Iron(III) Porphyrin Catalyzed Olefination of Aldehydes with 2,2,2-Trifluorodiazoethane (CF3CHN2)

Article abstract of DOI:10.1002/ejoc.201800325

An efficient method for the iron(III) porphyrin catalyzed olefination of various aldehydes with 2,2,2-trifluorodiazoethane under neutral conditions is described. This transformation was shown to have a broad substrate scope and provide the corresponding CF₃-substituted alkenes in good yields. The number of equivalents of PPh₃ that is used in this reaction is crucial to the success of the olefination process. This reaction is a useful supplement to the synthetic applications of CF₃CHN₂.

Full text of DOI:10.1002/ejoc.201800325

A Journal of
Accepted Article
Title: Iron(III) Porphyrin Complex-Catalyzed Olefination of Aldehydes
with 2,2,2-trifluorodiazoethane (CF3CHN2)
Authors: Chao Liu, Yang Lu, Yong Guo, Qing-Yun Chen, and Chuyu
Huang
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201800325
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10.1002/ejoc.201800325
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Iron(III) Porphyrin Complex-Catalyzed Olefination of Aldehydes
with 2,2,2-trifluorodiazoethane (CF3CHN2)
Yang Lu, Chuyu Huang, Chao Liu*, Yong Guo, Qing-Yun Chen*
Dedication ((optional))
substrates with tedious functional group interconversion and
costly CF3 reagents. As comparison, the classic olefination
approaches of various aldehydes by Julia-Kocienski,[7] Horner[8]
or Wittig[9] olefination reactions generate the target products with
good functional group compatability by the use of relative
inexpensive sources of CF3 (Figure 1, pathway c). However,
they often involve multistep synthesis of corresponding ylide
precursors, and require the use of a strong base to achieve the
desired reactions, which may result in the formation of some by-
products and limit the substrate scope of the reaction.
Abstract: An efficient iron(III) porphyrin complex-catalyzed
olefination of various aldehydes with 2,2,2-trifluorodiazoethane
(CF3CHN2) under neutral conditions is described for the first time,
providing good yields of the corresponding CF3-substituted alkenes
with broad substrate scope. The equivalents of PPh3 used have a
key role in the olefination process. This reaction is a useful
supplement to the synthetic application of CF3CHN2.
2,2,2-Trifluorodiazoethane (CF3CHN2) is a very practical
and versatile CF3-bearing reagent from cheap and readily
available trifluoroethylamine hydrochloride and sodium nitrite[10]
and has found regular application in organic synthetic chemistry.
Its main reactivities include CF3CH:-carbene insertion,
cyclopropanation, dipolar cycloadditions, C-nucleoplilic addition,
Introduction
Fluorine-containing functional groups have played an
increasing importance role in both medical and material science
due to their unique properties. Among them, trifluoromethyl
(CF3) moiety undoubtedly is one of the most popular fluorine-
containing functional groups and has attracted much attention
since its introduction into biologically active compounds usually
could significantly improve their activity, lipophilicity and
metabolic stability.[1] Besides direct insertion of a CF3 group by
construction of C-CF3 bonds,[2] an efficient method for the
introduction of a CF3 group into organic scaffolds is to utilize
versatile CF3-bearing building blocks.[3] Specifically, 3,3,3-
trifluoropropenyl (CF3CH=CH) group is an important
trifluoromethylated building block and has found valuable
implications in organic synthesis.[3c] However, selective and
general synthetic methods of the preparation of CF3-substitued
alkenes remain relatively under-explored and highly desirable.
C-electrophilic
addition,
and
N-electrophilic
addition
reactions.[3c,11] Surprisingly, olefination of aldehydes with
CF3CHN2 to CF3-substituted alkenes has not been reported to
date. Inspired by the olefination of carbonyl compounds with
ethyl
diazoacetate
(N2CHCOOEt)
catalyzed
by
a
metalloporphyrin[12] and considering the similar electronic
property and stability of CF3CHN2 with N2CHCOOEt, we
reasoned that the key ylide intermediate Ph3P=CHCF3 may be
directly formed from the reaction of CF3CHN2 with PPh3 in the
presence of an appropriate metalloporphyrin catalyst, and the
consequent reaction with aldehydes can result in the desired
CF3-substituted alkenes (Scheme 1). Herein, we report our
results on the preparation of CF3-substituted alkenes via such an
approach.
Scheme 1. Proposed reaction pathway for the preparation of
CF3-substituted alkenes with CF3CHN2 under neutral conditions.
Figure 1. Three main strategies for the synthesis of CF3-
substituted alkenes.
Results and Discussion
So far, three main strategies have been successfully
developed for the synthesis of various CF3-substituted alkenes
(Figure 1). One is the transition metal mediated or catalyzed
trifluoromethylation of prefunctionalized vinyl derivatives by
cross-coupling reactions[4] or radical addition of corresponding
alkenes or alkynes[5] (Figure 1, pathway a). The second
approach is by palladium catalyzed trifluoromethylvinylation of
aryl halides (Figure 1, pathway b).[6] Although these methods
can efficiently result in construction of the desired CF3-
substituted alkenes, they commonly require prefunctionalized
We initiated this study by exploring the olefination of 4-
cyanobenzaldehyde (1a) with CF3CHN2 under catalytic amounts
of iron(III) meso-tetraphenylporphyrin chloride (FeTPPCl). To
our surprise, the olefination of 1a with CF3CHN2 led to the
desired product 2a in only 27% yield in addition to 48% yield of
by-product azine 3a, while the olefination of 1a with
N2CHCOOEt resulted in excellent yield of the corresponding
olefination product 4a under similar conditions (Scheme 2).
Interestingly, by-product azines were generated in high yields in
the case of both CF3CHN2 and N2CHCOOEt in the absence of a
catalyst, which is consistent with the reported results.[13] These
results demonstrate that CF3 group has profound effect on the
reactivity of CF3CHN2 in the olefination reaction of aldehydes.
[a]
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of
Organic Chemistry, University of Chinese Academy of Sciences,
Chinese Academy of Sciences, 345 Lingling Road, Shanghai
200032, China
E-mail: chaoliu@sioc.ac.cn; chenqy@sioc.ac.cn.
Supporting information for this article areavailable on the WWW
under https://doi.org/10.1002/ejoc.201800325.
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10.1002/ejoc.201800325
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Scheme 2. Comparision of olefination reactivity of 1a with
CF3CHN2 and N2CHCOOEt under similar reaction conditions.
In order to improve the yield of the desired product 2a and
suppress the by-product 3a, we supposed the catalyst might
play an important role and then evaluated several
metalloporphyrins for the olefination reaction. Among the
metalloporphyrins tested, iron(III) porphyrin complex exhibited
the highest catalytic activity, while the other metalloporphyrins
showed poor catalytic olefination activity (Table 1, entries 1-7).
Reaction temperatures had a limited influence on the formation
of the desired product 2a, but higher reaction temperatures were
beneficial for the suppression of the by-product 3a with 80 oC as
suitable reaction temperature (Table 1, entries 1,8,9). The
reactions resulted in no better yields of the desired product 2a in
the other reaction solvents, including THF, CH2Cl2, CHCl3,
ClCH2CH2Cl, CH3CN (Table 1, entries 10-14). Notably, the
equivalents of PPh3 had significant effect on the reaction, and
the desired olefin 2a improved smoothly with increasing the
equivalents of PPh3 used (Table 1, entries 1,15-20). When 4.0
equivalent of PPh3 was used, the yield of 2a was quantitative
and no formation of by-product azine 3a was observed (Table 1,
entry 19). Thus, the optimal reaction conditions can be identified
as FeTPPCl (2 mol%) as the catalyst, aldehyde (1.0 equiv),
CF3CHN2 (1.5 equiv) in toluene at 80 oC overnight (Table 1,
entry 19).
