Ligand-Free Iron-Catalyzed Carbon(sp2)-Carbon(sp2) Cross-Coupling of Alkenyllithium with Vinyl Halides

Article abstract of DOI:10.1021/acs.joc.8b00510

An efficient ligand-free iron-catalyzed cross-coupling reaction involving alkenyllithium and vinyl iodides was developed to form diene species in moderate to good yields. This new iron-catalyzed cross-coupling reaction provides a mild, inexpensive, and environmentally friendly avenue toward synthesis of diversified diene derivatives.

Full text of DOI:10.1021/acs.joc.8b00510

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Article
Ligand-Free Iron-Catalyzed Carbon(sp2)-Carbon(sp2)
Cross-Coupling of Alkenyllithium with Vinyl halides
Qiang Liu, Zhi-Yong Wang, Xiao-Shui Peng, and Henry Nai Ching Wong
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00510 • Publication Date (Web): 23 May 2018
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Ligand-Free Iron-Catalyzed Carbon(sp2)-Carbon(sp2) Cross-
Coupling of Alkenyllithium with Vinyl halides
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Qiang Liu,[†] Zhi-Yong Wang,[†] Xiao-Shui Peng,*[†,§] Henry N.C. Wong*[†,§]
[†] Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of
Hong Kong, Shatin, New Territories, Hong Kong SAR, China
[§] Shenzhen Municipal Key Laboratory of Chemical Synthesis of Medicinal Organic Molecules, Shenzhen
Research Institute, The Chinese University of Hong Kong, No.10, Second Yuexing Road, Shenzhen 518507,
China.
Email: hncwong@cuhk.edu.hk; xspeng@cuhk.edu.hk
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Abstract
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An efficient ligand-free iron-catalyzed cross-coupling reaction involving alkenyllithium and vinyl iodides was
developed to form diene species in moderate to good yields. This new iron-catalyzed cross-coupling reaction provides a
mild, inexpensive and environmentally friendly avenue towards synthesis of diversified diene derivatives.
Introduction
Transition metal-catalyzed, especially palladium-catalyzed, cross-coupling reactions of organometallic
reagents with organic halides represent one of the most powerful methods in the field of carbon-carbon bond
construction in the quest for structurally diverse organic molecules.1,2 Notwithstanding that Murahashi and co-workers
pioneered the development of a palladium-catalyzed cross-coupling procedure making use of alkenyl halides with
alkyllithium and aryllithium reagents in the 1970s,3 the use of organolithium reagents have not been considerably
explored in cross-coupling reactions due to limitations such as high reactivity and low selectivity,4 although Capriati and
co-workers achieved very interesting foundation of reshaping organolithium-mediated organic transformation.4e-4g
However, the direct use of organolithium reagents as nucleophiles in cross-coupling reactions is highly desirable4c,5
because they are commercially available or easily prepared via lithium-halogen exchange or direct lithiation. It is
noteworthy that organolithium compounds are usually employed as precursors to generate organomagnesium,
organozinc, organotin and organoboron compounds that are used widely in metal-catalyzed cross-coupling reactions.6
Recently, Feringa and co-workers reported elegant palladium-catalyzed cross-coupling protocols involving
organolithium nucleophiles and organic halides [Figure 1(a)].7 Moreover, Feringa also disclosed for the first time
palladium-based catalytic systems for alkenyllithium as cross-coupling partners [Figure 1(a)].8 On the other hand, an
increasing interest has been triggered in an attempt to replace palladium with iron due to its earth-abundant,
inexpensive and environmentally benign nature.9 In this context, Kochi was the first to report an iron-catalyzed cross-
coupling reaction in 1971 [Figure 1(b)].10 Subsequently, Fürstner,11 Nakamura,12 Bedford13 and Cahiez14 have all
contributed significantly to iron-catalyzed cross-coupling reactions.
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Figure 1. Transition metal-catalyzed cross-coupling to form carbon-carbon bonds.
Results and Discussion
Recently, our group developed an efficient iron-catalyzed cross-coupling protocol under mild conditions,
employing organolithium compounds and a variety of organic bromides. Our examples included formation of C(sp2)-
C(sp3) bonds and C(sp3)-C(sp3) bonds [Figure 1(c)].15 These approaches have therefore provided a valuable alternative
to existing methodologies by showing for the first time that organolithium reagents could be employed as cross-coupling
partners in iron-catalyzed cross-coupling procedures. Furthermore, our results have also prompted us to further
investigate C(sp2)-C(sp2) (vinyl-vinyl) construction. Herein, we report a new catalytic protocol that allows (E)-β-aryl vinyl
halides to couple with (E)-alkenyllithium reagents, resulting in moderate to good yields and with the retention of
stereochemistry. The catalytic system is based on FeCl3, under a mild (0 ℃) and ligand-free condition with a short
reaction time (1 h) [Figure 1(d)].
Our research began with the preliminary screening on this cross-coupling route by using (E)-propenyllithium (2a),
prepared by treatment of (E)-bromopropene with elemental lithium,8 with diverse (E)-β-phenyl vinyl halides (1)16 in the
presence of various commonly used iron catalysts in toluene (Table 1) or THF (see Supplementary Table S2). The most
effective cross-coupling combination with high conversion (100%) and acceptable yield (52.5%) could be concluded
when (E)-β-phenyl vinyl iodide (1c) was used as the cross-coupling partner in the presence of catalytic iron(III) chloride
in toluene as shown in Table 1 (Entry 6). From the GC-MS spectra, polymers were detected as major by-products. To
avoid this, we thereafter examined several series of NHC ligands,12a,17,18 Buchwald ligands, other commonly used
phosphine-containing, amine-containing monodentate as well as bidentate ligands, and “pincer” ligands.19
Disappointingly, none of these ligands could improve the yield (see Supplementary Tables S3.1  S3.3). Moreover, we
didn’t detect any trace amount of palladium from FeCl3 using ICP-EAS analysis. In the absence of iron catalysts, the
relevant control experiments were also performed, resulting in only trace amounts of cross-coupling products with major
reductive by-products being formed via a fast lithium-halogen exchange.
