(30 mL ꢂ 2), and dried over anhydrous Na2SO4. Evaporation
and column chromatography on silica gel (eluent: 30–608C
petroleum ether/ethyl acetate=10/1 to 5/1 to DCM) afford-
ed (E)-4b as an orange solid; yield: 370.6 mg (100%); mp
239–2418C (DCM/hexane); 1H NMR (300 MHz, THF-d8):
d=11.34 (s, 1H, CH=N), 9.00 (s, 1H, NH), 8.35 (s, 1H, Ar-
H), 8.24 (d, J=8.7 Hz, 1H, Ar-H), 7.65–7.38 (m, 4H, Ar-H),
7.38–7.18 (m, 2H, Ar-H), 6.17 (d, J=9.9 Hz, 1H, CH=),
3.35–3.08 (m, 1H, CH), 1.26 (d, J=6.6 Hz, 3H, CH3);
13C NMR (75 MHz, THF-d8): d=152.7, 146.3, 145.0, 139.7,
136.3, 135.3 (d, J=2.3 Hz), 131.4, 131.0, 130.8, 129.8, 129.5,
128.7 (q, J=277.9 Hz), 124.0, 117.9, 40.2 (q, J=27.9 Hz),
14.9 (d, J=2.6 Hz); 19F NMR (282 MHz, THF-d8): d=
À71.7; IR (neat): n=3294, 3093, 1618, 1515, 1504, 1338,
1325, 1262, 1188, 1138, 1083, 1017 cmÀ1; MS (EI, 70 eV): m/z
(%)=408 (M+, 52.0), 311 (100); elemental analysis calcd.
for C18H15F3N4O4: C 52.95, H 3.70, N 13.72; found: C 52.67,
H 3.81, N 13.72.
[6] For the Wittig olefination reactions, see: B. E. Maryan-
off, A. B. Reitz, Chem. Rev. 1989, 89, 863.
[7] For the aldol condensations and Mannich reactions,
see: a) P. R. Mackie, C. E. Foster, in: Comprehensive
Organic Group Transformations II, (Eds.: A. R. Ka-
tritzky, R. J. K. Taylor, K. Jones), Elsevier, Dordrecht,
2004, vol. 3, pp 59–97; b) R. Brettle, in: Comprehensive
Organic Chemistry: The Synthesis and Reactions of Or-
ganic Compounds, (Eds.: D. Barton, W. D. Ollis), Per-
gamon, Oxford, 1979, vol. 1, pp 979–992; c) R. C.
Larock, Comprehensive Organic Transformations: A
Guide to Functional Group Preparations, Wiley-VCH,
Weinheim, 1999, pp 317–340.
[8] For the Saegusa oxidation, see: a) Y. Ito, T. Hirao, T.
Saegusa, J. Org. Chem. 1978, 43, 1011; b) R. C. Larock,
T. R. Hightower, G. A. Kraus, P. Hahn, D. Zhang, Tet-
rahedron Lett. 1995, 36, 2423.
[9] For the palladium-mediated dehydrogenation, see: J.
Muzart, Eur. J. Org. Chem. 2010, 3779.
[10] a) E. W. Colvin, Silicon in Organic Synthesis, Butter-
worths, London, 1984, pp 288; b) A. H. Schmidt, Aldri-
chimica Acta 1981, 14, 31.
[11] a) S. Irifune, T. Kibayashi, Y. Ishii, M. Ogawa, Synthesis
1988, 366; b) T. Kanai, S. Irifune, Y. Ishii, M. Ogawa,
Synthesis 1989, 283; c) N. Kamiya, Y. Chikami, Y. Ishii,
Synlett 1990, 675.
[12] For a review on the reaction of allenols, see: Y.-Q.
Deng, Z.-H. Gu, S.-M. Ma, Chin. J. Org. Chem. 2006,
26, 1468.
Adv. Synth. Catal. 2014, 356, 1343 – 1358
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1357

FULL PAPERS
Rong Zeng et al.
[13] For selected reviews on the reactions of allenes, see:
a) Modern Allene Chemistry, (Eds.: N. Krause, A. S. K.
