Rhodium-catalyzed allylic substitution reactions with indium(III) organometallics

Article abstract of DOI:10.1002/ejoc.201200104

A novel rhodium-catalyzed allylic substitution reaction using indium organometallics is reported. Aryl- and heteroarylindium reagents reacted in THF at 80 °C with primary and secondary allyl halides and their derivatives under rhodium(I) catalysis to afford the α-substituted products in good yields and with high regio- and stereoselectivity. The reaction takes place with substoichiometric amounts of the triorganoindium reagents, which demonstrates the efficiency of the indium-rhodium transmetallation process in carbon-carbon bond-forming reactions. Copyright

Full text of DOI:10.1002/ejoc.201200104

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
FULL PAPER
DOI: 10.1002/ejoc.201200104
Rhodium-Catalyzed Allylic Substitution Reactions with Indium(III)
Organometallics
Ricardo Riveiros,[a] Rubén Tato,[a] José Pérez Sestelo,*[a] and Luis A. Sarandeses*[a]
Keywords: Organometallics / Indium / Rhodium / Allylic compounds / C–C coupling
A novel rhodium-catalyzed allylic substitution reaction using
and with high regio- and stereoselectivity. The reaction takes
indium organometallics is reported. Aryl- and heteroarylind- place with substoichiometric amounts of the triorganoindium
ium reagents reacted in THF at 80 °C with primary and sec-
ondary allyl halides and their derivatives under rhodium(I)
catalysis to afford the α-substituted products in good yields
reagents, which demonstrates the efficiency of the indium–
rhodium transmetallation process in carbon–carbon bond-
forming reactions.
pling reactions with aryl or alkenyl halides in which all
three groups are efficiently transferred.[6] Based on the gen-
erally accepted mechanism for the Cu-catalyzed reactions,
and in accordance with the stereochemical evidence for the
Pd-catalyzed substitution reactions, the allylic substitution
reactions take place through a key transmetallation step in
the π-allylmetal intermediate. Recently, we discovered that
organoindium reagents can also be used in Rh-catalyzed
conjugate additions to electron-deficient olefins.[9] Herein
we report that triorganoindium reagents react with allylic
halides under rhodium catalysis.
The use of rhodium complexes activated by phosphanes
in allylic substitution reactions with soft nucleophiles was
pioneered by Tsuji and co-workers.[10] Evans and Takeuchi
and their co-workers subsequently improved the method
and reported that the combination of Rh complexes and
phosphites promotes the highly regioselective allylic alkyl-
ation of unsymmetrical allylic esters.[11,12] Furthermore, the
use of optically active ligands allowed the development of
enantioselective reactions.[13] On the other hand, the Rh-
catalyzed allylic substitution reaction has been extended to
unstabilized carbon nucleophiles with some examples per-
formed with zinc organometallics[14] and arylboronic ac-
ids.[15]
Introduction
Transition-metal-catalyzed allylic substitution reactions
represent a powerful methodology for the regio- and
stereocontrolled formation of C–C bonds.[1] Allylic substi-
tution with soft nucleophiles, such as malonates and related
anions,[2] can be performed with several transition metals
(e.g., Pd, Mo, Ir, Rh), whereas the reaction with hard nu-
cleophiles, such as organometallic reagents, takes place un-
der copper catalysis,[3] although some examples with other
transition metals have been reported recently.[4] Metal-cata-
lyzed allylic substitution reactions involve the formation of
a π-allylmetal complex as a key intermediate; the soft car-
bon nucleophiles usually attack the allyl ligand anion from
the opposite side to the metal, whereas hard carbon nucleo-
philes usually undergo transmetallation at the metal center
of the π-allyl intermediate and substitution occurs by a re-
ductive elimination step.[2] The regioselectivity is a function
of the allylic electrophile and the metal catalyst, and the
use of asymmetric ligands has allowed the development of
enantioselective transformations.[5]
As part of a program focused on the development of new
applications of indium organometallics in organic synthe-
sis,[6,7] we reported the regioselective copper- and palla-
dium-catalyzed allylic substitution reactions with triorgano-
indium compounds.[8] Interestingly, copper catalysis pro-
vides the γ-substituted product (SN2Ј) and palladium catal-
ysis the α-substituted product (SN2). In these transforma-
tions the R3In reagents transfer one of the three organic
groups, a reaction pattern that contrasts that of cross-cou-
Results and Discussion
As a starting point, we studied the reaction of tri-
phenylindium (35 mol-%) with cinnamyl chloride (1a) in
THF at room temp. by using [Rh(cod)Cl]2 (2 mol-%) as cat-
alyst (Table 1, entry 1). Initially, after 10 h, the α-substi-
tuted product 2 was obtained in 36% yield, but when the
reaction was performed at 80 °C the yield increased to 53%
(entry 2) and a significant amount of 1,1Ј-biphenyl was ob-
tained as a byproduct, probably formed by reductive dimer-
ization of the organometallic reagent during the reaction.
[a] Departamento de Química Fundamental, Universidade da
Coruña,
15071 A Coruña, Spain
Fax: +34-981-167-065
E-mail: qfsarand@udc.es
sestelo@udc.es
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200104.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
R. Riveiros, R. Tato, J. Pérez Sestelo, L. A. Sarandeses
FULL PAPER
For this reason, the amount of Ph3In was increased to 6 (76–92% yields, entries 3–5). Analogously, the reaction of
50 mol-% and compound 2 was then obtained in good yield tri(1-naphthyl)indium with 1a afforded the α-substituted
(77%, entry 3). Other RhI complexes, such as product 7 (60% yield, entry 6). Interestingly, heteroarylind-
[Rh(acac)(CO)2] or [Rh(acac)(nbd)], gave similar results (65 ium reagents such as 2-thienyl, benzo[b]thien-2-yl, 2-fur-
and 70% yields, respectively, entries 4 and 5), whereas the anyl, and 2-benzofuranyl could also be used in the rho-
use of [Rh(cod)]2BF4 gave a lower yield (46%, entry 6). dium-catalyzed allylic substitution reaction to give the cor-
Comparable yields (70–78%, entries 7–8) were obtained responding α-substitution products 8–11 in moderate-to-
when the reaction was performed in the presence of phos- good yields (50–71%, entries 7–10).
phane ligands such as xantphos or dpephos. Note that more
than one phenyl group of the organoindium reagent is
transferred to 1a and this represents an improvement on
our previous results with Cu- and Pd-catalyzed allylic sub-
stitution reactions.[8]
Table 2. Reaction of triaryl- and triheteroarylindium organometal-
lics with 1a under rhodium catalysis.
