Transition-Metal Catalyzed Stereoselective γ-Arylation and Friedel-Crafts Alkylation: A Concise Synthesis of Indenes

Article abstract of DOI:10.1002/ejoc.202000030

A highly stereoselective [Pd]-catalyzed arylation of tert-alkenols, is presented and applied to the synthesis of indenes using intramolecular Friedel–Crafts alkylation sequence. The initial Heck reaction is performed by using water as the green solvent. A simple acid triggers intramolecular alkylation in short reaction times at room temperature. Notably, indenes have been accomplished using a single column chromatography technique.

Full text of DOI:10.1002/ejoc.202000030

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Transition-Metal Catalyzed Stereoselective γ-Arylation and
Friedel-Crafts Alkylation: A Concise Synthesis of Indenes
Authors: Karu Ramesh and Gedu Satyanarayana
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202000030
Link to VoR: https://doi.org/10.1002/ejoc.202000030
01/2020

10.1002/ejoc.202000030
European Journal of Organic Chemistry
COMMUNICATION
Transition-Metal Catalyzed Stereoselective -Arylation and
Friedel-Crafts Alkylation: A Concise Synthesis of Indenes
Karu Ramesh[a] and Gedu Satyanarayana*[a]
[a]
Prof. G. Satyanarayana, Department of Chemistry
Indian Institute of Technology (IIT) Hyderabad, Kandi – 502 285, Sangareddy District, Telangana, INDIA
Fax: +91(40) 2301 6032
E-mail: gvsatya@iith.ac.in
Home page: https://sites.google.com/site/gsresearchgrouphomepage/home
biological significance.13 Hence, many research groups have
been attracted towards the synthesis of indenes in different paths
using transition metal catalysis14 and acid-mediated
transformations.15 In continuation of our interest in developing
transition-metal catalysis16 as well as acid-mediated
cyclizations,17 herein, we report the synthesis of indenes. The
strategy involves intermolecular Heck and intramolecular Friedel-
Crafts alkylation of tert-alkenols. Significantly, the entire process
is achieved by a single column chromatography technique.
To initiate the optimization study, the reaction was carried
out with cinnamyl tertiary alcohol 1a and bromobenzene 2a
by taking 5 mol% of Pd(OAc)2, 10 mol% of BINAP, 1 equiv of
TBAI (tetrabutylammonium iodide), 4 equiv of K2CO3, and
Abstract: A highly stereoselective [Pd]-catalyzed arylation of
tert-alkenols, is presented. Further, applied to the synthesis of
indenes using intramolecular Friedel-Crafts alkylation sequence.
The initial Heck reaction is performed by using water as the
green solvent. A simple acid triggers intramolecular alkylation in
short reaction times at room temperature. Notably, indenes have
been accomplished using a single column chromatography
technique.
Establishing new carbon-carbon bond-forming processes are vital
in organic chemistry. An innumerable number of examples have
developed towards C–C bond-forming reactions.1 Notably,
various acids have been employed to construct the C–C bond.2
Also, transition-metals3 attained much interest in constructing
diverse C–C bonds through coupling reactions, few of them are
Fujiwara-Moritani,4 Mizoroki-Heck,5 Suzuki,6 Sonogashira,7 and
Glaser couplings.8 Amongst, Fujiwara-Moritani and Mizoroki-
Heck reactions are a class of reactions, in which synthesis of
substituted olefins are accomplished. Specifically, these two
named reactions are differentiated in terms of aryl ring couples
with the olefin moiety. In the Fujiwara-Moritani reaction, the simple
arene couples with olefin double bond, while aryl halide is the
coupling partner in Mizoroki-Heck reaction. Later, numerous
transition metal-mediated Heck type coupling reactions are
reported on different functional group-containing olefins.9 To the
best of our knowledge, there are very few reports of arylation on
a double bond of unprotected hydroxyl group-containing olefins,
that too with poor selectivity.10 This may be attributed to the fact
that the hydroxyl group is Lewis basic in nature and competent
enough to engage the metal catalyst. This sort of alcohol reactivity
is well known from the degradative coupling of propargylic
alcohols with haloarenes, under [Pd]-catalysis.11 Also, hydroxyl
functionality is known to be reactive toward oxidative couplings
that are facilitated by a transition-metal catalyst.12 With this
viewpoint, we still believed that, under suitable conditions, it would
be feasible to touch the double bond stereoselectively without
effecting the hydroxyl group. So that it becomes possible to
perform some useful subsequent transformations on the arylated
tert-alkenols centered at a free hydroxyl group. Therefore, we
aimed at stereoselective [Pd]-catalyzed -arylation (Mizoroki-
Heck) on tert-alkenols. Intramolecular Friedel-Crafts alkylation of
the resulted arylated tert-alkenols would lead to indenes efficiently.
Due to the presence of unprotected OH group, -
arylated/Mizoroki-Heck tertiary alcohol would rather reactive
towards the cyclization (Friedel-Crafts alkylation). Indenes are an
essential class of compounds as they are of significant structural
motifs found as core structures in natural as well as products of
toluene (0.5 mL) as a solvent, at 100 C for 24 h. However,
there was no progress in the reaction; only the starting
material 1a (88%) was recovered (entry 1, Table 1). More or
less, the same result was noted when the temperature was
increased to 120
was conducted at a relatively higher temperature and longer
reaction times, i.e., 140 C for 36 h (entry 3, Table 1). To our
C (entry 2, Table 1). Thus, the reaction