Hashmi), Wiley-VCH, Weinheim, 2004; b) R. Zimmer,
C. U. Dinesh, E. Nandanan, F. A. Khan, Chem. Rev.
2000, 100, 3067; c) A. Hoffmann-Rçder, N. Krause,
Angew. Chem. 2002, 114, 3057; Angew. Chem. Int. Ed.
2002, 41, 2933; d) L. K. Sydnes, Chem. Rev. 2003, 103,
1133; e) S. Ma, Chem. Rev. 2005, 105, 2829; f) S. Ma,
Aldrichimica Acta 2007, 40, 91; g) B. Alcaide, P. Al-
mendros, T. M. del Campo, Chem. Eur. J. 2010, 16,
5836; h) R. W. Bates, V. Satcharoen, Chem. Soc. Rev.
2002, 31, 12; i) S. Ma, Acc. Chem. Res. 2003, 36, 701;
j) S. Ma, in: Topics in Organometallic Chemistry, (Ed.:
J. Tsuji), Springer Verlag, Heidelberg, Vol. 14, 2005;
pp 183–210; k) S. Ma, Acc. Chem. Res. 2009, 42, 1679;
l) T. Lechel, F. Pfrengle, H.-U. Reissig, R. Zimmer,
ChemCatChem 2013, 5, 2100.
servations [> 2s(I)] 4017, parameters: 638. CCDC
937725 contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[17] M. Petit, C. Aubert, M. Malacria, Tetrahedron 2006, 62,
10582.
[18] (E)-4b: C18H15F3N4O4, MW=408.34, triclinic, space
group P À1, final R indices [I> 2s(I)], R1=0.0817,
wR2=0.2167; R indices (all data), R1=0.1102, wR2=
0.2415; a=6.7914 (5) ꢆ, b=7.6553 (6) ꢆ, c=18.2337
(16) ꢆ, a=96.436 (7)8, b=99.617 (7)8, g=99.386 (6)8,
V=912.63 (13) ꢆ3, T=170 (2) K, Z=2, reflections col-
lected/unique 5940/3327 (Rint =0.0235), number of ob-
servations [> 2s(I)] 2380, parameters: 280. CCDC
937724 contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[19] For iron-catalyzed oxidation reaction developed by our
group, see: a) S. Ma, J. Liu, S. Li, B. Chen, J. Cheng, J.
Kuang, Y. Liu, B. Wan, Y. Wang, J. Ye, Q. Yu, W.
Yuan, S. Yu, Adv. Synth. Catal. 2011, 353, 1005; b) J.
Liu, X. Xie, S. Ma, Synthesis 2012, 1569; c) S. Gao, Y.
Liu, S. Ma, Beilstein J. Org. Chem. 2011, 7, 396; d) Y.
Liu, S. Ma, Chin. J. Chem. 2012, 30, 29.
[14] Z. Ma, R. Zeng, Y. Yu, S. Ma, Tetrahedron Lett. 2009,
50, 6472.
[15] D. Neuhaus, M. P. Williamson, The Nuclear Overhauser
Effect in Structural and Conformational Analysis, 2nd
edn.; Wiley-VCH, New York, 2000. See the Supporting
Information for the spectrum.
[16] ACHTUNGTRENNUNG(E,Z)-4a: C23H22F4N4O4, MW=494.45, triclinic, space
group P À1, final R indices [I> 2s(I)], R1=0.1005,
wR2=0.3061; R indices (all data), R1=0.1679, wR2=
0.3824; a=9.7451 (7) ꢆ, b=10.7825 (7) ꢆ, c=23.1668
(17) ꢆ, a=83.034 (6)8, b=86.977 (6)8, g=87.499 (6)8,
V=2411.2 (3) ꢆ3, T=293 (2) K, Z=4, reflections col-
lected/unique 15383/8490 (Rint =0.0320), number of ob-
[20] M. Petit, C. Aubert, M. Malacria, Tetrahedron 2006, 62,
10582.
[21] M. E. Piotti, H. Alper, J. Org. Chem. 1997, 62, 8484.
1358
asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 1343 – 1358