Table 1. Reaction of triphenylindium with cinnamyl derivatives 1a–
1e under rhodium catalysis.
Entry
X
Catalyst
Yield [%]
1
2
3
4
5
6
7
8
Cl (1a)
[Rh(cod)Cl]2
[Rh(cod)Cl]2
36[a,b]
53[a]
77 (79)[c]
65
Cl (1a)
Cl (1a)
[Rh(cod)Cl]2
Cl (1a)
[Rh(acac)(CO)2][d]
[Rh(acac)(nbd)][d]
Cl (1a)
70
[d]
Cl (1a)
[Rh(cod)2]BF4
46
Cl (1a)
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
78[e]
70[f]
61
Cl (1a)
9
Br (1b)
10
11
12
OAc (1c)
OBz (1d)
OCO2Me (1e)
65
62
80
[a] Reaction using 35 mol-% of Ph3In. [b] Reaction performed at
room temperature. [c] In parentheses, yield using 100 mol-% of
Ph3In. [d] Reaction using 4 mol-% of catalyst. [e] Reaction in the
presence of 4 mol-% xantphos. [f] Reaction in the presence of
4 mol-% dpephos.
Under the optimized reaction conditions, we studied the
rhodium-catalyzed allylic substitution of Ph3In with other
cinnamyl derivatives, such as the bromide, esters, and a carb-
onate. The reaction of Ph3In with cinnamyl bromide (1b)
afforded the α-substituted product 2 (SN2) in 61% yield (en-
try 9) and the reaction with cinnamyl acetate (1c), benzoate
(1d), and methyl carbonate (1e) also provided 2 as the only
product in good yields (62–80%, entries 10–12).
We also explored the versatility of the reaction by using
other indium organometallics and allylic electrophiles. It
was found that a variety of functionalized aryl- and het-
eroarylindium reagents react efficiently with cinnamyl
In addition, we studied the Rh-catalyzed allylic substitu-
chloride (1a) and provide regioselectively the α-substituted tion of indium organometallics with the secondary allylic
products in good yields. For example, the reaction of tri(p- chloride 12.[16] Under the previously developed conditions
tolyl)indium (50 mol-%) with 1a under the above conditions (50 mol-% of Ph3In, 10 h, 80 °C), the α-substitution prod-
gave the allylic substitution product 3 in excellent yield uct 13 was obtained regioselectively in moderate yield
(96%, Table 2, entry 2). Arylindium reagents furnished with (57%). This yield was improved by using 70 mol-% of Ph3In
methoxy or fluoro groups also reacted with 1a to give good (80%, Table 3, entry 1). Unfortunately, partial isomeriza-
yields of the corresponding allylic substitution products 4– tion of the double bond was observed in both cases (E/Z =
2
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
Rhodium-Catalyzed Allylic Substitution Reactions
85:15).[17] As a continuation of this study, the reactions of
substituted triarylindium reagents, such as the 4-methyl-, 2-
and 4-methoxy-, and 4-fluorophenyl systems, with 12 gave
the corresponding α-substituted products 14–17 regioselec-
tively in good yields (72–97%, entries 2–5). Only in the re-
action with tris(2-methoxyphenyl)indium was a small
amount of the γ-substituted regioisomer also observed (α/γ
Scheme 1. Reaction of Ph3In with 18 under rhodium catalysis.
= 82:18, entry 4), which can be attributed to the steric hin- Conclusions
drance of the nucleophile. On the other hand, partial iso-
We have reported herein the first examples of rhodium-
merization of the double bond was detected in all cases,
which supports the formation of a π-allylrhodium complex
as the intermediate.
catalyzed allylic substitution reactions with indium organo-
metallics. In this reaction, arylindium reagents (50–70 mol-
%) reacted with primary and secondary allyl halides and
their derivatives under rhodium catalysis to afford the α-
substituted products in good yields. The reaction is cata-
lyzed by a RhI complex and proceeds efficiently with sub-
stoichiometric amounts of the triorganoindium reagents. It
was also demonstrated that more than one aryl group at-
tached to the metal is transferred to the electrophile. Fur-
ther studies concerning the synthetic utility of this method-
ology and efforts to develop an enantioselective version are
under investigation in our laboratory.
Table 3. Reaction of triarylindium organometallics with 12 under
rhodium catalysis.
Experimental Section
General Methods: All reactions were carried out in flame-dried
glassware under argon using standard gas-tight syringes, cannulae,
and septa. THF was dried by distillation from the sodium ketyl of
benzophenone. Reaction temperatures refer to external bath tem-
peratures. 3-Phenyl-2-propenyl benzoate (1d),[20] methyl (2E)-3-
phenyl-2-propenyl carbonate (1e),[21] [(1E)-3-chloro-1-butenyl]-
benzene (12),[22] and methyl 1-phenyl-2-propenyl carbonate (19)[23]
were prepared according to standard literature procedures. Organo-
lithium reagents were titrated prior to use. All other commercially
available reagents were used as received. Organic extracts were
dried with anhydrous MgSO4, filtered, and concentrated by using
a rotary evaporator at aspirator pressure. Reactions were moni-
tored by TLC using precoated silica gel plates (Alugram® Xtra SIL
G/UV254, thickness 0.20 mm) with UV light as the visualizing agent
and ethanolic phosphomolybdic acid as the developing agent.