delight, the reaction was progressed well and delivered the
desired product 3aa in 60% of yield. When 10 mol% of
Xantphos was employed as the ligand, afforded the product
3aa in moderate yields (entry 4, Table 1). On the other hand,
with 10 mol% of P(Cy)3 ligand, under similar conditions,
furnished 3aa in 65% yield (entry 5, Table 1). Notably,
switching the ligand to L-proline improved the yield of 3aa to
73% (entry 6, Table 1). Besides, when the reaction was
screened with other solvents like xylene and DMF, the
product 3aa was formed in 72% and 75% yields, respectively
(entry 7 & 8, Table 1). Based on the above outcomes, it was
believed that water, the green solvent, may also promote the
reaction, under similar conditions. Gratifyingly, 80% of the
requisite product 3aa was obtained by employing water as
the sole solvent, under similar reaction conditions (entry 9,
Table 1). In the similar context, other additives like BTEAC
(benzyl
triethylammonium
chloride),
TBAB
(tetrabutylammonium bromide), TBAC (tetrabutylammonium
chloride) were also afforded the desired product 3aa, but in
78%, 70% and 61% of yields, respectively (entries 10, 11 &
12, Table 1). When the temperature was decreased to 130

C, parallelly, the yield was also reduced to 55% (entry 13,
Table 1). Likewise, further decreasing the temperature to 120
C, the starting material was not consumed completely and

recovered the starting material 1a in 70% (entry 14, Table 1).
On the other hand, the reaction was also screened with
regards to time scale; i.e., the reaction was conducted for 24
1
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10.1002/ejoc.202000030
European Journal of Organic Chemistry
COMMUNICATION
and 30 h (entries 15 & 16, Table 1). However, there was no
complete conversion, despite recovered the starting material
1a 61% and 46% respectively. While the reaction for
prolonged time 48 h, led to the formation of 3aa, in 60% yield
only (entry 17, Table 1), which may be due to the
decomposition of the starting materials or product. Whereas,
the reaction with Pd(TFA)2 (5 mol%), TBAI (1 equiv), L-
proline (10 mol%), K2CO3 (4 equiv), and solvent water at 140
cinnamyl tertiary alcohols like (3E)-4-(4-ethylphenyl)-2-methylbut-
3-en-2-ol 1e and (1E)-1-phenyl-3-propylhex-1-en-3-ol 1f was
rather smooth and yielded the products 3ea+3ea' and 3fa, in 70%
and 59% of yields, respectively (Table 2). Moreover, arylation on
vinyl tertiary alcohols 1h was also successful and resulted the
products 3ha (70%), 3hd (72%) and 3he (75%) as exclusive E-
isomers (Table 2). Further, the stereochemistry of compound 3ha
was confirmed based on the NMR data analysis. In the 1H-NMR
spectrum, olefinic protons resonate at  6.63 (1H, J = 16.1 Hz)
and  6.35 (1H, J = 16.1 Hz). Thus, the large coupling constant (J
= 16.1 Hz) for both olefinic protons reveals the E-geometry of the
double bond. Moreover, the spectral data of the synthetic
compound 3ha was in good agreement with the reported data,
thus confirmed the stereochemistry of 3ha as E-stereoisomer.18
Based on this observation, the stereochemistry of other related
products such as, 3hd and 3he was also predicted as E isomer.