[a] Reactions were carried out with 1a (0.2 mmol, 1.0 equiv),
CF3CHN2 (1.5 equiv), PPh3, catalyst (2 mol %) in solvent (2 mL)
under Ar overnight. [b] Yields were determined by 19F NMR
spectroscopy with trifluorotoluene as an internal standard. [c]
The ratio of Z/E isomers was determined by 19F NMR
spectroscopy.
Table 1. Optimization of reaction conditions for olefination of 1a
with CF3CHN2
[a]
With the best reaction conditions in hand, we turned our
attention to explore the substrate scope of the FeTPPCl-
catalyzed olefination of aldehydes with CF3CHN2. As shown in
Scheme 3, a very wide range of aldehydes with either electron-
withdrawing, electron neutral or electron-donating groups were
applicable to the olefination reaction, providing good to excellent
yields of the desired CF3-substituted alkenes in most cases.
Sterically
demanding
benzaldehydes,
like
2,6-
dimethoxybenzaldehyde, 2,6-dichlorobenzaldehyde and 9-
enthraldehyde were also suitable for the olefination reaction (2o,
2m, 2s). Furthermore, heterocyclic aromatic aldehydes as well
as α,β-unsaturated aldehydes were subjected to the reaction,
leading to good yields of the desired products (2x-z, 2aa, 2v and
2w). Interestingly, bis-aldehydes could also be utilized in the
olefination reactions with the formation of good yields of the
corresponding bis-olefination products (2dd, 2ee, 2ff). In
addition, moderate yields were achieved for the olefination
reactions of aliphatic aldehydes (2bb, 2cc). Unfortunately, no
olefination products were observed in the case of ketones (2gg)
or aldehydes with active groups, including hydroxyl (2hh), amino
(2ii), or pyridinyl (2jj), groups, which might be due to the
coordination of these active groups with the catalyst. In addition,
a series of synthetically useful functional groups, including cyano
(2a-c), bromo (2d-e), fluoro (2f), chloro (2g), trifluoromethylthio
(2h), nitro (2i), methylsulphonyl (2j) and acetyloxy (2k) were well
tolerated under the reaction conditions. As for the stereo
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10.1002/ejoc.201800325
European Journal of Organic Chemistry
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selectivity of the products, E selectivity was observed in most
cases. However, Z selectivity was observed for 2b and 2p. The
detailed explanation needs for further investigation at this stage.
Notably, in some cases, the isolated yields of the desired olefin
products were much less than the NMR yields due to high
volatility of the products or difficulties in purification of crude
products by flash column chromatography (2d-f, 2h, 2x). Finally,
gram-scale synthesis of CF3-substituted alkene 2q was
conducted to explore the synthetic applicability of the reaction
and good yield of the desired product was obtained,
demonstrating its good applicability. It is worth mentioning that
the high stability of FeTPPCl permits effective olefination of
aldehydes with low catalytic loading (0.5 mol %), exhibiting the
potential practicality in the scale-up production.
the direct combination of PPh3 with CF3CHN2 readily generates
Ph3P=N-N=CHCF3 probably due to the N-electrophilicity of
trifluoro diazoethane,[11] and its subsequent reaction with
aldehydes is presumably responsible for the formation of the
main by-product azines in the reactions (Scheme 2). It should be
noted that compared with N2CHCOOEt, CF3CHN2 shows lower
olefination reactivity with corresponding aldehydes under similar
reaction conditions and much more by-product azines are
formed. We speculate that, owing to the strong electron-
withdrawing ability of CF3 group, the direct combination of PPh3
with CF3CHN2 to Ph3P=N-N=CHCF3 is accelerated and results in
the obvious formation of by-product azines. However, increasing
PPh3 concentration significantly enhances the rate of the desired
olefination reaction without influencing obviously the
combination of CF3CHN2 with PPh3, and thus suppresses
successfully the formation of by-product azines.[14]
Scheme 4. Proposed mechanism for the olefination reaction of
aldehydes with CF3CHN2 catalyzed by FeTPPCl.
Conclusions
In summary, we have first developed the olefination of
aldehydes with CF3CHN2 catalyzed by iron(III) porphyrin
complex to prepare various CF3-substituted alkenes in good
yields. The reaction exhibits broad substrate scope and good
functional group compatibility. It is an important supplement to
the synthetic application of CF3CHN2. Utilization of increased
amounts of PPh3 is the key point to the success of the reaction.
Scheme 3. Substrate scope of the olefination reactions of
aldehydes with CF3CHN2. [a] Unless otherwise noted, the
reaction conditions are as follows: 1a (1.0 mmol), CF3CHN2 (1.5
mmol), PPh3 (4.0 mmol), Fe(TPP)Cl (2 mol %), toluene (4.0 mL),
Experimental Section
100 MHz and 376 MHz, respectively. Chemical shifts were
reported in parts per million (ppm) relative to TMS as an internal
o
80 C, Ar atmosphere, overnight. All the yields refer to those of
1
standard (δTMS = 0 ppm) for H and 13C NMR spectra and CFCl3
the isolated products unless otherwise noted. The ratio of Z/E
isomers was determined by 19FNMR spectroscopy. [b] Yields
were determined by 19F NMR spectroscopy using
trifluorotoluene as an internal standard. [c] Gram-scale synthesis
using 1a (6.0 mmol), CF3CHN2 (9.0 mmol), PPh3 (24 mmol),
Fe(TPP)Cl (0.5 mol %) and toluene (25 mL).
as an external standard (negative for upfield) for 19F NMR
spectra. GC-MS (EI) data were determined on an Agilent 5975C.
HRMS (EI) data were tested on a Water Micromass GCT
Premier. Element analysis data were determined on Elementar
VARIO EL apparatus. IR spectra were recorded on a Thermo
Scientific Nicolet 380 FT-IR spectrometer. Toluene was distilled
from CaH2. All the other solvents or reagents were used as
commercial sources without purification if not noted. All
reactions were performed in standard sealed tubes and
monitored by thin-layer chromatography (TLC), 19F NMR or GC-
MS. Flash column chromatography was carried out using 300-
400 mesh silica gel.
Based on the above results and the literature,[12,14] we
proposed a similar mechanism for this olefination process to that
of olefination reactions of aldehydes with N2CHCOOEt (Scheme
4). The Fe (III) center of FeTPPCl is readily reduced to Fe (II) in
the reaction system. Fe(II)TPP forms the metal-carbene active
intermediate with CF3CHN2 with the extrusion of N2. CF3CH:
carbene transfers from the metal center to PPh3 to generate a
phosphorene. Its subsequent Wittig reaction with aldehydes
leads to the desired CF3-substituted alkenes. On the other hand,
Typical procedure for the preparation of the stock solution
of CF3CHN2. CF3CHN2 was prepared according to a reported
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10.1002/ejoc.201800325
European Journal of Organic Chemistry
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method[15] with some modifications. To an oven-dried 500 mL
three-necked round-bottom flask equipped with a stir bar and
sealed with a septum was added dry CF3CH2NH2·HCl (13.55 g,
100 mmol) under Ar atmosphere. Degassed toluene (200 mL)
was added under Ar, and the mixture, while stirring, was cooled
(d, J = 8.7 Hz). GC-MS (EI): m/z = 197.1 (M+). Spectral data are
in accordance with the literature. [7a]
(Z/E)-1-bromo-4-(3,3,3-trifluoroprop-1-en-1-yl)benzene
89% (Z/E = 1/1.8) 19F NMR yield. The product (132 mg, 53%)
was obtained as colorless liquid by flash column
(2d).
a
o
to 0 C. The solution of NaNO2 (7.59 g, 110 mmol) in degassed
chromatography (Petroleum ether/DCM = 10/1). Data for Z/E
1
H2O (20 mL) was slowly added to the mixture above under Ar.
