A Visible Light and Iron-mediated Carbocationic Route to Polysubstituted 1-Halonaphthalenes by Benzannulation using Allylbenzenes and Polyhalomethanes

Article abstract of DOI:10.1002/adsc.202001249

A wide array of polysubstituted 1-bromo and chloronaphthalenes are obtained from coupling of allylbenzenes and polyhalomethanes. The reaction is mediated by iron metal under visible light irradiation and proceeds via a Kharasch addition intermediate followed by intramolecular Fe^III mediated Friedel-Crafts alkylation, with the formation of two Csp²?Csp² bonds in the process. This method gives easy access to 1-halonaphthalenes with substituent(s) at C-5 to C-8 that are otherwise hard to synthesize. (Figure presented.).

Full text of DOI:10.1002/adsc.202001249

Title: A Visible Light and Iron-mediated Carbocationic Route to
Polysubstituted 1-Halonaphthalenes by Benzannulation using
Allylbenzenes and Polyhalomethanes
Authors: Irwan Iskandar Roslan, Hongwei Zhang, Kian Hong Ng,
Stephan Jaenicke, and Gaik-Khuan Chuah
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202001249
Link to VoR: https://doi.org/10.1002/adsc.202001249

10.1002/adsc.202001249
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
A Visible Light and Iron-mediated Carbocationic Route to
Polysubstituted 1-Halonaphthalenes by Benzannulation using
Allylbenzenes and Polyhalomethanes
Irwan Iskandar Roslan,a Hongwei Zhang,a Kian-Hong Ng,a Stephan Jaenickea and
Gaik-Khuan Chuaha*
a
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543
Fax: +65-6779-1691; phone: +65-6516-2839; e-mail: chmcgk@nus.edu.sg
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
naphthalenes.[7] However, the majority of these
Abstract. A wide array of polysubstituted 1-bromo and
halogenations occur on the same benzene ring as the
directing group so that access to 1-halonaphthalenes
with substituent(s) on the C-5, 6, 7 or 8 positions are
hard to come by.[8] Quayle and collaborators developed
the CuI-catalyzed benzannulation reaction of
chloronaphthalenes are obtained from coupling of
allylbenzenes and polyhalomethanes. The reaction is
mediated by iron metal under visible light irradiation and
proceeds via a Kharasch addition intermediate followed by
intramolecular FeIII mediated Friedel-Crafts alkylation, with
the formation of two Csp2-Csp2 bonds in the process. This
method gives easy access to 1-halonaphthalenes with
substituent(s) at C-5 to C-8 that are otherwise hard to
synthesize.
allylbenzenes
with
an
ortho-substituted
trichloroacetate group to obtain 1-halonaphthalenes
via extrusion of CO2 and two equivalents of HCl.[9]
However, their substrates are not commercially
available and the reaction requires high temperatures.
It is thus desirable to introduce a methodology that
allows access to these rare scaffolds, particularly from
commercially available and cheap substrates and
reagents.
Keywords: Halogenation; Iron; Cyclization; C-H
Activation; Intramolecular Friedel-Crafts
There has been growing interest in halogen atom
transfer radical cyclization (HATRC) of unsaturated
polyhalomethyl substrates to form halo-substituted
(hetero)aromatics.[10] Inspired by these reports and in
continuation of our previous work employing
polyhaloalkanes,[11] we envision that allylbenzenes
could couple with a trihalomethyl moiety using a
polyhalomethane to form a Kharasch addition
intermediate in situ which then undergoes a
benzannulation reaction to yield 1-halonaphthalenes
(Scheme 1). The availability of polyhalomethanes
which have been used as a one-carbon synthon in
recent times is an advantage.[12] Furthermore,
1-Bromo and 1-chloronaphthalene moieties are
important bicyclic scaffolds present in compounds that
are used as fungicides, insecticides, phosphorescent
materials, solar cell solvent additives and for the
determination of refractive indexes of crystals.[1] More
importantly, these halogenated naphthalenes are
frequently employed as intermediates in transition
metal catalyzed cross-coupling reactions such as the
various variants of Suzuki, Heck, Negishi and Stille
coupling.[2] 1-Halonaphthalenes have traditionally
been synthesized from naphthalenes by electrophilic
substitution with various halogenating agents,[3]
usually in the presence of a Lewis acid catalyst.[4]
Functional group interconversions of naphthalenes
containing amines, aroyl chlorides and trifluoroborates
to their respective 1-halo derivatives have also been
demonstrated.[5] However, these methods are often
prone to producing mixtures of positional isomers,
multiple halogenation, or they require stoichiometric
amounts of oxidant or high temperatures. Over the
years, a variety of methods for halogenating activated