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Table 1.Preliminary screening reactions in toluene.[a]
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Entry
X
Iron catalyst
Conversion[b]
Yield[b]
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9
1a: Cl
1b: Br
1c: I
59%
70%
83%
28%
10%
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1
Fe(acac)3
43.5%
1a: Cl
1b: Br
1c: I
24%
92%
Full
15%
2%
2
3
4
5
6
FeBr3
FeF2
43%
1a: Cl
1b: Br
1c: I
89%
42%
Full
10%
1%
12%
1a: Cl
1b: Br
1c: I
23%
43%
Full
3%
2.5%
FeF3
18.5%
1a: Cl
1b: Br
1c: I
48%
43%
Full
6%
2%
FeCl2
FeCl3
35%
1a: Cl
1b: Br
1c: I
65%
68%
Full
20%
14%
52.5%
[a] Initial conditions: To a solution of vinyl halides 1 (0.2 mmol) and
iron catalyst (5 mol%) in toluene (1 mL) was added a solution of 2a
(0.24 mmol, 1.2 eq.) in toluene (1 mL) over 1 h by a syringe pump at
RT; [b] GC-MS yield of the crude reaction mixture.
Next, both (E)-1-propenyllithium (2a) and (Z)-1-propenyllithium (2b) were also examined to couple with (E)-2-
iodoethenylbenzene (1c) with the aim to study the stereochemistry of this cross-coupling reaction (Scheme 1). It is
noteworthy that (E)-2-iodoethenylbenzene (1c) and (E)-alkenyllithium (2a) were coupled to exclusively form conjugated
(E,E)-dienes (3ca) with full retention of stereochemistry, illustrating that the geometrical configurations of both vinyl
iodide and alkenyllithium were fully maintained. These results were confirmed by 1H NMR spectroscopic studies and the
comparison with the relevant known compound (see SI). Meanwhile, (Z)-1-propenyllithium (2b) was also examined with
(E)-2-iodoethenylbenzene (1c), affording a diene mixture of [(1E,3Z)-1,3-pentadien-1-yl]benzene (3cb) and [(1E,3E)-
1,3-pentadien-1-yl]benzene (3ca) with an approximate ratio of 4.5 to 1,19 meaning that there was isomerization during
the reaction.
Scheme 1. Stereochemistry study.
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Table 2. Further optimizations based on iron(III) chloride.[a]
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Entry
Equiv.
of 2a
Vol. of
Toluene
(mL)
T (℃)
Conversion[a]
Yield[a]
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1
2
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2
2
4
2
RT
RT
0
Full
Full
Full
53%
63%
66%
1.2
1.2
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7
1.2
2
2
2
4
4
–20
–20
–20
–20
81%
88%
71%
78%
32%
35%
17%
21%
1.2
2
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9
1.2
2
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6
0
0
87%
93%
56%
60%
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2
1.2
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2
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4
0
0
0
0
0
77%
Full
67.5%
47%
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12[c]
13[b]
14[d]
Full
64.5%
76.5%
72%
2
Full
Full
2
[a] GC-MS yield of the crude reaction mixture; [b] Standard condition:
To a solution of 1c (0.2 mmol) and FeCl3 (5 mol%, 1.6 mg) in toluene (2
mL) was added a solution of 2a (0.4 mmol) in toluene (2 mL) over 1 h
by a syringe pump at 0 ℃; [c] 2a was added over 2 h; [d] 3 mol% FeCl3
was used.
With the carbon(sp2)-carbon(sp2) cross-coupling results achieved, we decided to carry out further optimization
based on the aforementioned iron(III) chloride catalytic system as shown in Table 2. In order to retard the formation of
polymer by-products, we first used two equivalents of the nucleophiles with the target to increase the rate of cross-
coupling reaction. We also attempted to dilute the reaction concentration and lowered the reaction temperature to 0 ℃,
respectively, aiming to reduce the rate of polymerization. To our delight, these three optimizations all worked out well to
improve the reactions (Table 2). The results of entry 3 showed that reaction temperature at 0 ℃ could increase the
reaction yield. Consequently, we reduced the reaction temperature to –20 ℃. However, the results were not
encouraging (entries 4-7). In the same manner, the outcomes were also unsatisfactory when we further diluted the
reaction concentration (from 2 mL to 6 mL) at room temperature (entries 8 and 9). In the case of entries 12 and 13, slow
addition of 2a (2a was added in a dropwise manner over 2 hours) could also not improve the yield (entry 12). As shown
in entry 13, the combination of the aforementioned factors did lead to a better reaction. Moreover, the lower loading of
iron catalyst (3 mol%) was found to deduct slightly the overall transformation efficiency (entry 14).
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Table 3. Iron-catalyzed cross-coupling of (E)-β-(hetero)aryl vinyl iodides (1)
with (E)-propenyllithium (2a).[a]
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F
Cl
Br
3ca 68%[e]
3da 59%[e]
3ea 63%[e]
3ia 59%[e]
3fa 64%[e]
MeO
I
F3C
Me
3ja 61%[e]
3ha 63%[e]
3la 54%[e]
3ga trace[b]
3ka 65%[e]
Me
tBu
Me
tBu
3ma trace[b]
3na 41%
[c,e]
Me
tBu
O
S
O
3pa trace[b]
3qa 43%[e]
3ra 71%[e]
3oa 63%[e]
F
F
3sa 40%[d,e]
3ta 56%[e]
F
[a] Conditions: To a solution of 1 (0.2 mmol) and FeCl3 (5 mol%) in toluene (2
mL) was added a solution of 2a (0.4 mmol) in toluene (2 mL) over 1 h by a
syringe pump at 0 ℃; [b] GC-MS yield was less than 3%; [c] 2a (0.8 mmol) in
toluene (4 mL) was added over 2h; [d] 0.8 mmol 2a (0.8 mmol) in toluene (4
mL) was added over 1 h; [e] Isolated yields.
With the optimal catalytic conditions in hand, the scope of the iron-catalyzed cross-coupling reaction of (E)-
propenyllithium (2a) with (E)-β-(hetero)aryl vinyl iodides (1) was further examined (Table 3). As we expected, a broad
range of fluorine, chlorine and bromine substituted phenyl vinyl iodides successfully underwent the cross-coupling with
an excellent chemoselectivity and moderate to good yields, affording the corresponding desired products (3da-3fa).