The resulting solution was stirred for 3 h at 0 C and then for an
isomers: H NMR (400 MHz, CDCl3): δ 7.56 – 7.45 (m, 2 H, Ar-
o
H), 7.34 – 7.21 (m, 2 H, Ar-H), 7.08 (dq, J = 16.1, 2.2 Hz, 0.6 H,
E), 6.84 (d, J = 12.6 Hz, 0.4 H, Z), 6.18 (dq, J = 16.2, 6.5 Hz, 0.6
H, E), 5.79 (dq, J = 12.6, 9.0 Hz, 0.4 H, Z). 19F NMR (376 MHz,
CDCl3): δ -57.64 (d, J = 8.9 Hz, 0.4 F, Z), δ -63.51 (dd, J = 6.2,
2.1 Hz, 0.6 F, E). GC-MS (EI): m/z = 250.0 (M+). Spectral data
are in accordance with the literature.[7b]
additional 1 h at room temperature. The aqueous layer was
frozen in the freezer overnight (~ -40 oC). The organic layer was
then transferred using a Teflon needle to a flame-dried round
bottom flask and dried (K2CO3, 10 g) for at least 1 h prior to use.
The concentration of this stock solution is determined by 19F
NMR spectroscopy with trifluorotoluene as an internal standard.
It can be stored and used in refrigerator at temperatures < 4 C
under dark for at least two months without apparent
concentration change.
CAUTION: Although it was found that CF3CHN2 is stable in
solution under dark, neither impact nor static sensitive, it is
potentially explosive, toxic and prone to cause development of
specific sensitivity, and therefore must be handled with adequate
caution and protective measures.
(Z/E)-1-bromo-3-(3,3,3-trifluoroprop-1-en-1-yl)benzene
93% (Z/E = 1/2.3) 19F NMR yield. The product (113 mg, 45%)
was obtained as colorless liquid by flash column
(2e).
o
a
1
chromatography (Petroleum ether). Data for Z/E isomers: H
NMR (400 MHz, CDCl3): δ 7.59 (s, 0.77 H, Ar-H), 7.53 – 7.44 (m,
1.15 H, Ar-H), 7.36 (m, 1 H, Ar-H), 7.24 (m, 1 H, Ar-H), 7.06 (dq,
J = 16.1, 2.2 Hz, 0.77 H, E), 6.86 (d, J = 12.6 Hz, 0.22 H, Z),
6.19 (dq, J = 16.1, 6.4 Hz, 0.77 H, E), 5.81 (dq, J = 12.5, 8.8 Hz,
0.22 H, Z). 19F NMR (376 MHz, CDCl3): δ -57.65 (d, J = 8.8 Hz,
0.22 F, Z), δ -63.63 (dd, J = 6.4, 2.3 Hz, 0.78 F, E). GC-MS (EI):
m/z = 250.0 (M+). Spectral data are in accordance with the
literature.[5e]
Typical procedure for FeTPPCl-catalzyed olefination
reactions of aldehydes with CF3CHN2. An oven-dried and
resealable Schlenk tube capped with a Teflon screwcap was
charged with FeTPPCl (0.02 mmol, 14 mg, 2 mol %) and PPh3
(4 mmol, 1.05 g, 4 equiv) under Ar atmosphere. Aldehyde (1
mmol, 1.0 equivalent) and toluene (4 mL) were added in turn.
(Z/E)-1-fluoro-4-(3,3,3-trifluoroprop-1-en-1-yl)benzene (2f). 99%
(Z/E = 1/1.8) 19F NMR yield. The product (80 mg, 42%) was
obtained as a colorless liquid by flash column chromatography
1
(Petroleum ether). Data for Z/E isomers: H NMR (400 MHz,
o
The mixture was heated to 80 C and CF3CHN2 (1.5 mmol, 1.5
CDCl3): δ 7.47 – 7.35 (m, 2 H, Ar-H), 7.16 – 6.99 (m, 2.72 H),
6.86 (d, J = 12.6 Hz, 0.26 H, Z), 6.12 (dq, J = 16.2, 6.5 Hz, 0.76
H, E), 5.74 (dq, J = 12.6, 9.0 Hz, 0.24 H, Z). 19F NMR (376 MHz,
CDCl3): δ -57.67 (d, J = 8.9 Hz, 0.24 F, Z), δ -63.38 (dd, J = 6.3,
2.3 Hz, 0.76 F, E), -110.25 – -110.37 (m, 0.25 F, Ar-F), -111.60
– -111.72 (m, 0.08 F, Ar-F), GC-MS (EI): m/z = 190.0 (M+).
Spectral data are in accordance with the literature.[16a]
equivalents) stock solution in toulene was dropwise added to the
mixture under Ar in 10 minutes. The resulting solution was
o
stirred at 80 C overnight, and cooled to room temperature and
concentrated under reduced pressure. The residue was purified
by flash column chromatography on silica gel to afford the
desired product. The ratio of Z/E isomers in the products was
determined by 19F NMR spectroscopy of the reaction system
without any purification.
(Z/E)-1-chloro-4-(3,3,3-trifluoroprop-1-en-1-yl)benzene
75% (Z/E = 1/1.3) 19F NMR yield. The product (126 mg, 61%)
was obtained as colorless liquid by flash column
(2g).
(Z/E)-4-(3,3,3-trifluoroprop-1-en-1-yl)benzonitrile (2a). 98% (Z/E
= 1/2.4) 19F NMR yield, The product (Z: 46 mg, 23%, yellow oil;
E: 122 mg, 62%, white soild) was obtained by flash column
chromatography (Petroleum ether/DCM = 10/1). Data for Z
a
chromatography (Petroleum ether). Data for Z/E isomers: 1H
NMR (400 MHz, CDCl3): δ 7.41 – 7.29 (m, 4 H, Ar-H), 7.09 (dq,
J = 16.1, 2.2 Hz, 0.7 H, E), 6.86 (d, J = 12.6 Hz, 0.3 H, Z), 6.17
(dq, J = 16.0, 6.4 Hz, 0.7 H, E), 5.78 (dq, J = 12.6, 9.0 Hz, 0.3 H,
Z). 19F NMR (376 MHz, CDCl3): δ -57.65 (d, J = 9.3 Hz, 0.3 F, Z),
δ -63.48 (dd, J = 6.5, 2.2 Hz, 0.7 F, E). GC-MS (EI): m/z = 206.0
(M+). Spectral data are in accordance with the literature.[8]
(Z/E)-(trifluoromethyl)(4-(3,3,3-trifluoroprop-1-en-1-
1
isomer: H NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.3 Hz, 2 H),
7.45 (d, J = 8.1 Hz, 2 H), 6.94 (d, J = 12.5 Hz, 1 H), 5.91 (dq, J =
12.5, 8.7 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -57.72 (d, J =
8.7 Hz). GC-MS (EI): m/z = 197.1 (M+). Data for E isomer: 1H
NMR (400 MHz, CDCl3): δ 7.15 (dq, J = 16.2, 2.0 Hz, 1 H), 6.30
(dq, J = 16.2, 6.3 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -63.92
(dd, J = 6.5, 2.2 Hz). GC-MS (EI): m/z = 197.0 (M+). Spectral
data are in accordance with the literature.[7a]
(Z/E)-2-(3,3,3-trifluoroprop-1-en-1-yl)benzonitrile (2b). 96% (Z/E
= 3.8/1) 19F NMR yield. The product (Z: 148 mg, 75%, yellow oil;
E: 32 mg, 16%, yellow oil) was obtained by flash column
chromatography (Petroleum ether/DCM = 10/1). Data for Z
isomer: 1H NMR (400 MHz, CDCl3): δ 7.69 (dd, J = 7.7, 1.4 Hz, 1
H), 7.60 (td, J = 7.7, 1.4 Hz, 1 H), 7.52 (d, J = 7.9 Hz, 1 H), 7.45
(td, J = 7.7, 1.3 Hz, 1 H), 7.15 (d, J = 12.4 Hz, 1 H), 6.04 (dq, J =
12.4, 8.4 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -58.10 (d, J =
8.6 Hz). GC-MS (EI): m/z = 197.0 (M+). Data for E isomer: 1H
NMR (400 MHz, CDCl3): δ 7.71 (dd, J = 7.8, 1.6 Hz, 1 H), 7.70 –
7.59 (m, 2 H), 7.52 – 7.44 (m, 2 H), 6.40 (dq, J = 16.0, 6.3 Hz, 1
H). 19F NMR (376 MHz, CDCl3): δ -64.01 (dd, J = 6.4, 2.4 Hz).