Flash column chromatography was performed by using 230–
400 mesh silica gel packed into glass columns. 1H and 13C NMR
spectra were recorded in CDCl3 at 300 MHz for 1H and at 75 MHz
for 13C at ambient temperature and calibrated to the solvent peak.
DEPT data was used to assign carbon types. Mass spectra were
obtained with EI ionization at 70 eV.
1
[a] Measured by H NMR spectroscopy. [b] α/γ = 82:18.
To explore further the versatility of the reaction and to
gain an insight into the mechanism, we also studied the
reactivity of the secondary allylic carbonate 18. Under the
optimized reaction conditions, the reaction with Ph3In gave
the SN2Ј product 2 in 82% yield as the only regioisomer
Triorganoindium Reagents: Triorganoindium compounds were pre-
pared according to previously published methods[6f] by treatment
of the corresponding organolithium or Grignard reagent (3 equiv.,
ca. 0.5 m in dry THF) with a solution of InCl3 (1.1 equiv., ca.
0.05 m in dry THF) at –78 °C and warming to room temperature.
1
detected by H NMR spectroscopy (Scheme 1). This result
contrasts with the regioselectivity observed in Rh-catalyzed
allylic substitution reactions with soft nucleophiles, which
are generally associated with the rapid formation of a σ-
allyl-Rh complex rather than a π-allyl complex, as classi-
cally occurs under palladium catalysis.[17,18] In our reactions
we believe that σ–π–σ isomerization could take place under
the reaction conditions (80 °C) and that this would favor
the formation of the σ-allyl-Rh complex at the less hindered
position.[19]
Furan, benzofuran, and benzo[b]thiophene were lithiated by treat-
ment with nBuLi (1 equiv.) at –78 °C and warming to room tem-
perature. 1-Naphthyllithium and 2-thienyllithium were prepared by
metal/halogen exchange reactions with nBuLi (1 equiv.) at –78 °C
in dry THF from 1-iodonaphthalene and 2-bromothiophene,
respectively.
General Procedure for the Rhodium-Catalyzed Allylic Substitution
Reactions: A solution of [Rh(cod)Cl]2 (9.9 mg, 0.02 mmol) in dry
THF (2 mL) was placed in an argon-filled Schlenk tube. After stir-
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
R. Riveiros, R. Tato, J. Pérez Sestelo, L. A. Sarandeses
FULL PAPER
ring for 10 min at room temperature, the allylic chloride (1 mmol)
and a solution of R3In in dry THF [ca. 0.0625 m, 8 mL, 0.5 mmol
(reactions with 1a–e and 19), 11 mL, 0.7 mmol (reactions with 12)]
were successively added and the resulting mixture was heated at
80 °C for 8–10 h. The reaction was quenched by the addition of a
few drops of MeOH, diluted with hexanes (25 mL), and filtered
through a short pad of Celite, washing the solids with hexanes (2ϫ
25 mL). The filtrate was concentrated in vacuo and the residue was
purified by flash chromatography.
CDCl3): δ = 4.03 (d, J = 4.8 Hz, 2 H), 6.33–6.73 (m, 2 H), 7.19–
7.58 (m, 9 H), 7.79 (dd, J = 7.4, 1.9 Hz, 1 H), 7.86–7.94 (m, 1 H),
8.08–8.15 (m, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 36.4
(CH2), 124.0 (CH), 125.5 (CH), 125.6 (CH), 125.9 (CH), 126.1 (2
CH), 126.4 (CH), 127.1 (CH), 127.1 (CH), 128.5 (2 CH), 128.7
(CH), 128.9 (CH), 131.3 (CH), 132.0 (C), 133.9 (C), 136.3 (C),
137.5 (C) ppm. MS (EI): m/z (%) = 244 (100) [M]+. HRMS (EI):
calcd. for C19H16 244.1247; found 244.1254.
2-[(2E)-3-Phenyl-2-propen-1-yl]thiophene (8):[22] Yellow oil (142 mg,
71%). IR (ATR): ν
= 3027, 2896, 1497, 1449, 964 cm–1. 1H
[(1E)-1-Propene-1,3-diyl]dibenzene (2):[24] Colorless oil (152 mg,
˜
max
= 3025, 2895, 1494, 1451, 963 cm–1. 1H
NMR (300 MHz, CDCl3): δ = 3.76 (d, J = 6.6 Hz, 2 H), 6.38 (dt,
J = 15.7, 6.6 Hz, 1 H), 6.53 (d, J = 15.7 Hz, 1 H), 6.88 (m, 1 H),
6.97 (dd, J = 5.1, 3.4 Hz, 1 H), 7.17–7.41 (m, 6 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 33.3 (CH2), 123.7 (CH), 124.7 (CH), 126.2
(2 CH), 126.9 (CH), 127.3 (CH), 128.2 (CH), 128.5 (2 CH), 131.4
(CH), 137.2 (C), 143.1 (C) ppm. MS (EI): m/z (%) = 200 (100)
[M]+. HRMS (EI): calcd. for C13H12S 200.0654; found 200.0654.
78%). IR (ATR): ν
˜
max
NMR (300 MHz, CDCl3): δ = 3.55 (d, J = 6.3 Hz, 2 H), 6.39 (dt,
J = 15.9, 6.3 Hz, 1 H), 6.46 (d, J = 15.9 Hz, 1 H), 7.20–7.38 (m,
10 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 39.4 (CH2), 126.2 (2
CH), 126.2 (CH), 127.2 (CH), 128.6 (4 CH), 128.7 (2 CH), 129.3
(CH), 131.1 (CH), 137.5 (C), 140.2 (C) ppm. MS (EI): m/z (%) =
194 (37) [M]+, 193 (23) [M – H]+, 115 (100). HRMS (EI): calcd.
for C15H14 194.1090; found 194.1093.