Nevertheless, iodophenyl vinyl iodide was chemoselectively incompatible with this protocol. As can be seen, the result
as detected by GC-MS was messy with a trace amount of 3ga. Vinyl iodides with both electron-deficient aromatic ring,
for example the pharmaceutical useful trifluoromethylphenylvinyl iodide,20 and electron-rich aromatic ring both could
smoothly underwent this coupling reaction to generate desired dienes in moderate to good yields (3ha, 3ia, 3ra).
Moreover, ortho-, and para-methylphenyl-related vinyl iodides were also studied. The steric hindrance exerted by mono-
ortho-methyl group was less obvious than that shown by di-ortho-methyl groups (3ja vs. 3na). Similarly, bulky para-
tertiary-butyl group has much stronger steric hindrance effect as compared with para-methyl group (3la vs. 3ka) and the
more bulky di-meta-tertiary-butyl phenyl vinyl iodide only led to a trace amount of diene (3ma). It was also uncovered
that the less-hindered (E)-2-(2-iodovinyl)naphthalene formed the coupling product (3oa) in 63% yield, while more
sterically hindered (E)-9-(2-iodovinyl)anthracene only produced a trace amount of the desired diene (3pa). To our
delight, freshly prepared (E)-β-3-thienyl vinyl iodide also successfully furnished the corresponding product (3qa).
Moreover, a double coupling alkenylation product (3sa) and trifluorophenyl alkenylation product (3ta) were also
obtained in 40% and 56% yields, respectively.
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Table 4. Iron-catalyzed cross-coupling of (E)-β-(hetero)aryl vinyl iodides (1)
with alkenyllithiums (2c, 2d).[a]
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[a] Conditions: To a solution of 1 (0.2 mmol) and FeCl3 (5 mol%) in toluene (2
mL) was added the solution of 2c or 2d (0.4 mmol) in toluene (2 mL) over 1 h
by a syringe pump at 0 ℃; [b] GC yield; [c] Isolated yields.
Encouraged by these results, we envisioned to explore the electronic effect of vinyl iodides with 1-methyl-(Z)-
propenyllithium (2c) for this optimized coupling reaction. Gratifyingly, either electron-withdrawing/donating group
substituted phenyl vinyl iodides or (E)-2-(2-iodovinyl)naphthalene and (E)-3-(2-iodovinyl)thiophene successfully
underwent this cross-coupling reaction to afford the corresponding dienes in acceptable yields (Table 4, 4). Similarly,
(E)-(2-(trimethylsilyl)vinyl)lithium (2d) also underwent successfully this coupling reaction with relevant vinyl iodides to
form respective dienes in moderate yields (Table 4, 5). However, 1,2-dimethylpropenyllithium (2e) was not able to
undergo this iron-catalyzed coupling reaction, presumably due to steric hindrance (see Supplementary Table S5).
It is noteworthy that a very essential goal in the field of catalysis is to extend basic research to procedures involving
scalable quantities for industrial application. Therefore, we also investigated the scale-up of our iron-catalyzed
procedure to multi-gram quantities. As shown in Scheme 2, both typical gram-scale reactions smoothly provided
relevant dienes in satisfactory yields in a similar procedure.
Scheme 2. Gram-scale reactions.
[a] Conditions: To a solution of 1 (10 mmol) and FeCl3 (5 mol%) in toluene
(100 mL) was added a solution of the corresponding 2a or 2c (20 mmol) in
toluene (100 mL) over 25 h by a syringe pump at 0 ℃; [b] isolated yield.
Conclusion
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In conclusion, we have developed an efficient iron-catalyzed cross-coupling reaction involving alkenyllithium and
vinyl iodides, forming useful dienes with moderate to good yields. The relevant diene products of (E)-(2-
(trimethylsilyl)vinyl)lithium and vinyl iodides could be conveniently converted further to other fine chemicals. Our newly
developed iron-catalyzed cross-coupling reactions would provide a mild, ligand-free, inexpensive, and environmentally
friendly route towards syntheses of diversified diene derivatives. To further investigate its mechanistic nature, several
applications of this procedure are underway in our laboratories.
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EXPERIMENTAL SECTION
General Information. All reactions were carried out under an atmosphere of dry argon with the rigid exclusion of air
and moisture using standard Schlenk techniques or in a glove box unless otherwise specified. All organic solvents were
freshly distilled from Na or CaH2 immediately prior to use. Analytical thin layer chromatography (TLC) was performed
with Merck silica gel 60 F254 aluminum plates. Visualization was done under a UV lamp (254 nm) and by immersion in
ethanolic phosphomolybdic acid (PMA) or potassium permanganate (KMnO4), followed by heating using a heat gun.
Purification of crude products was generally done by preparative thin layer chromatography (PLC) with Qingdao
Haiyang silica gel plates (GF254 type, 0.200.25 mm or 0.400.50 mm plate coating thickness, 200×200 mm size). For
the gram-scale reactions, the purification of crude products was generally done by flash column chromatography with
Grace Materials Technologies 230400 mesh silica gel. All other chemicals were purchased from Aldrich, Acros, J&K
Scientific, Shaoyuan Scientific and Energy Chemical and used as received unless otherwise specified.
Proton nuclear magnetic resonance spectra (1HNMR) spectra, carbon nuclear magnetic resonance spectra (13C
NMR) and fluorine nuclear magnetic resonance spectra (19F NMR) were recorded at 23 °C on a Bruker DPX 400
spectrometer in CDCl3at 400 MHz for 1H, 100 MHz for 13C and 376 MHz for 19F.Chemical shifts (1H and 13C) are
reported as parts per million in δ scale and referenced to the residual solvent peak (CDCl3, 7.27 ppm, 77.0 ppm
respectively).Chemical shifts of 19F NMR are reported as parts per million in δ scale using fluorobenzene (113.15 ppm)
or benzotrifluoride (63.72 ppm) as internal standards. Data are represented as follows: chemical shift, integration,
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, dd =doublet of doublets, dq = doublet of quartets, m =
multiplet, br = broad), and coupling constant (J, Hz). High resolution mass spectra (HRMS) were obtained on a Finnigan
MAT 95XL GC Mass Spectrometer (Magnetic sector-double focusing) or a Thermo Scientific Q Exactive Focus Mass
Spectrometer (Orbitrap). GC/MS was performed on an Agilent 7890B system (HP-5ms column) with an Agilent
5977AMSD.