GC-MS (EI): m/z = 197.0 (M+). Spectral data are in accordance
with the literature.[7b]
yl)phenyl)sulfane (2h). 71% (Z/E = 1/2) 19F NMR yield. The
product (158 mg, 58%) was obtained as a colorless liquid by
flash column chromatography (Petroleum ether). Data for Z/E
1
isomers: H NMR (400 MHz, CDCl3): δ 7.70 – 7.62 (m, 2 H, Ar-
H), 7.48 (d, J = 8.2 Hz, 1.45 H, Ar-H), 7.42 (d, J = 8.1 Hz, 0.6 H,
Ar-H), 7.15 (dq, J = 16.1, 2.2 Hz, 0.7 H, E), 6.93 (d, J = 12.5 Hz,
0.29 H, Z), 6.26 (dq, J = 16.1, 6.4 Hz, 0.7 H, E), 5.86 (dq, J =
12.6, 8.8 Hz, 0.3 H, Z). 19F NMR (376 MHz, CDCl3): δ -42.46 (s,
0.7 F, SCF3), δ -42.49 (s, 0.3 F, SCF3), -57.74 (d, J = 8.9 Hz, 0.3
F, Z), -63.79 (dd, J = 6.6, 2.2 Hz, 0.7 F, E). GC-MS (EI): m/z =
272.0 (M+). HRMS (EI): calcd for C10H6F6S (M+) 272.0094, found
272.0096. IR (film): νmax (cm-1) =1666.6, 1563.4, 1494.7, 1405.7,
1330.0, 1313.9, 1277.6, 1224.3, 1205.8, 1119.1, 1084.6, 1016.3,
973.1, 951.6, 880.2, 856.6, 837.2, 812.1, 756.5, 641.5, 581.9,
569.6, 514.5.
(Z/E)-1-nitro-4-(3,3,3-trifluoroprop-1-en-1-yl)benzene (2i). 77%
(Z/E = 1/2.5) 19F NMR yield. The product (163 mg, 75%) was
obtained as a yellow liquid by flash column chromatography
(Petroleum ether/DCM = 10/1). Data for Z isomer: 1H NMR (400
MHz, CDCl3): δ 8.22 (d, J = 8.5 Hz, 2 H, Ar-H), 7.51 (d, J = 8.4
Hz, 2 H, Ar-H), 6.99 (d, J = 12.6 Hz, 1 H), 5.96 (dq, J = 12.4, 8.8
Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -57.76 (d, J = 8.7 Hz).
(Z/E)-3-(3,3,3-trifluoroprop-1-en-1-yl)benzonitrile (2c). 93% (Z/E
= 1/2.6) 19F NMR yield. The product was obtained as a colorless
liquid (177 mg, 90%) by flash column chromatography
(Petroleum ether/DCM = 10/1). The spectroscopic data were
only analyzed for the major Z isomer: 1H NMR (400 MHz,
CDCl3): δ 7.70 – 7.45 (m, 4 H), 6.91 (d, J = 12.5 Hz, 1 H), 5.90
(dq, J = 12.4, 8.8 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -57.76
1
GC-MS (EI): m/z = 217.0 (M+).Data for E isomer: H NMR (400
MHz, CDCl3): δ 8.24 (d, J = 8.4 Hz, 2 H, Ar-H), 7.61 (d, J = 8.4
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201800325
European Journal of Organic Chemistry
FULL PAPER
Hz, 2 H, Ar-H), 7.32 – 7.05 (m, 1 H), 6.35 (dq, J = 16.1, 6.3 Hz, 1
H). 19F NMR (376 MHz, CDCl3): δ -64.03 (d, J = 5.8 Hz). GC-MS
(EI): m/z = 217.0 (M+). Spectral data are in accordance with the
literature.[7b]
124.54 (q, J = 268.9 Hz), 118.30 (q, J = 32.4 Hz), 110.96,
103.71, 55.76. GC-MS (EI): m/z = 232.1 (M+). HRMS (EI): calcd
for C11H11F3O2 (M+) 232.0711, found 232.0971. IR (film): νmax
(cm-1) =3008.1, 2945.3, 2843.1, 1651.9, 1596.2, 1477.4, 1435.5,
1345.2, 1313.7, 1293.5, 1253.6, 1204.2, 1181.3, 1105.0, 1036.4,
983.7, 916.6, 862.3, 838.3, 775.3, 723.0, 669.0, 616.3, 567.9,
541.5, 511.6, 416.0.
(Z/E)-1-(methylsulfonyl)-4-(3,3,3-trifluoroprop-1-en-1-yl)benzene
(2j). 80% (Z/E = 1/2.2) 19F NMR yield. The product (Z: 60 mg,
24%, yellow oil; E: 136 mg, 55%, white soild) was obtained by
flash column chromatography (Petroleum ether/DCM = 10/1).
Data for Z isomer: 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.4
Hz, 2 H, Ar-H), 7.53 (d, J = 8.2 Hz, 2 H, Ar-H), 6.98 (d, J = 12.5
Hz, 1 H), 5.93 (dq, J = 12.6, 8.7 Hz, 1 H), 3.05 (s, 3 H). 19F NMR
(376 MHz, CDCl3): δ -57.65 (d, J = 8.8 Hz). GC-MS (EI): m/z =
250.0.0 (M+). HRMS (EI): calcd for C10H9F3O2S (M+) 250.0275,
found 250.0278. 13C NMR (101 MHz, CDCl3): δ 140.66, 139.20,
137.58 (q, J = 5.8 Hz), 129.53 (q, J = 2.6 Hz), 127.38, 112.06 (q,
J = 270.0 Hz), 121.11 (q, J = 34.9 Hz), 44.42. Data for E isomer:
1H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 8.4 Hz, 2H), 7.63 (d, J
= 8.4 Hz, 2H), 7.19 (dq, J = 16.2, 2.2 Hz, 1H), 6.33 (dq, J = 16.2,
6.3 Hz, 1H), 3.06 (s, 3H). 19F NMR (376 MHz, CDCl3): δ -63.93
(dd, J = 6.5, 2.3 Hz). 13C NMR (101 MHz, CDCl3): δ 141.59,
138.63, 135.76 (q, J = 6.7 Hz), 128.31, 128.10, 122.92 (q, J =
269.4 Hz), 119.69 (q, J = 34.4 Hz), 44.44. GC-MS (EI): m/z =
250.0 (M+). HRMS (EI): calcd for C10H9F3O2S (M+) 250.0275,
found 250.0279.