naphthalenes have been developed to access various
polysubstituted
1-halonapthalenes.[6]
Hydrogen
bromide, N-halosuccinimides, halogen-based ionic
liquids and tetrabutylammonium tribromide have
emerged as convenient reagents to halogenate
Scheme 1. Coupling between allylbenzenes and
polyhalomethanes mediated by iron and visible light to the
Kharasch addition intermediate followed by benzannulation.
1
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10.1002/adsc.202001249
Advanced Synthesis & Catalysis
Kharasch addition of polyhalomethanes across olefins
is a well-known method of atom transfer radical
Table 1. Optimization parameters.[a]
addition
(ATRA)
to
access
halogenated
hydrocarbons.[13] Peroxides have been used as radical
initiators in ATRA but over the years, metal
complexes based on ruthenium,[14] copper,[15] nickel,[16]
iron[17] rhodium[18] and sodium[19] have become widely
employed. High yields and good chemoselectivities
can be achieved with these metal-based reagents
although issues of long reaction times, high reaction
temperature and costs remain. Amongst the metals, the
reported use of iron powder as a radical initiator is an
attractive proposition as it is cheap, non-toxic, and
readily available.[20]
Entry Solvent
Equiv. of
Fe
Equiv. of
CBr4
Yield
(%)[b]
1
DMF
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.2
0.5
1.1
1.5
4.0
1.0
-
2.0
2.0
2.0
2.0
2.0
2.0
1.5
2.5
3.0
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
73
65
42
84
66
0
53
92
96
trace
38
94
98
n.d.
0
2
3
4
5
6
7
8
9
10
11
12
13
14
15[c]
16[d]
17[e]
18[f]
19[g]
20[h]
21[i]
MeCN
MeNO2
EtOH
i-PrOH
dioxane
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
In comparison to the formation of the Kharasch
addition intermediate, the further transformation
involving its benzannulation is challenging and has -
to the best of our knowledge - not been described
before. Here, we report the viability of our proposed
protocol for the synthesis of polysubstituted 1-
halonaphthalenes by coupling of inexpensive and
commercially
available
allylbenzenes
and
polyhalomethanes under photo-irradiation. An
extensive array of C-5 to C-8 substituted 1-
bromonaphthalenes and 1-chloronaphthalenes has
been synthesized with good to excellent yields under
mild reaction conditions, using white light-emitting
diodes (LED) as the visible light source and mediated
by Fe powder.
0
15
0
67
n.d.
n.d.
1.0
1.0
1.0
1.0
1.0
We began our optimization studies by choosing
allylbenzene 1 as a model substrate to couple with
tetrabromomethane 2b in the presence of 1 equivalent
iron powder in N,N-dimethylformamide (DMF) as
solvent. A 9.5 W white LED lamp was employed as
the light source. Satisfyingly, 73 % yield of 3b was
obtained after 2 hours (Table 1, entry 1). Various polar
aprotic and protic solvents were screened for this
reaction and ethanol, which readily dissolves 2b, gave
the best yield of 3b (Table 1, entries 2 - 6). Next, the
amount of polyhalomethane used in the reaction was
varied. The yield decreased significantly when the
number of equivalents of 2b was reduced to 1.5
whereas 2.5 and 3.0 equivalents gave excellent yields
(Table 1, entries 7 to 9). This suggests that other than
as a substrate, 2b plays additional roles in the reaction.
For instance, polyhalomethanes have been employed
as mild oxidants in many organic reactions.[21] The
effect of varying the amount of Fe was investigated.
Substoichiometric amounts of Fe gave only traces or
very poor yields of 3b, with mainly the Kharasch
intermediate and some unconverted 1 present in the
reaction mixture (Table 1, entries 10 and 11). However,
excellent yields were obtained when the Fe was
increased above the stoichiometric amount (Table 1,
entries 12 and 13). This implies that metallic Fe is most
likely the precursor to an active species formed during
reaction and is not regenerated. However, when a large
excess of Fe was used (Table 1, entry 14), the reaction
became highly exothermic and the reaction mixture
turned viscous, suggesting that some polymerization
of 1 occurred. When FeCl3 was used in place of Fe, 3b
was not formed, instead the Kharasch intermediate
[a]
Reaction conditions: 1 (1.0 mmol), 2b (2.0 mmol) Fe
powder (1.0 mmol) in 1 mL solvent were irradiated using a
[b]
[c]
9.5 white LED lamp at r.t. for 2h. Isolated yields 1.0
equiv. of FeCl3 was used instead of Fe powder. [d] Reaction
performed without Fe powder under light irradiation. [e] 1.0
equiv. of FeBr2 was used. [f] Reaction performed in the dark.
[g] Reaction performed under Ar atmosphere. [h] 2.0 equiv. of
K2CO3 was used. [i] 2.0 equiv. of N,N-diisopropylethylamine
was used.
could be detected together with unconverted 1 (Table