Preparation of (E)-β-(hetero)aryl Vinyl Halides. Aryl vinyl iodides 1c, 1d, 1f, 1h, 1i, 1j, 1k, 1o, 1r and 1s were
prepared in accordance with a previously reported procedure.16 The spectral data are in full accordance with the
literature report.16 Aryl vinyl iodides 1e, 1l and 1q were prepared in accordance with a previously reported procedure.16
The spectral data are in full accordance with the literature report, respectively.16,21 Aryl vinyl iodide 1g, 1m, 1n and 1p
were prepared in accordance with a previously reported procedure.16
Preparation of Organolithium Reagents:
Method 1: (E)-propenyllithium (2a), (Z)-propenyllithium (2b) and 1-Methyl-(Z)-propenyllithium (2c).22 In a dry
Schlenk flask the corresponding bromide (12.85 mmol) dissolved in diethyl ether (9 mL) was added dropwise at room
temperature to a suspension of lithium shot (0.4 g) in diethyl ether (14 mL) by a syringe pump in 1.5 h. The crude
organolithiums were used for cross-coupling reaction without further purification and titration.
Method 2: (1E)-2-(Trimethylsilyl)ethenyllithium (2d), 1,2-Dimethyl-propenyllithium (2e).22-23 In a dry Schlenk flask
the corresponding bromide (3 mmol) was dissolved in dry THF (1 mL) and the solution was cooled down to 78 ℃.
tBuLi (1.3 M in pentane, 2.1 equiv, 5 mL) was added slowly and the solution was stirred for 30 min. Then the solution
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was allowed to reach room temperature and stirred for another 30 min. The crude organolithiums were used for cross-
coupling reaction without further purification and titration.
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Iron-catalysed cross-coupling of (1E)-2-iodoethenylbenzene (1c) and (E)-propenyllithium (2a). An oven-dried test
tube was equipped with a magnetic stirring bar and transferred into a glove box. FeCl3 (1.6 mg, 0.01 mmol, 5 mol%)
was charged and (1E)-2-iodoethenylbenzene (1c) (0.2 mmol) and toluene (2 mL) were added subsequently. Then, the
test tube was sealed properly with a rubber stopper and taken out from the glove box. At 0 ℃, (E)-propenyllithium (2a)
(0.4 mmol, 0.5 M in diethyl ether, diluted with 2 mL toluene) was added by a syringe pump in 1 h. After the addition was
completed, the reaction mixture was stirred at 0 ℃ for 0.5 h. Then, a saturated solution of aqueous NH4Cl was added
and the aqueous layer was extracted three times with CH2Cl2.The organic phases were collected, and the solvent
evaporation under reduced pressure afforded the crude product, which was then purified by preparative thin layer
chromatography (pure cyclohexane).
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Procedure for synthesis of 1-methoxy-3-((1E,3E)-1,3-pentadien-1-yl)benzene (3ia) and 1-((1E,3E)-3-methyl-1,3-
pentadien-1-yl)-4-(trifluoromethyl)benzene (4hc) in a multi-gram scale. An 500 mL oven-dried round bottom flask
was equipped with a magnetic stirring bar and transferred into a glove box. FeCl3 (80 mg, 0.5 mmol, 5 mol%) was
charged. Then, the flask was sealed properly with a rubber stopper and taken out from the glove box. (1E)-2-
iodoethenyl-3-methoxybenzene (1i) and vinyl iodide (1h) (10 mmol) and toluene (100 mL) were added subsequently.
The flask was transferred to 0 ℃ (ice bath), (E)-propenyllithium (2a) or 1-Methyl-(Z)-propenyllithium (2c) (20 mmol, 0.5
M in diethyl ether, diluted with 100 mL toluene) was added by a syringe pump in 25 h. After the addition was completed,
the reaction mixture was stirred at 0 ℃ for 0.5 h. Then, a saturated solution of aqueous NH4Cl (100 mL) was added and
the aqueous layer was extracted three times with CH2Cl2 (200 mL).The organic phases were collected, and the solvent
evaporation under reduced pressure afforded the crude product, which was then purified by silica gel flash column
chromatography (pure cyclohexane).
1-((E)-2-Iodoethenyl)-4-iodobenzene (1g).16 Prepared according to the general procedure and purified by preparative
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thin layer chromatography. Colorless oil (61% yield, 430.8 mg, 2.0 mmol scale). H NMR (400 MHz, CDCl3) δ 7.65 (d, J
= 8.4 Hz, 2H), 7.34 (d, J = 15.0 Hz, 1H), 7.02 (d, J = 8.3 Hz, 2H), 6.88 (d, J = 15.0 Hz, 1H). 13C NMR (100 MHz, CDCl3)
δ 144.0, 137.9, 137.2, 127.7, 94.1, 77.9. HRMS m/z (ESI): calcd. for C8H6I2 [M+H]+: 355.8553; found: 355.8553.
1-((E)-2-Iodoethenyl)-3,5-di-tert-butylbenzene (1m).16 Prepared according to the general procedure and purified by
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preparative thin layer chromatography. Colorless oil (52% yield, 355.7 mg, 2.0 mmol scale). H NMR (400 MHz, CDCl3)
δ 7.51 (d, J = 15.0 Hz, 1H), 7.427.41 (m, 1H), 7.18 (d, J = 1.8 Hz,2H), 6.84 (d, J = 15.0 Hz, 1H), 1.37 (s, 18H). 13C
NMR (100 MHz, CDCl3) δ 151.3, 146.1, 137.2, 122.8, 120.5, 75.9, 35.0, 31.6. HRMS m/z (ESI): calcd. for C16H23I
[M+H]+: 343.0917; found: 343.0912.
1-((E)-2-Iodoethenyl)-2,6-dimethylbenzene (1n).16 Prepared according to the general procedure and purified by
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preparative thin layer chromatography. Colorless oil (58% yield, 299.3 mg, 2.0 mmol scale). H NMR (400 MHz, CDCl3)
δ 7.47 (d, J = 15.1 Hz,1H), 7.147.10 (m, 1H), 7.067.03 (m, 2H), 6.33 (d, J = 15.0 Hz, 1H), 2.30 (s, 6H). 13C NMR (100
MHz, CDCl3) δ 143.6, 137.7, 135.7, 128.0, 127.6, 80.4, 21.0. HRMS m/z (ESI): calcd. for C10H11I [M]+: 257.9899; found:
257.9895.