2-[(2E)-3-Phenyl-2-propen-1-yl]benzo[b]thiophene (9): White solid
1-Methyl-4-[(2E)-3-phenyl-2-propen-1-yl]benzene (3):[19] Colorless
(150 mg, 60%); m.p. 77–79 °C. IR (ATR): νmax = 3026, 2919, 1447,
˜
1
968 cm–1. H NMR (300 MHz, CDCl3): δ = 3.83 (d, J = 6.7 Hz, 2
oil (200 mg, 96%). IR (ATR): νmax = 3027, 2920, 1692, 1269 cm–1.
˜
1H NMR (300 MHz, CDCl3): δ = 2.37 (s, 3 H), 3.55 (d, J = 6.4 Hz,
2 H), 6.38 (dt, J = 15.9, 6.4 Hz, 1 H), 6.49 (d, J = 15.9 Hz, 1 H),
7.14–7.41 (m, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 21.0
(CH3), 38.9 (CH2), 126.1 (2 CH), 127.0 (CH), 128.4 (2 CH), 128.5
(2 CH), 129.1 (2 CH), 129.5 (CH), 130.8 (CH), 135.6 (C), 137.0
(C), 137.5 (C) ppm. MS (EI): m/z (%) = 208 (100) [M]+, 193 (89)
[M – CH3]+. HRMS (EI): calcd. for C16H16 208.1247; found
208.1244.
H), 6.43 (dt, J = 15.7, 6.7 Hz, 1 H), 6.60 (d, J = 15.7 Hz, 1 H),
7.10 (d, J = 0.7 Hz, 1 H), 7.20–7.43 (m, 7 H), 7.70 (dd, J = 7.1,
1.4 Hz, 1 H), 7.75–7.83 (m, 1 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 34.1 (CH2), 121.2 (CH), 122.2 (CH), 122.9 (CH), 123.6
(CH), 124.1 (CH), 126.3 (2 CH), 127.3 (CH), 127.4 (CH), 128.6 (2
CH), 132.0 (CH), 137.1 (C), 139.7 (C), 140.2 (C), 144.2 (C) ppm.
MS (EI): m/z (%) = 250 (100) [M]+. HRMS (EI): calcd. for C17H14S
250.0811; found 250.0813.
2-[(2E)-3-Phenyl-2-propen-1-yl]furan (10):[28] Colorless oil (105 mg,
1-Methoxy-4-[(2E)-3-phenyl-2-propen-1-yl]benzene (4):[19] Colorless
57%). IR (ATR): ν
= 3027, 2898, 1504, 1448, 963 cm–1. 1H
˜
max
oil (206 mg, 92%). IR (ATR): ν
= 3027, 2835, 1511, 1243,
˜
max
NMR (300 MHz, CDCl3): δ = 3.58 (d, J = 6.6 Hz, 2 H), 6.10 (m,
1 H), 6.34 (tdd, J = 7.6, 6.6, 0.9 Hz, 2 H), 6.50 (t, J = 15.9 Hz, 1
H), 7.21–7.41 (m, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 31.8
(CH2), 105.6 (CH), 110.3 (CH), 125.6 (CH), 126.2 (2 CH), 127.3
(CH), 128.5 (2 CH), 132.0 (CH), 137.2 (C), 141.4 (CH), 153.9
(C) ppm. MS (EI): m/z (%) = 184 (100) [M]+. HRMS (EI): calcd.
for C13H12O 184.0883; found 184.0879.
966 cm–1. H NMR (300 MHz, CDCl3): δ = 3.51 (d, J = 6.2 Hz, 2
H), 3.81 (s, 3 H), 6.33 (dt, J = 15.9, 6.2 Hz, 1 H), 6.46 (d, J =
15.9 Hz, 1 H), 6.87 (dd, J = 6.6, 2.1 Hz, 2 H), 7.17–7.39 (m, 7
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 38.4 (CH2), 55.2 (CH3),
113.9 (2 CH), 126.1 (2 CH), 127.0 (CH), 128.4 (2 CH), 129.5 (2
CH), 129.6 (CH), 130.7 (CH), 132.1 (C), 137.5 (C), 158.0 (C) ppm.
MS (EI): m/z (%) = 224 (100) [M]+. HRMS (EI): calcd. for
C16H16O 224.1196; found 224.1191.
1
2-[(2E)-3-Phenyl-2-propen-1-yl]benzofuran (11):[29] Colorless oil
(117 mg, 50%). IR (ATR): νmax = 3027, 2953, 1453, 1252, 963 cm–1.
˜
1-Methoxy-2-[(2E)-3-phenyl-2-propen-1-yl]benzene (5):[25] Yellow oil
1H NMR (300 MHz, CDCl3): δ = 3.72 (dt, J = 6.8, 1.0 Hz, 2 H),
6.40 (dt, J = 15.8, 6.8 Hz, 1 H), 6.49 (d, J = 1.0 Hz, 1 H), 6.60 (d,
J = 15.8 Hz, 1 H), 7.17–7.53 (m, 9 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 32.2 (CH2), 102.7 (CH), 110.8 (CH), 120.4 (CH), 122.5
(CH), 123.4 (CH), 124.6 (CH), 126.2 (2 CH), 127.4 (CH), 128.5 (2
CH), 128.8 (C), 132.7 (CH), 137.1 (C), 154.9 (C), 157.1 (C) ppm.
MS (EI): m/z (%) = 234 (100) [M]+. HRMS (EI): calcd. for
C17H14O 234.1039; found 234.1032.