C for 36 h, furnished 3aa, in 64% yield (entry 18, Table 1).
When a relatively strong base Cs2CO3 was used, the yield of
3aa was dropped to 58% (entry 19, Table 1). While the
reaction with a weaker base Na2CO3, the starting material 1a
was not consumed completely, 68% of 1a was recovered
back (entry 20, Table 1).
Table 1: Optimization studies to generate arylated tert-alkenol 3aa.a-g
After achieving [Pd]-catalyzed selective -arylated tert-
alkenols, it was decided to implement acid-mediated
intramolecular Friedel-Crafts alkylation, to accomplish indene
products. Thus, the workup concentrated crude reaction mixture
of 3aa, was treated with triflic acid, under neat conditions at room
temperature, for 5 minutes. However, it led to the decomposition
(entry 1, Table 3). While with conc. H2SO4 at room temperature,
for 5 minutes, to our delight, furnished the cyclized indene product
4aa, in 78% of yield (entry 2, Table 3). Gratifyingly, the yield of
4aa was raised to 85% upon dropping the reaction time to 2
minutes (entry 3, Table 3). However, further decreasing the
reaction time (1 minute), dropped the yield of 4aa to 52% (entry 4,
Table 3). Further, to improve the yield of the product 4aa, it was
also checked with conc. H2SO4, solvent DCE (1 mL), at room
temperature, for 2 minutes. Nevertheless, no improvement in the
yield was observed, and afforded 4aa, in 60% yield (entry 5, Table
3).
entry
additive
(1 equiv)
ligand
(10 mol%)
solvent
(0.5 mL)
yield 3aa
temp (C)
& time (h)
100, 24
120, 24
140, 36
140, 36
140, 36
140, 36
140, 36
140, 36
140, 36
140, 36
140, 36
140, 36
130, 36
120, 36
140, 24
140, 30
140, 48
140, 36
140, 36
140, 36
b(%)
c
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18d
19e
20f
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
BTEAC
TBAB
TBAC
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
BINAP
BINAP
BINAP
Xantphos
P(cy)3
toluene
toluene
toluene
toluene
toluene
toluene
xylene
DMF
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
-
-
c
60
40
65
73
72
75
80
78
70
61
55
20 + -c
25 + -c
40 + -c
60
64
58
28 + -c
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
L-proline
On the other hand, the attempts to achieve indene in
a one-pot pathway without making workup were unsuccessful and
ended up in generating multiple spots on a TLC plate. Therefore,
it was concluded that the workup and concentration were
necessary after completion of the -arylation step and before
subjecting to acid-induced cyclization. Thus the entire process
was carried out using a single column chromatography technique.
aReaction conditions: 0.25 mmol of cinnamyl tertiary alcohol 1a, 0.62 mmol of
bromobenzene 2a, Pd(OAc)2 (5 mol%), ligand (10 mol%), additive (1 equiv),
Base = K2CO3 (4 equiv), solvent (0.5 mL). bIsolated yields of product 3aa.
cStarting material was recovered. d[Pd]-catalyst is Pd(TFA)2 (5 mol%). eBase is
Cs2CO3. fBase is Na2CO3. gTBAI: tetrabutylammonium iodide; TBAB:
tetrabutylammonium bromide; BTEAC: Benzyltriethylammonium chloride and
TBAC: tetrabutylammonium chloride.
The stereoselectivity in the arylation step (i.e., -selectivity)
is confirmed from NMR spectral analysis of indene product 4aa
as well as by comparing it with that reported in the literature. The
analysis is in support that the arylation has happened at -position
of the double bond of tert-alkenol 1a. Further, it can be
ascertained that in the present indene product 4aa, the chemical