(Z/E)-5-bromo-6-(3,3,3-trifluoroprop-1-en-1-
yl)benzo[d][1,3]dioxole (2p). 99% (Z/E = 2.8/1) 19F NMR yield.
The product (Z: 177 mg, 60%, white soild; E: 111 mg, 38%,
white soild) was obtained by flash column chromatography
(Petroleum ether/EA = 40/1). Data for Z isomer: 1H NMR (400
MHz, CDCl3): δ 7.02 (s, 1 H), 6.91 (d, J = 12.4 Hz, 1 H), 6.88 (s,
1 H), 6.00 (s, 2 H), 5.78 (dq, J = 12.2, 8.6 Hz, 1 H). 19F NMR
(376 MHz, CDCl3): δ -57.62 (d, J = 8.7 Hz). 13C NMR of Z isomer
(101 MHz, CDCl3): δ 149.82, 147.99, 136.25 (q, J = 7.0 Hz),
126.63, 123.37 (q, J = 269.0 Hz), 116.84 116.58 (q, J = 33.9 Hz),
113.07, 106.33, 102.26. GC-MS (EI): m/z = 294 (M+). HRMS
(EI): calcd for C10H6BrF3O2 (M+) 293.9503, found 293.9509. IR
(film): νmax (cm-1) = 2916.1, 1657.9, 1615.5, 1603.8, 1506.6,
1480.2, 1417.5, 1399.3, 1368.8, 1282.1, 1248.4, 1116.2, 1039.0,
978.8, 966.3, 938.7, 871.2, 854.4, 827.6, 694.3, 658.9, 584.1,
506.4, 450.8. Data for E isomer: 1H NMR (400 MHz, CDCl3): δ
7.49 – 7.40 (m, 1 H), 7.03 (s, 1 H), 6.97 (s, 1 H), 6.06 – 5.93 (m,
3 H). 19F NMR (376 MHz, CDCl3): δ -63.22 (dd, J = 6.3, 2.4 Hz).
GC-MS (EI): m/z = 294 (M+). HRMS (EI): calcd for C10H6BrF3O2
(M+) 293.9503, found 293.9508.
(Z/E)-4-(3,3,3-trifluoroprop-1-en-1-yl)phenyl acetate (2k). 65%
(Z/E = 1/1.5) 19F NMR yield. The product (141 mg, 61%) was
obtained as a brown solid by flash column chromatography
(Petroleum ether/EA = 100/1). Data for Z/E isomers: 1H NMR
(400 MHz, CDCl3): δ 7.50 – 7.38 (m, 2 H, Ar-H), 7.16 – 7.06 (m,
2.7 H), 6.87 (d, J = 12.7 Hz, 0.3 H, Z), 6.15 (dq, J = 16.3, 6.5 Hz,
0.7 H, E), 5.75 (dq, J = 12.7, 9.0 Hz, 0.3 H, Z), 2.31 – 2.29 (m, 3
(Z/E)-1,3-di-tert-butyl-5-(3,3,3-trifluoroprop-1-en-1-yl)benzene
(2q). 94% (Z/E = 1/2.9) 19F NMR yield. The product (243 mg,
86%) was obtained as a colorless liquid by flash column
chromatography (Petroleum ether). Gram-scale synthesis was
H). 19F NMR (376 MHz, CDCl3): δ -57.62 (d, J = 9.0 Hz, 0.3 F, Z), conducted with 3,5-bis(tert-butyl)benzaldehyde (6 mmol, 1.3 g,
δ -63.38 (dd, J = 6.5, 2.2 Hz, 0.7 F, E). GC-MS (EI): m/z = 230.0
(M+). Spectral data are in accordance with the literature.[5e]
(E)-1,2,3,4,5-pentafluoro-6-(3,3,3-trifluoroprop-1-en-1-
1.0 equiv), PPh3 (24 mmol, 6.3 g, 4.0 equiv), CF3CHN2 (9 mmol,
1.5 equiv) stock solution in toluene, FeTPPCl (0.03 mmol, 21 mg,
0.5 mol %) and toluene (25 mL) according to the general
procedures, affording the corresponding product as colorless
liquid (1.41 g, 83%, Z/E = 1/3). Data for Z/E isomers: 1H NMR
(400 MHz, CDCl3): δ 7.50 (t, J = 1.8 Hz, 0.76 H, Ar-H), 7.46 (t, J
= 1.8 Hz, 0.24 H, Ar-H), 7.35 – 7.30 (m, 2 H, Ar-H), 7.22 (dq, J =
16.1, 2.3 Hz, 0.76 H, E), 6.95 (d, J = 12.6 Hz, 0.24 H, Z), 6.24
(dq, J = 16.1, 6.6 Hz, 0.76 H, E), 5.74 (dq, J = 12.6, 9.2 Hz, 0.24
H, Z), 1.42 – 1.32 (m, 18 H). 19F NMR (376 MHz, CDCl3): δ -
57.39 (d, J = 9.3 Hz, 0.24 F, Z). -63.06 (dd, J = 6.7, 2.4 Hz, 0.76
F, E). 13C NMR (101 MHz, CDCl3): δ 151.52, 138.73 (q, J = 6.7
Hz), 132.75, 124.41, 123.87 (q, J = 268.9 Hz), 121.82, 115.14 (q,
J = 33.7 Hz), 34.89, 31.37. GC-MS (EI): m/z = 284.1 (M+).
HRMS (EI): calcd for C17H23F3 (M+) 284.1752, found 284.1743.
IR (film): νmax (cm-1) = 2965.4, 2869.1, 1666.1, 1596.7, 1478.8,
1394.9, 1364.3, 1329.9, 1309.6, 1297.6, 1272.3, 1249.5, 1200.5,
1180.5, 1124.9, 972.4, 900.3, 880.9, 867.4, 826.9, 704.4, 596.8.
(Z/E)-1-(but-3-en-1-yloxy)-4-(3,3,3-trifluoroprop-1-en-1-
yl)benzene (2l). 72% (E) 19F NMR yield. Characterization of 2l in
reaction solution. Crude 1H NMR (400 MHz, CDCl3): δ 7.11 (dq,
J = 16.7, 2.7, 2.3 Hz, 1 H), 6.58 (dq, J = 16.6, 6.1 Hz, 1 H).
Crude 19F NMR (376 MHz, CDCl3): δ -65.03 (m, 3 F, E), -140.03
– -140.58 (m, 2 F), -150.84 (t, J = 21.1 Hz, 1 F), -161.23 (tt, J =
20.3, 6.1 Hz, 2 F). GC-MS (EI): m/z = 262.0 (M+). HRMS (EI)
calcd for C9H2F8 (M+): 262.0029, found 262.0031.
(Z/E)-1,3-dichloro-2-(3,3,3-trifluoroprop-1-en-1-yl)benzene (2m).
81% (Z/E = 1/8.3) 19F NMR yield. The product (190 mg, 79%)
was obtained as
a
colorless liquid by flash column
chromatography (Petroleum ether). Data for Z/E isomers: 1H
NMR (400 MHz, CDCl3): δ 7.39 – 7.28 (m, 2 H, Ar-H), 7.27 –
7.16 (m, 1.92 H), 6.76 (d, J = 12.1 Hz, 0.09 H, Z), 6.39 (dq, J =
16.4, 6.3 Hz, 0.92 H, E), 6.03 (dq, J = 12.1, 7.9 Hz, 0.09 H, Z).