9-((E)-2-Iodoethenyl)anthracene (1p).16 Prepared according to the general procedure and purified by preparative thin
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layer chromatography. Colorless oil (47% yield, 310.2 mg, 2.0 mmol scale). H NMR (400 MHz, CDCl3) δ 8.44 (s, 1H),
8.258.20 (m, 3H), 8.01 (d, J = 8.0 Hz,2H), 7.547.46 (m, 4H), 6.69 (d, J = 15.1 Hz,1H). 13C NMR (100 MHz, CDCl3)
δ141.9, 133.0, 131.5, 129.2, 128.7, 127.3, 126.1, 125.7, 125.5, 83.5. HRMS m/z (ESI): calcd. for C16H11I [M]+: 329.9900;
found: 329.9902.
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((1E,3E)-1,3-Pentadien-1-yl)benzene (3ca).24 Prepared according to the general procedure and purified by
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preparative thin layer chromatography (cyclohexane). Colorless oil (68% yield from 1a, 19.7 mg). H NMR (400 MHz,
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CDCl3) δ 7.37 (d, J = 7.3 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 6.75 (dd, J = 15.7, 10.4 Hz, 1H), 6.42
(d, J = 15.7 Hz, 1H), 6.266.19 (m, 1H), 5.83 (dq, J = 14.9, 6.8 Hz, 1H), 1.82 (d, J = 6.8 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ 137.8, 132.0, 130.5, 129.9, 129.5, 128.7, 127.2, 126.3, 18.5. HRMS m/z (ESI): calcd. for C11H12 [M+H]+:
145.1012; found: 145.1010.
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1-Fluoro-4-((1E,3E)-1,3-pentadien-1-yl)benzene (3da).25 Prepared according to the general procedure and purified by
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preparative thin layer chromatography (cyclohexane). Colorless solid (59% yield from 1d, 19.1 mg). H NMR (400 MHz,
CDCl3) δ 7.357.31 (m, 2H), 7.016.96 (m, 2H), 6.65 (dd, J = 15.7, 10.4 Hz, 1H), 6.38 (d, J = 15.7 Hz, 1H), 6.246.17
(m, 1H), 5.83 (dq, J = 14.9, 6.8 Hz, 1H), 1.82 (dd, J = 6.7, 1.2 Hz, 3H).13C NMR (100 MHz, CDCl3) δ 163.4, 134.0, 131.8,
130.5, 129.3, 128.6, 127.7 (d, J = 17.7 Hz), 115.6 (d, J = 21.8 Hz), 18.5. 19F NMR (376 MHz, CDCl3) δ 116.4 (s, 1F).
HRMS m/z (EI): calcd. for C11H11F [M]+: 162.0845; found: 162.0846.
1-Chloro-4-((1E,3E)-1,3-pentadien-1-yl)benzene (3ea).26 Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Light yellow solid (63% yield from 1e, 22.4 mg). 1H NMR (400
MHz, CDCl3) δ 7.317.28 (m, 2H), 7.27 (s, 1H), 7.267.24 (m, 1H), 6.71 (dd, J = 15.7, 10.4 Hz, 1H), 6.37 (d, J = 15.7
Hz, 1H), 6.246.17 (m, 1H), 5.85 (dq, J = 14.9, 6.9 Hz, 1H), 1.82 (d, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
136.3, 132.7, 131.7, 131.2, 130.1, 128.8, 128.5, 127.4, 18.5. HRMS m/z (EI): calcd.for C11H11Cl [M]+: 178.0544; found:
178.0545.
1-Bromo-4-((1E,3E)-1,3-pentadien-1-yl)benzene (3fa).27 Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Light yellow solid (64% yield from 1f, 28.4 mg). 1H NMR (400
MHz, CDCl3) δ 7.41 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.4 Hz, 2H), 6.73 (dd, J = 15.7, 10.4 Hz, 1H), 6.35 (d, J = 15.7 Hz,
1H), 6.24-6.17 (m, 1H), 5.86 (dq, J = 14.9, 6.8 Hz, 1H), 1.82 (d, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 136.8,
131.8, 131.7, 131.3, 130.2, 128.5, 127.7, 120.8, 18.6. HRMS m/z (EI): calcd.for C11H11Br [M]+: 222.0039; found:
222.0041.
1-((1E,3E)-1,3-pentadien-1-yl)-4-(trifluoromethyl)benzene (3ha).28 Prepared according to the general procedure and
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purified by preparative thin layer chromatography (cyclohexane). White wax-like solid (63% yield from 1h, 26.7 mg). H
NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.2 Hz, 2H), 7.45 (d, J = 8.2 Hz, 2H), 6.82 (dd, J = 15.7, 10.4 Hz, 1H), 6.43 (d, J =
15.7 Hz, 1H), 6.276.21 (m, 1H), 5.92 (dq, J = 14.9, 6.8 Hz, 1H), 1.84 (d, J = 6.7 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
141.3, 132.5, 131.9, 131.6, 129.0, 128.7, 128.3, 126.3, 125.6 (q, J = 3.7 Hz), 18.6. 19F NMR (376 MHz, CDCl3) δ 62.4
(s, 3F). HRMS m/z (EI): calcd. for C12H11F3 [M]+: 212.0807; found: 212.0810.
1-Methoxy-3-((1E,3E)-1,3-pentadien-1-yl)benzene (3ia). Prepared according to the general procedure and purified by
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preparative thin layer chromatography (cyclohexane). Light yellow oil (59% yield from 1i, 35.9 mg). H NMR (400 MHz,
CDCl3) δ 7.22 (t, J = 7.9 Hz, 1H), 6.98 (d, J = 7.6 Hz,1H), 6.92 (s, 1H), 6.786.71 (m, 2H), 6.40 (d, J = 15.7 Hz, 1H),
6.266.19 (m, 1H), 5.85 (dq, J = 14.9, 6.8 Hz, 1H), 3.82 (s, 3H), 1.83 (d, J = 6.7 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
159.9, 139.3, 131.9, 130.7, 129.8, 129.7, 129.6, 119.0, 112.9, 111.5, 55.3, 18.5. HRMS m/z (ESI): calcd. for C12H14O
[M+H]+: 175.1117; found: 175.1117.