(170 mg, 76%). IR (ATR): ν
= 3027, 2836, 1492, 1241,
˜
max
1026 cm–1. H NMR (300 MHz, CDCl3): δ = 3.63 (d, J = 5.3 Hz,
2 H), 3.91 (s, 3 H), 6.25–6.67 (m, 1 H), 6.75–7.15 (m, 1 H), 7.09–
7.65 (m, 4 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 33.4 (CH2),
55.4 (CH3), 110.4 (CH), 120.6 (CH), 126.1 (2 CH), 126.9 (CH),
127.4 (CH), 128.4 (2 CH), 128.7 (C), 128.9 (CH), 129.9 (CH), 130.7
(CH), 137.8 (C), 157.3 (C) ppm. MS (EI): m/z (%) = 224 (100)
[M]+, 193 (52) [M – CH3O]+. HRMS (EI): calcd. for C16H16O
224.1196; found 224.1196.
1
(3-Methyl-1-propene-1,3-diyl)dibenzene (13):[30] Colorless oil
(167 mg, 80%, E/Z = 85:15). E isomer: IR (ATR): ν
= 3024,
˜
max
1-Fluoro-4-[(2E)-3-phenyl-2-propen-1-yl]benzene (6):[26] Colorless oil
2963, 1492, 1448, 962 cm–1. 1H NMR (300 MHz, CDCl3): δ = 1.49
(d, J = 7.0 Hz, 3 H), 3.62–3.71 (m, 1 H), 6.42 (d, J = 4.5 Hz, 2 H),
7.18–7.39 (m, 10 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 21.2
(CH3), 42.6 (CH), 126.1 (2 CH), 126.2 (CH), 127.0 (CH), 127.3 (2
CH), 128.49 (4 CH), 128.53 (CH), 135.2 (CH), 137.6 (C), 145.6
(C) ppm. MS (EI): m/z (%) = 208 (55) [M]+, 193 (82) [M – CH3]+,
131 (100). HRMS (EI): calcd. for C16H16 208.1247; found
208.1246. Z isomer: 1H NMR (300 MHz, CDCl3): δ = 1.43 (d, J =
6.9 Hz, 3 H), 4.06 (dq, J = 10.4, 6.9 Hz, 1 H), 5.87 (t, J = 11.2 Hz,
1 H), 6.52 (d, J = 11.2 Hz, 1 H), 7.21–7.39 (m, 10 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 22.9 (CH3), 37.8 (CH), 126.1 (CH),
126.7 (CH), 126.9 (2 CH), 127.8 (CH), 128.2 (2 CH), 128.6 (2 CH),
128.7 (2 CH), 137.1 (CH), 137.4 (C), 146.2 (C) ppm. MS (EI): m/z
(170 mg, 80%). IR (ATR): νmax = 3027, 2921, 1507, 1219 cm–1. 1H
˜
NMR (300 MHz, CDCl3): δ = 3.55 (d, J = 6.5 Hz, 2 H), 6.35 (dt,
J = 15.8, 6.5 Hz, 1 H), 6.47 (d, J = 15.8 Hz, 1 H), 7.02 (t, J =
8.7 Hz, 2 H), 7.17–7.44 (m, 7 H) ppm. 13C NMR (75 MHz,
2
CDCl3): δ = 38.4 (CH2), 115.2 (d, JCF = 21.2 Hz, 2 CH), 126.1 (2
3
CH), 127.2 (CH), 128.5 (2 CH), 129.0 (CH), 130.0 (d, JCF
=
4
7.8 Hz, 2 CH), 131.2 (CH), 135.7 (d, JCF = 3.2 Hz, C), 137.3 (C),
161.5 (d, 1JCF = 243.9 Hz, CF) ppm. MS (EI): m/z (%) = 212 (100)
[M]+. HRMS (EI): calcd. for C15H13F 212.0996; found 212.1004.
1-[(2E)-3-Phenyl-2-propen-1-yl]naphthalene (7):[27] White solid
(147 mg, 60%); m.p. 73–74 °C (lit.:[27] m.p. 69–71 °C). IR (ATR):
ν
= 3031, 2827, 1493, 1449, 970 cm–1. 1H NMR (300 MHz,
˜
max
4
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
Rhodium-Catalyzed Allylic Substitution Reactions
4
(%) = 208 (100) [M]+, 193 (28) [M – CH3]+. HRMS (EI): calcd. for 7.7 Hz, 2 CH), 128.6 (2 CH), 136.8 (CH), 137.3 (C), 141.8 (d, JCF
1
C16H16 208.1247; found 208.1239.
= 3.2 Hz, C), 161.3 (d, JCF = 243.9 Hz, CF) ppm. MS (EI): m/z
(%) = 226 (90) [M]+, 211 (100) [M – CH3]+. HRMS (EI): calcd. for
C16H15F 226.1152; found 226.1150.
1-Methyl-4-[1-methyl-3-phenyl-2-propen-1-yl]benzene
(14):[30,31]
Colorless oil (207 mg, 93%, E/Z = 66:34). E isomer: IR (ATR):
ν
˜
= 3023, 2963, 1512, 1447, 963 cm–1. 1H NMR (300 MHz,
Supporting Information (see footnote on the first page of this arti-
max
CDCl3): δ = 1.47 (d, J = 7.0 Hz, 3 H), 2.35 (s, 3 H), 3.59–3.67 (m,
1 H), 6.35–6.47 (m, 2 H), 7.14–7.39 (m, 9 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 21.0 (CH3), 21.3 (CH3), 42.1 (CH), 126.1 (2
CH), 127.0 (CH), 127.2 (2 CH), 128.3 (CH), 128.4 (2 CH), 129.2
(2 CH), 135.5 (CH), 135.7 (C), 137.6 (C), 142.6 (C) ppm. MS (EI):
m/z (%) = 222 (49) [M]+, 207 (100) [M – CH3]+. HRMS (EI): calcd.
cle): NMR spectra for compounds prepared.