19F NMR (376 MHz, CDCl3): δ -62.82 (d, J = 7.8 Hz, 0.08 F, Z), -
64.78 (dd, J = 6.1, 2.4 Hz, 0.92 F, E). GC-MS (EI): m/z = 240.0
(M+). Spectral data are in accordance with the literature.[7b]
yl)benzene (2r). 99% (Z/E = 1/1.9) 19F NMR yield. The product
(204 mg, 89%) was obtained as a brown solid by flash column
chromatography (Petroleum ether). Data for Z/E isomers: 1H
NMR (400 MHz, CDCl3): δ 7.41 – 7.34 (m, 2 H, Ar-H), 7.08 (dd,
J = 16.1, 2.4 Hz, 0.67 H, E), 6.93 – 6.86 (m, 2 H, Ar-H), 6.80 (d,
J = 12.7 Hz, 0.34 H, Z), 6.06 (dq, J = 16.0, 6.6 Hz, 0.67 H, E),
5.97 – 5.84 (m, 1 H), 5.63 (dq, J = 12.6, 9.4 Hz, 0.34 H, Z), 5.24
(Z/E)-1-methoxy-4-(3,3,3-trifluoroprop-1-en-1-yl)benzene (2n).
98% (Z/E = 1/2) 19F NMR yield. The product (182 mg, 90%) was
obtained as a colorless liquid by flash column chromatography
(Petroleum ether). Data for Z/E isomers: 1H NMR (400 MHz,
CDCl3): δ 7.38 (d, J = 8.5 Hz, 2H, Ar-H), 7.08 (dd, J = 16.1, 2.3
Hz, 0.7 H, E), 6.93 – 6.87 (m, 2 H, Ar-H), 6.81 (d, J = 12.7 Hz,
0.3 H, Z), 6.06 (dq, J = 16.1, 6.6 Hz, 0.7 H, E), 5.63 (dq, J = 12.7, – 5.08 (m, 2H), 4.03 (td, J = 6.7, 1.2 Hz, 2 H), 2.59 – 2.52 (m, 2
9.4 Hz, 0.3 H, Z), 3.84 – 3.81 (m, 3 H). 19F NMR (376 MHz,
CDCl3): δ -57.56 (d, J = 9.4 Hz, 0.32 F, Z), -62.87 (dd, J = 6.8,
2.3 Hz, 0.68 F, E). GC-MS (EI): m/z = 202.1 (M+). Spectral data
are in accordance with the literature.[7b]
H).19F NMR (376 MHz, CDCl3): δ -57.55 (d, J = 9.3 Hz, 0.33 F,
Z), -62.84 (dd, J = 6.7, 2.1 Hz, 0.67 F, E). 13C NMR of Z isomer
(101 MHz, CDCl3): δ 159.69, 139.21 (q, J = 6.0 Hz), 134.22,
130.91 (q, J = 2.8 Hz), 126.05, 123.12 (q, J = 271.2 Hz), 117.16,
115.59 (q, J = 34.9 Hz), 114.36, 67.23, 33.55. 13C NMR of E
isomer (101 MHz, CDCl3): δ 160.41, 137.12 (q, J = 6.9 Hz),
134.15, 130.91 (q, J = 2.8 Hz), 129.02, 123.96 (q, J = 268.1 Hz),
117.23, 114.89, 113.37 (q, J = 33.8 Hz), 67.32, 33.53. GC-MS
(EI): m/z = 242.1 (M+). HRMS (EI): calcd for C13H13F3O (M+)
242.0918, found 242.0917. IR (film): νmax (cm-1) = 3079.9, 2983.1,
2929.6, 2873.9, 1663.1, 1608.5, 1577.4, 1513.4, 1473.0, 1425.8,
(E)-1,3-dimethoxy-2-(3,3,3-trifluoroprop-1-en-1-yl)benzene (2o).
93% (E) 19F NMR yield. The product (211 mg, 91%) was
obtained as a yellow solid by flash column chromatography
(Petroleum ether/EA = 200/1). 1H NMR (400 MHz, CDCl3): δ
7.53 (dq, J = 16.5, 2.3 Hz, 1 H), 7.30 – 7.20 (m, 1 H), 6.71 (dq, J
= 16.5, 6.8 Hz, 1 H), 6.55 (d, J = 8.4 Hz, 2 H), 3.86 (s, 6 H). 19
F
NMR (376 MHz, CDCl3): δ -63.23 (dd, J = 6.8, 2.1 Hz). 13C NMR
(101 MHz, CDCl3): δ 159.53, 130.77, 127.75 (q, J = 7.4 Hz),
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201800325
European Journal of Organic Chemistry
FULL PAPER
1386.6, 1338.5, 1312.7, 1253.6, 1175.6, 1109.0, 1033.7, 973.3,
920.8, 878.1, 845.9, 815.8, 677.1, 637.9, 570.3, 516.7, 457.9.
(Z/E)-9-(3,3,3-trifluoroprop-1-en-1-yl)anthracene (2s). 70% (Z/E
= 1/2.9) 19F NMR yield. The product (Z: 41 mg, 15%, yellow
soild; E: 128 mg, 47%, yellow soild) was obtained by flash
column chromatography (Petroleum ether/EA = 100/1). Data for
Z isomer: 1H NMR (400 MHz, CDCl3): δ 8.44 (s, 1 H), 8.05 –
7.96 (m, 4 H), 7.59 (d, J = 12.2 Hz, 1 H), 7.55 – 7.43 (m, 4 H),
6.44 (dq, J = 12.1, 7.9 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -
61.19 (d, J = 7.7 Hz). GC-MS (EI): m/z = 272.1 (M+). Data for E
6.04 (dq, J = 16.1, 6.6 Hz, 0.72 H, E), 5.64 (dq, J = 12.7, 9.2 Hz,
0.28 H, Z). 19F NMR (376 MHz, CDCl3): δ -58.25 (d, J = 9.0 Hz,
0.27 F, Z), -63.29 (dd, J = 6.6, 2.1 Hz, 0.73 F, E). GC-MS (EI):
m/z = 178.0 (M+). Spectral data are in accordance with the
literature.[16b]
(Z/E)-1-(3,3,3-trifluoroprop-1-en-1-yl)ferrocene (2y). 98% (Z/E =
1/2.9) 19F NMR yield. The product (260 mg, 93%) was obtained
as a red solid by flash column chromatography (Petroleum
ether). Data for Z/E isomers: 1H NMR (400 MHz, CDCl3): δ 6.95
(dd, J = 15.9, 2.3 Hz, 0.77 H, E), 6.57 (d, J = 12.4 Hz, 0.23 H, Z),
5.78 (dq, J = 15.9, 6.6 Hz, 0.77 H, E), 5.51 (dq, J = 12.6, 9.3 Hz,
0.23 H, Z), 4.54 – 4.38 (m, 2 H, Ar-H), 4.37 – 4.32 (m, 2 H, Ar-H),
4.14 (s, 5 H, Ar-H). 19F NMR (376 MHz, CDCl3): δ -58.28 (d, J =
9.4 Hz, 0.23 F, Z), -62.88 (dd, J = 6.5, 2.1 Hz, 0.77 F, E). 13C
NMR of E isomer (101 MHz, CDCl3): δ 137.19 (q, J = 7.0 Hz),
123.89 (q, J = 268.2 Hz), 112.41 (q, J = 33.6 Hz), 70.29, 69.58,
69.53, 67.95. MS (EI): m/z = 279 (M+). HRMS (EI): calcd for
C13H12F3Fe (M+) 280.0162, found 279.0282. IR (film): νmax (cm-1)
= 3096.3, 1660.2, 1468.8, 1412.3, 1397.5, 1363.4, 1351.2,
1305.3, 1269.8, 1191.8, 1119.2, 1044.0, 1029.5, 1002.1, 965.3,
931.3, 868.3, 822.5, 748.8, 647.5, 633.7, 498.3, 482.6, 442.1,
430.2.