1-Methyl-2-((1E,3E)-1,3-pentadien-1-yl)benzene (3ja). Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Colorless oil (61% yield from 1j, 19.3 mg). 1H NMR (400 MHz,
CDCl3) δ 7.47 (d, J = 7.4 Hz, 1H), 7.187.11 (m, 3H), 6.676.65 (m, 2H), 6.31-6.24 (m, 1H), 5.84 (dq, J = 14.9, 6.8 Hz,
1H), 2.35 (s, 3H), 1.83 (dd, J = 6.8, 1.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 136.6, 135.5, 132.4, 130.6, 130.5, 130.3,
127.5, 127.2, 126.2, 125.0, 20.0, 18.5. HRMS m/z (ESI): calcd. for C12H14 [M+H]+: 159.1168; found: 159.1168.
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4-Methyl-2-((1E,3E)-1,3-pentadien-1-yl)benzene (3ka).29 Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). White solid (65% yield from 1k, 20.5 mg). 1H NMR (400 MHz,
CDCl3) δ 7.28 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.72 (dd, J = 15.5, 10.2 Hz, 1H), 6.41 (d, J = 15.7 Hz, 1H),
6.266.19 (m, 1H), 5.81 (dq, J = 14.6, 7.0 Hz, 1H), 2.34 (s, 3H), 1.83 (d, J = 6.9 Hz, 3H).13C NMR (100 MHz, CDCl3) δ
137.0, 135.0, 132.1, 129.8, 129.8, 129.4, 128.5, 126.2, 21.3, 18.5. HRMS m/z (ESI): calcd. for C12H14 [M+H]+: 159.1168;
found: 159.1167.
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1-((1E,3E)-1,3-Pentadien-1-yl)-4-tert-butylbenzene (3la). Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Colorless oil (54% yield from 1l, 21.6 mg). 1H NMR (400 MHz,
CDCl3) δ 7.377.33 (m, 4H), 6.73 (dd, J = 15.6, 10.4 Hz, 1H), 6.42 (d, J = 15.7 Hz, 1H), 6.266.19 (m, 1H), 5.82 (dq, J =
14.9, 6.9 Hz, 1H), 1.83 (d, J = 6.7 Hz, 3H), 1.32 (s, 9H).13C NMR (100 MHz, CDCl3) δ 150.3, 135.0, 132.2, 129.8, 129.7,
128.8, 126.0, 125.6, 34.7, 31.4, 18.5. HRMS m/z (EI): calcd. for C15H20 [M]+: 200.1560; found: 200.1561.
2,6-Dimethyl-1-((1E,3E)-1,3-pentadien-1-yl)benzene (3na). Prepared according to the general procedure and purified
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by preparative thin layer chromatography (cyclohexane). Colorless oil (41% yield from 1n, 14.1 mg). H NMR (400 MHz,
CDCl3) δ 7.04 (s, 3H), 6.466.42 (m,1H), 6.286.24 (m, 2H), 5.76 (dq, J = 14.0, 6.8 Hz, 1H), 2.32 (s, 6H), 1.83 (d, J =
6.5 Hz, 3H).13C NMR (100 MHz, CDCl3) δ 137.1, 136.2, 134.8, 132.3, 129.6, 128.0, 127.9, 126.5, 21.3, 18.4. HRMS m/z
(EI): calcd. for C13H16 [M]+: 172.1247; found: 172.1250.
2-((1E,3E)-1,3-Pentadien-1-yl)naphthalene (3oa).30 Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Light yellow solid (63% yield from 1o, 24.4 mg). 1H NMR (400
MHz, CDCl3) δ 7.78 (t,J = 7.6 Hz, 3H), 7.72 (s,1H), 7.62 (dd,J = 8.5, 1.4 Hz,1H), 7.487.40 (m,2H), 6.90 (dd, J = 15.6,
10.4 Hz, 1H), 6.60 (d, J = 15.7 Hz, 1H), 6.336.26 (m, 1H), 5.90 (dq, J = 14.6, 6.9 Hz, 1H), 1.87 (d, J = 6.6 Hz, 3H). 13
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NMR (100 MHz, CDCl3) δ 135.3, 133.9, 132.9, 132.1, 130.7, 130.0, 129.9, 128.3, 128.0, 127.8, 126.3, 126.0, 125.7,
123.6, 18.6. HRMS m/z (ESI): calcd. for C15H14 [M+H]+: 195.1168; found: 195.1167.
3-((1E,3E)-1,3-Pentadien-1-yl)thiophene (3qa). Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Light yellow solid (43% yield from 1q, 12.9 mg). 1H NMR(400
MHz, CDCl3) δ 7.277.25 (m, 1H), 7.22 (dd, J = 5.1, 1.0 Hz,1H), 7.11 (d, J = 2.1 Hz, 1H), 6.59 (dd, J = 15.6, 10.3 Hz,
1H), 6.44 (d, J = 15.7 Hz, 1H), 6.216.13 (m, 1H), 5.79 (dq, J = 14.9, 6.9 Hz, 1H), 1.82 (dd, J = 6.7, 1.0Hz, 3H). 13C
NMR (100 MHz, CDCl3) δ 140.5, 131.9, 129.9, 129.6, 126.0, 125.0, 124.1, 121.3, 18.5. HRMS m/z (ESI): calcd. for
C9H10S [M+H]+: 151.0576; found: 151.0575.
5-((1E,3E)-1,3-Pentadien-1-yl)-1,3-Benzodioxole (3ra). Prepared according to the general procedure and purified by
preparative thin layer chromatography (cyclohexane). Light yellow solid (71% yield from 1r, 26.7 mg). 1H NMR (400
MHz, CDCl3) δ 6.92 (s, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.74 (d, J = 8.0 Hz,1H), 6.58 (dd, J = 15.6, 10.3 Hz, 1H), 6.34 (d, J
= 15.6 Hz, 1H), 6.226.15 (m, 1H), 5.94 (s, 2H), 5.79 (dq, J = 14.9, 6.9Hz, 1H), 1.81 (d, J = 6.7Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 148.1, 147.0, 132.4, 131.9, 129.7, 129.5, 127.9, 121.0, 108.5, 105.4, 101.1, 18.5. HRMS m/z (ESI):
calcd. for C12H12O2 [M+H]+: 189.0910; found: 189.0914.