shift of olefinic proton appeared at  6.41 (1H-NMR), which falls in
the deshielding zone of the phenyl ring. If it were the olefinic
proton of indene olefin formed via the -arylation path, it appears
at further deshielding position (around  7.00 in its 1H-NMR
spectra), as it falls in the deshielding region of both the aromatic
rings.19
The above optimization studies reveal that entry 9 of Table
1 is the best-optimized conditions to deliver the desired product
3aa. Thus, by implementing these optimal conditions (entry 9,
Table 1), it was further aimed to exemplify with the other cinnamyl
tertiary alcohols. Hence, the arylation was carried out on cinnamyl
tertiary alcohols, under standard conditions. When iodobenzene,
as the arylating agent, gave the product 3aa in more or less same
yield (Table 2). As expected, the reaction was smooth with aryl
halides flanked to moderately as well as strongly electron-
donating substituents, such as 3-/4-bromotoluenes (2b & 2c) and
3-/4-bromoanisoles (2d & 2e). Hence, -arylated products were
isolated as E/Z stereoisomers in good yields 3ab+3ab' (72%),
3ac+3ac' (70%), 3ad+3ad' (68%), and 3ae+3ae' (65%)
respectively (Table 2). While the reaction with bromoveratrole 2f
was also amenable and afforded as E/Z stereoisomers 3af+3af'
(63%) in good yields (Table 2). Further, the reaction with other
2
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10.1002/ejoc.202000030
European Journal of Organic Chemistry
COMMUNICATION
Table 2: Synthesis of -arylated products 3aa-3he.a-d
3
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10.1002/ejoc.202000030
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COMMUNICATION
aReaction conditions: 0.25 mmol of cinnamyl/vinyl tertiary alcohols 1a-1h, 0.62 mmol of aryl halides 2a-2j, Pd(OAc)2 (5 mol%), TBAI (tetrabutylammonium iodide)
(1 equiv), L-proline (10 mol%), K2CO3 (4 equiv), solvent water (0.5 mL), 140 C, 36-48 h. bIsolated yields of products 3aa-3he. cThe ratio of E/Z stereoisomers was
determined by 1H-NMR analysis. d0.25 mmol of aryl halides used.
Table 3: Optimization study for Friedel-Crafts alkylation to give 4aa.a-d
entry
1
acid (mL)
triflic acid
solvent (mL)
-
yield
temp (C) & time
(4aa%)c
(min)
d
rt & 5
-
2
conc. H2SO4
-
rt & 5
78
3
conc. H2SO4
-
rt & 2
85
4
conc. H2SO4
-
rt & 1
52
5
conc. H2SO4
DCE (1 mL)
rt & 2
60
aReaction conditions for -aryalation: 0.25 mmol of cinnamyl tertiary alcohol 1a, 0.62 mmol of aryl halide 2a, Pd(OAc)2 (5 mol%), L-proline (10 mol%), TBAI
(tetrabutylammonium iodide) (1 equiv), K2CO3 (4 equiv), water (0.5 mL), 140 C, 36-48 h. bReaction conditions for Friedel-Crafts alkylation: conc. H2SO4 (0.5 mL),
DCE (1 mL), rt, 2 to 5 min. cIsolated yields of product 4aa. d3aa decomposed.
was further confirmed with the single-crystal X-ray of 4af.20
(Figure 1, for details, see: supporting information).
With the above-optimized conditions, for the single column based
protocol to give indene 4aa (entry 3, Table 3), further to showcase
the efficacy of the strategy, it was aimed at the synthesis of
various indenes. Hence, after a -arylation reaction of 1a with 3-
bromotoluene 2b, the concentrated crude reaction mixture of 3ab
was treated with conc. H2SO4. As anticipated, resulted a mixture
of two indene products 4ab+4ab' (1.2:1) in 70% yield (Table 4).
Similar results were obtained in the case of 4-bromotoluene 2c as
well (4ac+4ac', 2.1:1, 68%, Table 4). This may be due to the