(Z/E)-2-(3,3,3-trifluoroprop-1-en-1-yl)benzofuran (2z). 69% (Z/E
= 1/2.2) 19F NMR yield. The product (107 mg, 51%) was
obtained as a white solid by flash column chromatography
(Petroleum ether). The spectroscopic data were only analyzed
for the major E isomer: 1H NMR (400 MHz, CDCl3): δ 7.57 (d, J =
7.9 Hz, 1 H), 7.50 – 7.43 (m, 1 H), 7.38 – 7.31 (m, 1 H), 7.25 –
7.20 (m, 1 H), 7.03 (dq, J = 15.8, 2.1 Hz, 1 H), 6.40 (dq, J = 15.7,
6.9 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -63.62 (dd, J = 6.8,
2.0 Hz). GC-MS (EI): m/z = 212.0 (M+). Spectral data are in
accordance with the literature.[16c]
1
isomer: H NMR (400 MHz, CDCl3): δ 8.41 (s, 1 H), 8.15 – 8.09
(m, 2 H), 8.02 – 7.94 (m, 3 H), 7.56 – 7.46 (m, 4 H), 6.18 (dq, J =
16.4, 6.3 Hz, 1 H). 19F NMR (376 MHz, CDCl3): δ -63.91 (dd, J =
6.3, 2.4 Hz). GC-MS (EI): m/z = 272.1 (M+). Spectral data are in
accordance with the literature. [7a]
(Z/E)-1-(3,3,3-trifluoroprop-1-en-1-yl)naphthalene (2t). 81% (Z/E
= 1/2.2) 19F NMR yield. The product (173 mg, 78%) was
obtained as a colorless liquid by flash column chromatography
(Petroleum ether). The spectroscopic data were only analyzed
for the major E isomer: 1H NMR (400 MHz, CDCl3): δ 8.05 (d, J =
8.1 Hz, 1 H), 7.96 (dd, J = 15.9, 2.4 Hz, 1 H), 7.92 – 7.86 (m, 2
H), 7.63 (d, J = 7.1 Hz, 1 H), 7.56 (dq, J = 6.8, 1.5 Hz, 2 H), 7.48
(t, J = 7.7 Hz, 1 H), 6.27 (dq, J = 15.8, 6.5 Hz, 1 H). 19F NMR
(376 MHz, CDCl3): δ -63.41 (dd, J = 6.3, 2.5 Hz). GC-MS (EI):
m/z = 222.1 (M+). Spectral data are in accordance with the
literature. [7a]
(Z/E)-(3,3,3-trifluoroprop-1-en-1-yl)benzene (2u). 84% (Z/E =
1/1.5) 19F NMR yield. Characterization of 2u in reaction solution.
Crude 19F NMR (376 MHz, unlocked): δ -57.46 (d, J = 9.1 Hz,
0.32 F, Z), -63.14 – -63.23 (m, 0.68 F, E). GC-MS (EI): m/z =
172.0 (M+). HRMS (EI) calcd for C9H7F3 (M+): 172.0500, found
172.0497. Spectral data are in accordance with the literature.[8]
(Z/E)-((1E)-5,5,5-trifluoropenta-1,3-dien-1-yl)benzene (2v). 99%
(Z/E = 1.1/1) 19F NMR yield. The product (180 mg, 91%) was
obtained as a colorless liquid by flash column chromatography
(Z/E)-3-(3,3,3-trifluoroprop-1-en-1-yl)benzo[b]thiophene
(2aa).
93% (Z/E = 1/3) 19F NMR yield. The product (205 mg, 90%) was
obtained as a colorless liquid by flash column chromatography
(Petroleum ether). Data of the Z/E isomers: 1H NMR (400 MHz,
CDCl3): δ 7.94 – 7.86 (m, 1.5 H, Ar-H), 7.77 – 7.72 (m, 0.5 H, Ar-
H), 7.62 (s, 0.75 H), 7.52 – 7.36 (m, 3 H), 7.09 (d, J = 12.4 Hz,
1
(Petroleum ether). Data of the E,E/E,Z mixtures: H NMR (400
MHz, CDCl3): δ 7.51 – 7.42 (m, 2 H, Ar-H), 7.41 – 7.30 (m, 3 H,
Ar-H), 7.25 – 7.15 (m, 0.54 H), 6.97 – 6.86 (m, 0.53 H), 6.85 –
6.72 (m, 1.61 H), 6.58 (t, J = 11.6 Hz, 0.48 H), 5.80 (dq, J = 14.2, 0.25 H, Z), 6.31 (dq, J = 15.8, 6.5 Hz, 0.75 H, E), 5.94 (dq, J =
6.9 Hz, 0.52 H, E,E isomer), 5.57 (dq, J = 11.4, 8.9 Hz, 0.48 H,
E,Z isomer). 19F NMR (376 MHz, CDCl3): δ-57.23 (dd, J = 9.1,
2.2 Hz, 0.48 F, E,Z isomer), -63.18 (dd, J = 6.8, 2.0 Hz, 0.52 F,
E,E isomer). GC-MS (EI): m/z = 198.0 (M+). Spectral data are in
accordance with the literature.[8]
12.3, 8.8 Hz, 0.25 H, Z). 19F NMR (376 MHz, CDCl3): δ -58.26 (m,
0.25 F, Z), -63.29 (m, 0.75 F, E). GC-MS (EI): m/z = 228.0 (M+).
Spectral data are in accordance with the literature.[16d]
(Z/E)-1-(tert-butyl)-4-(5,5,5-trifluoro-2-methylpent-3-en-1-
yl)benzene (2bb). 55% (Z/E = 1/6.7 ) 19F NMR yield. The
product (148 mg, 55%) was obtained as a colorless liquid by
flash column chromatography (Petroleum ether). The
spectroscopic data were only analyzed for the major E isomer:
1H NMR (400 MHz, CDCl3): δ 7.29 (d, J = 8.3 Hz, 2 H), 7.04 (d, J
= 8.2 Hz, 2 H), 6.40 – 6.31 (m, 1 H), 5.52 (dq, J = 15.9, 12.8 Hz,
1 H), 2.73 – 2.61 (m, 1 H), 2.56 – 2.46 (m, 2 H), 1.29 (s, 9 H),
1.03 (d, J = 6.0 Hz, 3 H). 19F NMR (376 MHz, CDCl3): δ -63.82
(m). 13C NMR (101 MHz, CDCl3): δ 149.11, 145.23 (q, J = 6.3
Hz), 123.26 (q, J = 269.2 Hz), 136.17, 128.78, 125.21, 117.02 (q,
J = 33.2 Hz), 41.83, 37.45, 34.39, 31.38, 18.56. GC-MS (EI): m/z
= 270.2 (M+). HRMS (EI): calcd for C16H21F3 (M+) 270.1595,
found 270.1592. IR (film): νmax (cm-1) = 2964.4, 2871.2, 1677.8,
1510.7, 1460.0, 1414.3, 1394.4, 1362.0, 1312.1, 1277.6, 1195.9,
1122.8, 1019.9, 975.2, 865.8, 850.9, 827.1, 801.9, 674.5, 567.5.
(Z/E)-1,1,1-trifluoropentadec-2-ene (2cc). 63% (Z/E isomers,
1:2.2) 19F NMR yield. Characterization of 2cc in reaction solution.
Crude 19F NMR (376 MHz, CDCl3): δ -58.22 (d, J = 9.0 Hz, Z), -
64.11 (dd, J = 10.9, 4.8 Hz, E). GC-MS (EI): m/z = 264 (M+).
HRMS (EI) calcd for C15H27F3 (M+): 264.2065, found 264.2071.