1,3-Bis-((1E,3E)-1,3-pentadien-1-yl)benzene (3sa). Prepared according to the general procedure and purified by
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preparative thin layer chromatography (cyclohexane). Colorless oil (40% yield from 1s, 16.8 mg). H NMR (400 MHz,
CDCl3) δ 7.36 (s, 1H), 7.23 (s, 3H), 6.76 (dd, J = 15.6, 10.4 Hz, 2H), 6.41 (d, J = 15.7 Hz, 2H), 6.266.19 (m, 2H), 5.85
(dq, J = 14.9, 6.9 Hz, 2H), 1.83 (d, J = 6.7Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 138.0, 132.0, 130.6, 129.8, 129.6,
128.9, 125.0, 124.2, 18.5. HRMS m/z (ESI): calcd. for C16H18 [M+H]+: 211.1481; found: 211.1479.
1,2,3-Trifluoro-5-((1E,3E)-penta-1,3-dien-1-yl)benzene (3ta). Prepared according to the general procedure and
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MHz, CDCl3) δ 6.976.91 (m, 2H), 6.676.61 (dd, J = 12.0 Hz, 8.0 Hz, 1H), 6.25 (d, J = 16.0 Hz, 1H), 6.226.15 (m, 1H),
5.945.85 (m, 1H), 1.83 (d, J = 4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 132.7, 131.6 (d, J = 2Hz), 130.9, 126.6 (t, J =
5.0 Hz, 3Hz), 109.72, 109.66, 109.6, 109.5, 18.4. 19F NMR (376 MHz, CDCl3) δ 135.0 (d, J = 18.8 Hz, 3F), 162.4 (t, J
= 41.4 Hz, 18.8 Hz, 1F). HRMS m/z (ESI): calcd. for C11H9F3 [M+H]+: 199.0729; found: 199.0730.
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((1E,3E)-3-Methyl-1,3-pentadien-1-yl)benzene (4cc).31 Prepared according to the general procedure and purified by
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preparative thin layer chromatography (cyclohexane). Colorless oil (70% yield from 1c, 22.1 mg). H NMR (400 MHz,
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CDCl3) δ 7.41 (d, J = 7.6 Hz, 2H), 7.31 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 6.82 (d, J = 16.1 Hz, 1H), 6.45 (d, J =
16.1 Hz, 1H), 5.72 (q, J = 7.0 Hz, 1H), 1.87 (s, 3H), 1.80 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 138.2, 134.9,
134.1, 128.7, 128.4, 127.0, 126.3, 125.4, 14.3, 12.2. HRMS m/z (ESI): calcd. for C12H14 [M+H]+: 159.1168; found:
159.1167.
1-((1E,3E)-3-Methyl-1,3-pentadien-1-yl)-4-(trifluoromethyl)benzene (4hc). Prepared according to the general
procedure and purified by preparative thin layer chromatography (cyclohexane). White solid (69% yield from 1h, 31.2
mg). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.3 Hz, 2H), 6.87 (d, J = 16.1 Hz, 1H), 6.44 (d, J
= 16.1 Hz, 1H), 5.79 (q, J = 7.0 Hz, 1H), 1.87 (s, 3H), 1.82 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 141.7,
136.5, 134.6, 130.3, 128.7, 128.4, 126.3, 125.8, 125.6, 125.6 (q, J = 3.8 Hz), 124.0, 123.1, 14.4, 12.2. 19F NMR (376
MHz, CDCl3) δ 61.6 (s, 3F). HRMS m/z (ESI): calcd. for C13H13F3 [M+H]+: 227.1042; found: 227.1045.
1-Methoxy-3-((1E,3E)-3-methyl-1,3-pentadien-1-yl)benzene (4ic). Prepared according to the general procedure and
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purified by preparative thin layer chromatography (cyclohexane). Colorless oil (69% yield from 1i, 25.9 mg). H NMR
(400 MHz, CDCl3) δ 7.22 (t, J = 8.0 Hz,1H), 7.01 (d, J = 7.6 Hz, 1H), 6.966.94 (m, 1H), 6.80 (d, J = 16.0 Hz, 1H), 6.76
(dd, J = 8.2, 2.1 Hz, 1H), 6.42 (d, J = 16.0 Hz, 1H), 5.73 (q, J = 7.0 Hz, 1H), 3.83 (s, 3H), 1.86 (s, 3H), 1.80 (d, J = 7.0
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 159.9, 139.7, 134.8, 134.4, 129.6, 128.6, 125.3, 119.0, 112.7, 111.5, 55.3, 14.3,
12.2. HRMS m/z (ESI): calcd. for C13H16O [M+H]+: 189.1274; found: 189.1272.
2-((1E,3E)-3-Methyl-1,3-pentadien-1-yl)naphthalene (4oc).32 Prepared according to the general procedure and
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purified by preparative thin layer chromatography (cyclohexane). White solid (58% yield from 1o, 24.1 mg). H NMR
(400 MHz, CDCl3) δ 7.807.75 (m, 4H), 7.64 (d, J = 8.6 Hz, 1H), 7.477.39 (m, 2H), 6.95 (d, J = 16.0 Hz, 1H), 6.62 (d, J
= 16.0 Hz, 1H), 5.78 (q, J = 7.0 Hz, 1H), 1.92 (s, 3H), 1.83 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 135.7,
134.9, 134.5, 133.9, 132.8, 128.6, 128.2, 128.0, 127.8, 126.3, 126.0, 125.6, 125.5, 123.7, 14.3, 12.2. HRMS m/z (ESI):
calcd. for C16H16 [M+H]+: 209.1325; found: 209.1328.