Acknowledgments
We are grateful to the Ministerio de Ciencia e Innovación (MIC-
INN) (CTQ2009-07180) and the Xunta de Galicia (IN-
CITE08PXIB103167PR) for financial support.
for C17H18 222.1403; found 222.1399.
Z
isomer: 1H NMR
(300 MHz, CDCl3): δ = 1.42 (d, J = 6.9 Hz, 3 H), 2.36 (s, 3 H),
4.02 (dq, J = 10.4, 6.9 Hz, 1 H), 5.85 (dd, J = 11.4, 10.4 Hz, 1 H),
6.50 (d, J = 11.4 Hz, 1 H), 7.12–7.39 (m, 9 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 21.0 (CH3), 22.9 (CH3), 37.3 (CH), 126.7
(CH), 126.7 (2 CH), 127.6 (CH), 128.2 (2 CH), 128.7 (2 CH), 129.2
(2 CH), 135.5 (C), 137.3 (CH), 137.5 (C), 143.2 (C) ppm. MS (EI):
m/z (%) = 222 (48) [M]+, 207 (100) [M – CH3]+. HRMS (EI): calcd.
for C17H18 222.1403; found 222.1397.
[1] For a general overview, see: T. Tsuji, Transition Metal Reagents
and Catalysts, John Wiley & Sons, New York, 2000, pp. 109–
168.
[2] Y. Nishibayashi, S. Uemura, in: Comprehensive Organometallic
Chemistry III (Eds.: D. M. P. Mingos, R. H. Crabtree), Elsevier,
Oxford, UK, 2006, vol. 11, pp. 75–122.
[3] a) B. H. Lipshutz, in: Comprehensive Organometallic Chemistry
II (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon
Press, Oxford, UK, 1995, vol. 12, pp. 59–130; b) A. Sofia, E.
Karlström, J.-E. Bäckvall, in: Modern Organocopper Chemistry
(Ed.: N. Krause), Wiley-VCH, Weinheim, Germany, 2002, pp.
259–288; c) H. Yorimitsu, K. Oshima, Angew. Chem. 2005, 117,
4509; Angew. Chem. Int. Ed. 2005, 44, 4435–4439.
[4] E. Negishi, F. Liu, in: Handbook of Organopalladium Chemistry
for Organic Synthesis (Ed.: E. Negishi), John Wiley & Sons,
New York, 2002, vol. 1, pp. 551–589.
[5] a) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395–
422; b) A. H. Hoveyda, N. M. Heron, in: Comprehensive Asym-
metric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamam-
oto), Springer, Berlin, 1999, pp. 431–454; c) B. M. Trost, M. L.
Crawley, Chem. Rev. 2003, 103, 2921–2944.
1-Methoxy-4-[1-methyl-3-phenyl-2-propen-1-yl]benzene (15):[24] Col-
orless oil (203 mg, 85%, E/Z = 88:12). IR (ATR): ν
= 3024,
˜
max
2960, 2833, 1509, 1243 cm–1. 1H NMR (300 MHz, CDCl3): δ =
1.40 (d, J = 6.9 Hz, 3 H, Z isomer), 1.46 (d, J = 7.0 Hz, 3 H, E
isomer), 3.58–3.66 (m, 1 H), 3.82 (s, 3 H, E isomer), 3.84 (s, 3 H,
Z isomer), 6.40 (d, J = 4.3 Hz, 2 H), 6.89 (d, J = 8.8 Hz, 2 H), 7.21
(d, J = 8.8 Hz, 2 H), 7.27–7.39 (m, 5 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 21.3 (CH3), 41.7 (CH), 55.3 (CH3), 113.9 (2 CH),
126.1 (2 CH), 127.0 (CH), 128.2 (2 CH), 128.2 (CH), 128.5 (2 CH),
135.6 (CH), 137.6 (C), 137.7 (C), 158.0 (C) ppm. MS (EI): m/z (%)
= 238 (79) [M]+, 223 (100) [M – CH3]+. HRMS (EI): calcd. for
C17H18O 238.1352; found 238.1347.
1-Methoxy-2-[1-methyl-3-phenyl-2-propen-1-yl]benzene (16):[24] Yel-
[6] For contributions from this group, see: a) I. Pérez, J. Pérez Ses-
telo, L. A. Sarandeses, Org. Lett. 1999, 1, 1267–1269; b) I.
Pérez, J. Pérez Sestelo, L. A. Sarandeses, J. Am. Chem. Soc.
2001, 123, 4155–4160; c) M. A. Pena, I. Pérez, J. Pérez Sestelo,
L. A. Sarandeses, Chem. Commun. 2002, 2246–2247; d) M. A.
Pena, J. Pérez Sestelo, L. A. Sarandeses, Synthesis 2003, 780–
784; e) R. Riveiros, D. Rodríguez, J. Pérez Sestelo, L. A. Sa-
randeses, Org. Lett. 2006, 8, 1403–1406; f) M. A. Pena, J.
Pérez Sestelo, L. A. Sarandeses, J. Org. Chem. 2007, 72, 1271–
1275; g) J. Caeiro, J. Pérez Sestelo, L. A. Sarandeses, Chem.
Eur. J. 2008, 14, 741–746; h) R. Riveiros, L. Saya, J. Pérez Ses-
telo, L. A. Sarandeses, Eur. J. Org. Chem. 2008, 1959–1966; i)
A. Mosquera, R. Riveiros, J. Pérez Sestelo, L. A. Sarandeses,
Org. Lett. 2008, 10, 3745–3748; j) L. Bouissane, J. Pérez Sestelo,
L. A. Sarandeses, Org. Lett. 2009, 11, 1285–1288.
[7] For selected references from other groups, see: a) J. Y. Legros,
G. Primault, J. C. Fiaud, Tetrahedron 2001, 57, 2507–2514; b)
K. Takami, H. Yorimitsu, H. Shnokubo, S. Matsubara, K.
Oshima, Org. Lett. 2001, 3, 1997–1999; c) M. X. Qian, Z. H.