(Z/E)-1-methoxy-4-((1E)-5,5,5-trifluoropenta-1,3-dien-1-
yl)benzene (2w). 92% (Z/E = 1/1 ) 19F NMR yield. The product
(180 mg, 91%) was obtained as a white solid by flash column
chromatography (Petroleum ether). Data of the E,E/E,Z
mixtures: 1H NMR (400 MHz, CDCl3): δ 7.43 – 7.34 (m, 2 H, Ar-
H), 7.08 – 6.98 (m, 0.42 H, E,Z isomer), 6.93 – 6.81 (m, 2.58 H),
6.73 (t, J = 16.2 Hz, 1 H), 6.67 – 6.58 (m, 0.58 H, E,E isomer),
6.58 – 6.49 (m, 0.42 H, E,Z isomer), 5.72 (dq, J = 14.3, 7.0 Hz,
0.58 H, E,E isomer), 5.47 (dq, J = 11.2, 9.0 Hz, 0.42 H, E,Z
isomer). 19F NMR (376 MHz, CDCl3): δ -57.17 (dd, J = 8.9, 1.4
Hz, 0.42 F, E,Z isomer), -62.99 (d, J = 6.8 Hz, 0.58 F, E,E
isomer). 13C NMR (101 MHz, CDCl3): δ 160.30, 138.97 – 138.86
(m), 137.80 (q, J = 6.9 Hz), 128.72, 128.43, 123.64 (q, J = 268.2
Hz), 122.80, 117.08 (q, J = 33.6 Hz), 114.26, 55.34. GC-MS (EI):
m/z = 228 (M+). HRMS (EI): calcd for C12H11F3O (M+) 228.0762,
found 228.0765. IR (film): νmax (cm-1) = 3033.7, 2964.5, 2937.5,
2843.8, 1651.7, 1638.5, 1604.1, 1571.5, 1512.6, 1463.3, 1442.9,
1433.4, 1356.1, 1315.6, 1257.8, 1257.8, 1230.8, 1175.6, 1151.6,
1111.9, 1028.9, 989.5, 963.5, 950.2, 871.2, 839.3, 824.8, 801.5,
763.7, 685.2, 636.9, 586.4, 555.2, 530.9, 482.0, 464.6, 411.8.
(Z/E)-3-(3,3,3-trifluoroprop-1-en-1-yl)thiophene (2x). 96% (Z/E =
1/1.9) 19F NMR yield. The product (94 mg, 53%) was obtained
as a colorless liquid by flash column chromatography (Petroleum
ether). Data for Z/E isomers: 1H NMR (400 MHz, CDCl3): δ 7.48
(d, J = 2.5 Hz, 0.26 H, Ar-H), 7.40 (d, J = 2.9 Hz, 0.67 H, Ar-H),
7.37 – 7.29 (m, 1 H, Ar-H), 7.29 – 7.20 (m, 1 H, Ar-H), 7.13 (dq,
J = 16.0, 2.2 Hz, 0.72 H, E), 6.81 (d, J = 12.6 Hz, 0.28 H, Z),
1,2-bis(3,3,3-trifluoroprop-1-en-1-yl)benzene
(2dd).
56%
(Z,Z/Z,E/E,E isomers) 19F NMR yield. The product (136 mg,
79%) was obtained as a colorless liquid by flash column
chromatography (Petroleum ether). Data of the Z,Z/Z,E/E,E
1
isomers: H NMR (400 MHz, CDCl3): δ 7.55 – 7.46 (m, 1 H),
7.45 – 7.28 (m, 3.4 H), 7.27 – 7.20 (m, 0.6 H), 7.08 (d, J = 12.2
Hz, 0.6 H), 6.94 (d, J = 12.2 Hz, 0.4 H), 6.21 – 6.05 (m, 1 H),
5.98 (dq, J = 12.2, 8.2 Hz, 0.6 H), 5.87 (dq, J = 12.2, 8.3 Hz, 0.4
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10.1002/ejoc.201800325
European Journal of Organic Chemistry
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H). 19F NMR (376 MHz, CDCl3): δ -58.26 (d, J = 8.5 Hz, 0.2 F), -
58.30 (d, J = 8.3 Hz, 0.3F), -63.67 (dd, J = 6.5, 2.8 Hz, 0.3 F), -
63.80 (dd, J = 6.4, 3.0 Hz, 0.2 F). GC-MS (EI): m/z = 266.1 (M+).
Spectral data of E/E isomer are in accordance with the
literature.[6a]
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1,3-bis(3,3,3-trifluoroprop-1-en-1-yl)benzene
(2ee).
97%
(Z,Z/Z,E/E,E = 1/6.8/12.6) 19F NMR yield. The product (242 mg,
91%) was obtained as a colorless liquid by flash column
chromatography (Petroleum ether). Data of the Z,Z/Z,E/E,E
1
isomers: H NMR (400 MHz, CDCl3): δ 7.52 – 7.35 (m, 4 H, Ar-
H), 7.14 (dp, J = 16.1, 2.2 Hz, 1.6 H), 6.96 – 6.88 (m, 0.4 H),
6.24 (dq, J = 16.1, 6.6 Hz, 1.6 H), 5.83 (dq, J = 12.5, 8.9 Hz, 0.4
H). 19F NMR (376 MHz, CDCl3): δ -57.57 (d, J = 8.9 Hz, 0.17 F,
Z-CF3 of Z,E isomer), -57.72 (d, J = 8.9 Hz, 0.05 F, Z,Z isomer),
-63.52 (dd, J = 6.6, 2.2 Hz, 0.17 F, E-CF3 of Z,E isomer), -63.59
(dd, J = 6.8, 2.2 Hz, 0.63 F, E,E isomer). GC-MS (EI): m/z =
266.1 (M+). Spectral data of E/E isomer are in accordance with
the literature. 6a
1,4-bis(3,3,3-trifluoroprop-1-en-1-yl)benzene
(2ff).
81%
(Z,Z/Z,E/E,E isomers) 19F NMR yield. The product (210 mg,
79%) was obtained as a colorless liquid by flash column
chromatography (Petroleum ether). Data of the Z,Z/Z,E/E,E
1
isomers: H NMR (400 MHz, CDCl3): δ 7.47 – 7.45 (m, 2 H, Ar-
H), 7.44 – 7.39 (m, 2 H, Ar-H), 7.18 – 7.09 (m, 1.4 H), 6.95 –
6.87 (m, 0.6 H), 6.30 – 6.17 (m, 1.4 H), 5.88 – 5.73 (m, 0.6 H).
19F NMR (376 MHz, CDCl3): δ -57.60 – -57.70 (m, 0.31 F), -
63.49 – -63.55 (m, 0.69 F). GC-MS (EI): m/z = 266.1 (M+).
Spectral data of E/E isomer are in accordance with the literature.
[4g]
Acknowledgements ((optional))
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (Nos.
21421002, 21302207, 21672239, 21737004), the National Basic
Research Program of China (2012CB821600) and Science and
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1819525 (5a) contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
Technology
Commission
of
Shanghai
Municipality
(17ZR1437000).
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Keywords: Aldehydes•Olefination•2,2,2-
Trifluorodiazoethane•Iron•Porphyrin
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Olefination*
Yang Lu, Chao Liu*, Yong Guo, Qing-
Yun Chen*
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An efficient iron(III) porphyrin complex-catalyzed olefination of various aldehydes with
2,2,2-trifluorodiazoethane (CF3CHN2) under neutral conditions is reported for the first
time. It is an important supplement to the synthetic application of CF3CHN2.
Title
*one or two words that highlight the emphasis of the paper or the field of the study
[a]
Key Laboratory of Organofluorine Chemistry, Shanghai Insti
Organic Chemistry, , University of Chinese Academy of Scie
Chinese Academy of Sciences, 345 Lingling Road, Shangha
200032, China
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