reason that phenyl and tolyl groups are more or less exert the
same sort of electronic effects toward electrophile (due to the
small electron-donating ability of alkyl substituents via +ve
inductive effect). At the same time, 3-bromoanisole 2d gave 4ad
as an exclusive product in 62% yield (Table 4). Since the para-
position to electron releasing OMe group is free, electron-rich, and
is in the right proximity to be captured by the internal electrophile.
However, the reaction of 1a with 4-bromoanisole 2e afforded a
mixture of two products 4ae+4ae' (1.1:1) in 64% yield (Table 4).
This can be rationalized based on the fact that the electrophile
can only react at the meta-position to the electron releasing OMe
group of anisyl moiety, which is not much electron-rich site when
compared to the reactive ortho-para-sites to OMe group. Thus,
simple phenyl and para-anisyl moieties may compete with each
other toward aromatic electrophilic substitution. As a result, it led
to the formation of a mixture of two products. To our delight, in all
other examples, when one out of the two aromatic rings, is
sufficiently electron-rich nature, prevailed in participating in
cyclization step selectively and furnished the corresponding
indene products 4af-4ga (Table 4).
Figure 1: Single-crystal X-ray structure of indene 4af.
In conclusion, an efficient single column chromatography
based protocol was established for the synthesis of indenes. A
[Pd]-catalyzed stereoselective -arylation and intramolecular
Friedel-Crafts alkylation reactions were employed as key steps. It
is worth mentioning that the solvent water was utilized as the
green solvent.
In addition to the spectroscopic evidence toward the
chemical structures 4aa-4ga, the stereoselectivity of arylation
4
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10.1002/ejoc.202000030
European Journal of Organic Chemistry
COMMUNICATION
Table 4: Substrate scope for indenes 4aa-4ga.a-d
5
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10.1002/ejoc.202000030
European Journal of Organic Chemistry
COMMUNICATION
aReaction conditions for -arylation: 0.25 mmol of cinnamyl tertiary alcohols 1a-1g, 0.62 mmol of aryl halides 2a-2g, Pd(OAc)2 (5 mol%), TBAI (tetrabutylammonium
iodide) (1 equiv), L-proline (10 mol%), K2CO3 (4 equiv), solvent water (0.5 mL), 140 C, 36-48 h. bReaction conditions for Friedel-Crafts alkylation: conc. H2SO4 (0.5
mL), rt, 2 min. cIsolated yields of products 4aa-4ga. dThe ratio of E/Z stereoisomers was determined by 1H-NMR analysis.
6
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Acknowledgements
We are grateful to the Department of Science and
Technology-Science and Engineering Research Board
(DST-SERB) [NO: EMR/2017/005312], New Delhi, for
financial support. K.R. thanks MHRD, New Delhi, for the
award of a research fellowship.
Keywords: [Pd]-Catalysis • -Arylation • Friedel-Crafts alkylation
• Indenes • tert-alkenols
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8
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Entry for the Table of Contents
A concise synthesis of Mizoroki-Heck products and corresponding indenes starting with simple tert-alkenols and aryl halides is
presented. Notably, the -arylation was done under [Pd]-catalysis by using water as the sole green solvent and the synthesis of indenes
via acid-mediated intramolecular Friedel-Crafts cyclization.
9
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