Huang, E. Negishi, Org. Lett. 2004, 6, 1531–1534; d) V. Gopal-
samuthiram, W. D. Wulff, J. Am. Chem. Soc. 2004, 126, 13936–
13937; e) B. W. Fausett, L. S. Liebeskind, J. Org. Chem. 2005,
70, 4851–4853; f) M. Barbero, S. Cadamuro, S. Dughera, C.
Giaveno, Eur. J. Org. Chem. 2006, 4884–4890; g) A. Meyer, M.
Brunjes, F. Taft, T. Frenzel, F. Sasse, A. Kirschning, Org. Lett.
2007, 9, 1489–1492; h) F. Font-Sanchis, F. J. Céspedes-Guirao,
A. Sastre-Santos, F. Fernández-Lázaro, J. Org. Chem. 2007, 72,
3589–3591; i) M. Barbero, S. Cadamuro, S. Dughera, G. Ghigo,
Eur. J. Org. Chem. 2008, 862–868; j) W. Lee, Y. Kang, P. H.
Lee, J. Org. Chem. 2008, 73, 4326–4329; k) L. Zhang, Y. Luo, J.
Wu, Synlett 2010, 1845–1848; l) Z.-L. Shen, Y.-C. Lai, C. H. A.
Wong, K. K. K. Goh, Y.-S. Yang, H.-L. Cheong, T.-P. Loh,
Org. Lett. 2011, 13, 422–425.
low oil (172 mg, 72%, α/γ = 82:18, E/Z = 85:15). IR (ATR): ν
˜
max
= 3024, 2960, 2834, 1490, 1238 cm–1. 1H NMR (300 MHz, CDCl3):
δ = 1.35 (dd, J = 6.9, 1.4 Hz, 3 H, Z isomer), 1.43 (dd, J = 7.0,
0.9 Hz, 3 H, E isomer), 1.74 (d, J = 6.3 Hz, 3 H, γ isomer), 3.78
(s, 3 H, γ isomer), 3.83 (m, 3 H, Z isomer), 3.87 (s, 3 H, E isomer),
4.11 (dd, J = 7.0, 3.5 Hz, 1 H), 6.44 (d, J = 0.9 Hz, 1 H), 6.46 (d,
J = 0.9 Hz, 1 H), 6.88–6.98 (m, 2 H), 7.17–7.40 (m, 7 H) ppm. 13
C
NMR (75 MHz, CDCl3): δ = 20.0 (CH3), 35.1 (CH), 55.4 (CH3),
110.7 (CH), 120.7 (CH), 126.1 (2 CH), 126.8 (CH), 127.1 (CH),
127.5 (CH), 128.2 (CH), 128.4 (2 CH), 134.1 (C), 135.0 (CH), 137.9
(C), 156.8 (C) ppm. MS (EI): m/z (%) = 238 (70) [M]+, 223 (100)
[M – CH3]+. HRMS (EI): calcd. for C17H18O 238.1352; found
238.1350.
1-Fluoro-4-[1-methyl-3-phenyl-2-propen-1-yl]benzene (17):[32] Color-
less oil (220 mg, 97%, E/Z = 75:25); E isomer: IR (ATR): ν
=
˜
max
3031, 2917, 1508, 1222 cm–1. 1H NMR (300 MHz, CDCl3): δ =
1.48 (d, J = 7.0 Hz, 3 H), 3.66 (dq, J = 7.0, 5.4 Hz, 1 H), 6.33–
6.46 (m, 1 H), 7.00–7.06 (m, 1 H), 7.21–7.40 (m, 9 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 21.3 (CH3), 41.8 (CH), 115.1 (d, 2JCF
= 21.1 Hz, 2 CH), 126.1 (2 CH), 127.1 (CH), 128.5 (2 CH), 128.6
(d, 3JCF = 7.8 Hz, 2 CH), 128.7 (CH), 135.0 (CH), 137.4 (C), 141.2
4
1
(d, JCF = 3.2 Hz, C), 161.4 (d, JCF = 243.9 Hz, CF) ppm. MS
(EI): m/z (%) = 226 (93) [M]+, 211 (100) [M – CH3]+. HRMS (EI):
calcd. for C16H15F 226.1152; found 226.1149. Z isomer: H NMR
1
(300 MHz, CDCl3): δ = 1.40 (d, J = 6.8 Hz, 3 H), 4.01 (dq, J =
10.3, 6.8 Hz, 1 H), 5.80 (dd, J = 11.5, 10.3 Hz, 1 H), 6.51 (d, J =
11.5 Hz, 1 H), 6.98–7.32 (m, 9 H) ppm. 13C NMR (75 MHz,
2
CDCl3): δ = 22.9 (CH3), 37.0 (CH), 115.2 (d, JCF = 21.1 Hz, 2
3
CH), 126.8 (CH), 128.0 (CH), 128.2 (2 CH), 128.2 (d, JCF
=
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
R. Riveiros, R. Tato, J. Pérez Sestelo, L. A. Sarandeses
FULL PAPER
[8] a) D. Rodríguez, J. Pérez Sestelo, L. A. Sarandeses, J. Org.
Chem. 2003, 68, 2518–2520; b) D. Rodríguez, J. Pérez Sestelo,
L. A. Sarandeses, J. Org. Chem. 2004, 69, 8136–8139.
[9] R. Tato, R. Riveiros, J. Pérez Sestelo, L. A. Sarandeses, Tetra-
hedron 2012, 68, 1606–1611.