3-((1E,3E)-3-Methyl-1,3-pentadien-1-yl)thiophene (4qc). Prepared according to the general procedure and purified by
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preparative thin layer chromatography (cyclohexane). Light yellow solid (40% yield from 1q, 13.1 mg). H NMR (400
MHz, CDCl3) δ 7.30-7.26 (m, 1H), 7.257.23 (m, 1H), 7.137.12 (m, 1H), 6.67 (d, J = 16.0 Hz, 1H), 6.47 (d, J = 16.0
Hz,1H), 5.67 (q, J = 7.0 Hz, 1H), 1.83 (s, 3H), 1.78 (d, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 140.9, 134.7,
134.1, 127.7, 126.0, 125.1, 121.0, 119.8, 14.2, 12.1. HRMS m/z (ESI): calcd. for C10H12S [M+H]+: 165.0732; found:
165.0731.
((1E,3E)-4-(Trimethylsilyl)-1,3-butadien-1-yl)benzene (5cd).33 Prepared according to the general procedure and
1
purified by preparative thin layer chromatography (cyclohexane). Colorless oil (53% yield from 1c, 21.4 mg). H NMR
(400 MHz, CDCl3) δ 7.41 (d, J = 7.4 Hz, 2H), 7.32 (t, J = 7.5 Hz, 3H), 6.80 (dd, J = 15.4, 10.0 Hz, 1H), 6.69 (dd, J = 10.0,
8.0 Hz, 1H), 6.59 (d, J = 15.4 Hz, 1H), 6.01 (d, J = 17.9 Hz, 1H), 0.13 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 144.2,
137.4, 135.1, 133.0, 131.8, 128.8, 127.8, 126.7, 1.1. HRMS m/z (ESI): calcd. for C13H18Si [M]+: 202.1178; found:
202.1175.
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1-(Trifluoromethyl)-4-((1E,3E)-4-(trimethylsilyl)-1,3-butadien-1-yl)benzene (5hd).34 Prepared according to the
general procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow oil (37% yield from
1h, 20.0 mg). 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.3 Hz, 2H), 6.85 (dd, J = 15.6, 10.0 Hz,
1H), 6.69 (dd, J = 10.0, 8.0 Hz, 1H), 6.58 (d, J = 15.5 Hz, 1H), 6.10 (d, J = 18.1 Hz, 1H), 0.13 (s, 9H).13C NMR (100
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MHz, CDCl3) δ 143.6, 140.9, 137.5, 134.1, 131.2, 129.1 (q, J = 33.0 Hz), 126.7, 125.7 (q, J = 4.0 Hz), 124.3 (q, J = 259.0
Hz), 1.21. 19F NMR (376 MHz, CDCl3) δ 61.7 (s, 3F). HRMS m/z (ESI): calcd. for C14H17F3Si [M+H]+: 271.1124; found:
271.1124.
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1-Methoxy-3-((1E,3E)-4-(trimethylsilyl)-1,3-butadien-1-yl)benzene (5id). Prepared according to the general
procedure and purified by preparative thin layer chromatography (cyclohexane). Light yellow oil (61% yield from 1i, 28.3
1
mg). H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 7.9 Hz, 1H), 7.01 (d, J = 6.7 Hz, 1H), 6.94 (s, 1H), 6.816.79 (m, 1H),
6.76 (d, J = 10.1 Hz, 1H), 6.68 (dd, J = 10.0, 8.0 Hz, 1H), 6.55 (d, J = 15.2 Hz, 1H), 6.02 (d, J = 17.9 Hz, 1H), 3.82 (s,
3H), 0.12 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 159.9, 144.1, 138.8, 135.4, 132.9, 132.1, 129.7, 119.4, 113.5, 111.8,
55.3, 1.1. HRMS m/z (ESI): calcd. for C14H20OSi [M]+: 232.1283; found: 232.1279.
2-((1E, 3E)-4-(Trimethylsilyl)-1,3-butadien-1-yl)naphthalene (5od).35 Prepared according to the general procedure
and purified by preparative thin layer chromatography (cyclohexane). Light yellow solid (59% yield from 1o, 29.7 mg). 1H
NMR (400 MHz, CDCl3) δ 7.827.77 (m, 3H), 7.76 (s, 1H), 7.63 (d, J = 8.4 Hz, 1H), 6.496.41 (m, 2H), 6.93 (dd, J =
15.5, 10.0 Hz,1H), 6.78 (d, J = 8.0 Hz, 1H),6.73 (t, J = 4.9 Hz, 1H), 6.06 (d, J = 18.2 Hz, 1H), 0.15 (s, 9H). 13C NMR
(100 MHz, CDCl3) δ 144.3, 135.4, 134.9, 133.8, 133.2, 133.1, 132.2, 128.4, 128.1, 127.8, 126.8, 126.4, 126.1, 123.7,
1.1. HRMS m/z (ESI): calcd. for C17H20Si [M]+: 252.1329; found: 252.1329.
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI:XXXX.
Experimental results for “Optimization of Reaction Conditions”, “Iron-catalyzed Cross-coupling with (Z)-
Propenyllithium and 1,2-Dimethyl-propenyllithium”. 1H NMR and 13C NMR spectra of compounds 3ca, 3da,
3ea, 3fa, 3ha, 3ia, 3ja, 3ka, 3la, 3na, 3oa, 3qa, 3ra, 3sa, 3ta, 4cc, 4hc, 4cc, 4oc, 4qc, 5cd, 5hd, 5id, 5od. 19F
NMR spectra of compounds 3da, 3ha, 3ta, 4hc, 5hd.
AUTHOR INFORMATION
Corresponding Author
*E-mail: hncwong@cuhk.edu.hk
*E-mail: xspeng@cuhk.edu.hk
Author Contributions
The manuscript was written through contributions of all authors. / All authors have given approval to the final version of
the manuscript.
Notes
Any additional relevant notes should be placed here.
ACKNOWLEDGMENT
Grants from the National Natural Science Foundation of China (NSFC Project Nos. 21672181/21272199), Shenzhen
Science and Technology Innovation Committee (JCYJ20160608151520697/JCYJ20140425184428455), NSFC/RGC
Joint Research Scheme (N_CUHK451/13), Research Grants Council of Hong Kong (GRF Projects
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403012/CUHK14309216/CUHK14303815 and CRF PolyU C5023-14G), a grant to the State Key Laboratory of
Synthetic Chemistry and GHP/004/16GD from Innovation and Technology Commission, The Chinese Academy of
Sciences-Croucher Foundation Funding Scheme for Joint Laboratories are gratefully acknowledged.
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