[10] I. Minami, I. Shimizu, J. Tsuji, J. Organomet. Chem. 1985, 296,
269–280.
[11] a) P. A. Evans, J. D. Nelson, Tetrahedron Lett. 1998, 39, 1725–
1728; b) P. A. Evans, J. D. Nelson, J. Am. Chem. Soc. 1998,
120, 5581–5582; c) P. A. Evans, L. J. Kennedy, Org. Lett. 2000,
2, 2213–2215; d) P. A. Evans, L. J. Kennedy, J. Am. Chem. Soc.
2001, 123, 1234–1235; e) P. A. Evans, J. E. Robinson, J. Am.
Chem. Soc. 2001, 123, 4609–4610; f) P. A. Evans, D. K. Leahy,
J. Am. Chem. Soc. 2003, 125, 8974–8975; g) P. A. Evans, M. J.
Lawler, J. Am. Chem. Soc. 2004, 126, 8642–8643.
[12] R. Takeuchi, N. Kitamura, New J. Chem. 1998, 22, 659–660.
[13] a) K. Selvakumar, M. Valentini, P. S. Pregosin, A. Albinati,
Organometallics 1999, 18, 4591–4597; b) T. Hayashi, A. Okada,
T. Suzuka, M. Kawatsura, Org. Lett. 2003, 5, 1713–1715.
[14] a) P. A. Evans, D. Uraguchi, J. Am. Chem. Soc. 2003, 125,
7158–7159; b) H. Yasui, K. Mizutani, H. Yorimitsu, K. Osh-
ima, Tetrahedron 2006, 62, 1410–1415.
[15] a) F. Menard, T. M. Chapman, C. Dockendorff, M. Lautens,
Org. Lett. 2006, 8, 4569–4572; b) F. Menard, D. Perez, D. S.
Roman, T. M. Chapman, M. Lautens, J. Org. Chem. 2010, 75,
4056–4068. See also: c) T. Miura, Y. Takahashi, M. Murakami,
Chem. Commun. 2007, 595–597.
[16] V. K. Yadav, K. G. Babu, Tetrahedron 2003, 59, 9111–9116.
[17] For a related E/Z isomerization in Rh-catalyzed allylic substi-
tution, see: U. Kazmaier, D. Stolz, Angew. Chem. 2006, 118,
3143; Angew. Chem. Int. Ed. 2006, 45, 3072–3075.
[19]
G. W. Kabalka, G. Dong, B. Venkataiah, Org. Lett. 2003, 5,
893–895.
[20]
[21]
R. Correia, P. DeShong, J. Org. Chem. 2001, 66, 7159–7165.
a) G. V. Rao, C. Reddy, Tetrahedron Lett. 2008, 49, 824–826;
b) R. Matsubara, T. F. Jamison, J. Am. Chem. Soc. 2010, 132,
6880–6881.
G. Onodera, H. Imajima, M. Yamanashi, Y. Nishibayashi, M.
Hidai, S. Uemura, Organometallics 2004, 23, 5841–5848.
S. Shekhar, B. Trantow, A. Leitner, J. F. Hartwig, J. Am. Chem.
Soc. 2006, 128, 11770–11771.
a) Y. Pan, Z. Zhang, H. Hu, Synthesis 1995, 245–247; b) Y.
Liu, B. Yao, C.-L. Deng, R.-Y. Tang, X.-G. Zhang, J.-H. Li,
Org. Lett. 2011, 13, 1126–1129.
[22]
[23]
[24]
[25]
Y. Yamamoto, K. Itonaga, Chem. Eur. J. 2008, 14, 10705–
10715.
[26] Y. M. A. Yamada, T. Watanabe, T. Beppu, N. Fukuyama, K.
Torii, Y. Uozumi, Chem. Eur. J. 2010, 16, 11311–11319.
[27] E. Alacid, C. Nájera, J. Org. Chem. 2009, 74, 2321–2327.
[28] a) J. Hine, S.-M. Linden, J. Org. Chem. 1981, 46, 1635–1638;
b) Z. Yang, P. Tang, J. F. Gauuan, B. F. Molino, J. Org. Chem.
2009, 74, 9546–9549.
[29] J. Le Bras, J. Muzart, Tetrahedron 2007, 63, 7942–7948.
[30] Z.-Q. Liu, Y. Zhang, L. Zhao, Z. Li, J. Wang, H. Li, L.-M.
Wu, Org. Lett. 2011, 13, 2208–2211.
[31] Y. Nishimoto, M. Kajioka, T. Saito, M. Yasuda, A. Baba,
Chem. Commun. 2008, 6396–6398.
[32] L. K. Thalen, A. Sumic, K. Bogar, J. Norinder, A. K. A.
Persson, J.-E. Bäckvall, J. Org. Chem. 2010, 75, 6842–6847.
Received: January 30, 2012
Published Online: ᭿
[18] B. Wucher, M. Moser, S. A. Schumacher, F. Rominger, D.
Kunz, Angew. Chem. 2009, 121, 4481; Angew. Chem. Int. Ed.
2009, 48, 4417–4421.
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20104
/KAP1
Date: 04-04-12 16:17:03
Pages: 7
Rhodium-Catalyzed Allylic Substitution Reactions
Indium Organometallics
R. Riveiros, R. Tato, J. Pérez Sestelo,*
L. A. Sarandeses* ............................. 1–7
Rhodium-Catalyzed Allylic Substitution
Reactions with Indium(III) Organometall-
ics
Keywords: Organometallics / Indium / Rho-
dium / Allylic compounds / C–C coupling
Aryl- and heteroarylindium reagents react
with primary and secondary allyl halides
and their derivatives under rhodium cataly-
sis to afford the α-substituted products in
good yields and with high regio- and
stereoselectivity. This new methodology
shows the usefulness of the indium–rho-
dium transmetallation process in carbon–
carbon bond-forming reactions.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7