1, entry 15). This was also the case when the reaction
was performed without any Fe (Table 1, entry 16). On
the other hand, with FeBr2 the reaction proceeded with
a modest yield of 3b (Table 1, entry 17). From these
results, it can be surmised that visible light can partly
mediate the Kharasch addition of tetrabromomethane
2b to allylbenzene 1 but in the presence of Fe, the
reaction is greatly accelerated. The active species is
FeII that is formed in situ during the reaction.[22]
However, when the reaction was conducted in the dark
at room temperature in the presence of Fe, neither 3b
nor the Kharasch addition intermediate were detected.
This is not surprising as Fe-catalyzed/mediated
Kharasch addition of polyhalomethanes to olefins
normally requires higher temperatures and longer
reaction times.[17] When the reaction was performed
under Ar atmosphere, 3b was obtained at a reduced
yield of 67 %. Thus, O2 seems to be involved in the
reaction, either as oxidant or as radical initiator.
Attempts to add two equivalents of a base such as
K2CO3 and N,N-diisopropylethylamine to neutralize
2
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10.1002/adsc.202001249
Advanced Synthesis & Catalysis
Table 2. Scope of reaction.[a]
halonaphthalenes (Table 2, 6a, 6a’, 6b and 6b’), due
to the two available positions of attack during the
benzannulation reaction which we were unable to
separate. Allylbenzenes with 4- and 2-substituted
halogen and trifluoromethyl groups were well
tolerated under the reaction conditions, with
significantly higher yields for 1-halonaphthalenes
containing electron withdrawing F and CF3 groups
(Table 2, 7 – 10). Allylbenzenes substituted in the 4-
or 2-position with electron donating groups such as
alkoxy and benzyloxy were also suitable substrates for
this protocol, producing high yields (Table 2, 11 – 14)
whereas a 2-substituted hydroxyl group gave a modest
yield of 15b. In addition, reactions employing 4-
allylbiphenyl proceeded smoothly with good yields of
7-phenyl substituted 1-halonaphthalenes (Table 2, 16a
and 16b). Next, we screened various di- and tri-
substituted allylbenzenes towards forming multiply
substituted 1-halonaphthalenes (Table 2, 17 – 20).
Eugenyl methyl ether, eugenol and methyl 5-allyl-3-
methoxysalicylate gave the major products 17, 18 and
19, respectively, in moderate yields whereas good
yields of tetra-substituted 1-halonaphthalenes 20a and
20b were obtained using 4-allyl-2,6-dimethoxyphenol
as the substrate. Gratifyingly, 1-allylnaphthalenes
reacted smoothly under these conditions with either
CBrCl3 or CBr4 to give excellent yields of 1-
halophenanthrenes 21a and 21b. Last but not least, a
couple of methallylbenzenes were also screened and
found to be excellent substrates for the reaction (Table
2, 22 and 23).
A series of experiments were conducted to gain
insights into the reaction mechanism (Scheme 2).
Exposing 4-allylanisole to visible light without the Fe
powder gave the Kharasch addition intermediate 24 in
36 % isolated yield after 2 hours. There was still
unconverted substrate in the reaction mixture. The
termination of the reaction at the Kharasch addition
intermediate points towards the involvement of Fe in
[a]
Reaction conditions: 1 (1.0 mmol), 2 (2.5 mmol). Fe
the
subsequent
benzannulation
reaction.
powder (1.1 mmol) in 1 mL EtOH were irradiated using a
9.5 white LED lamp at r.t. for 2h. [b] Using 2.5 mmol of CCl4
instead of CBrCl3 in 1 mL DMF for 8 h.
Photoexcitation was necessary, and no reaction
occurred in the dark (Table 1, entry 17). Visible light
can cause homolytic cleavage of the C-Br bond in
CBrCl3 and CBr4 which explains its role in the
reaction.[23] This dispenses with the need for heating as
the C-Br bond can also cleave under thermal
conditions in the presence of the iron catalyst.[24] Next,
the Kharasch addition intermediate 24 was employed
as the substrate and subjected to the optimized
conditions in the absence of the polyhalomethane.
Stoichiometric amounts of iron as metallic Fe, FeBr2
and FeCl3 were added (Scheme 2, b). Interestingly, the
desired product 5b was not observed in any of these
three experiments. The reactions were repeated with
addition of 1.5 equivalents of CBr4 (Scheme 2, c). This
time, 5b was formed in 33 % yield with FeBr2, but not
with Fe or FeCl3. These results show that both FeII and
polyhalomethane are required for the benzannulation
step and that the latter is required in an
overstoichiometric amount. Under visible light, an
FeII-polyhalomethane species is formed in situ. This
active species has been observed during Kharasch
the HBr liberated in the process proved to be futile as
the reactions were messy due to competing side
reactions (Table 1, entries 20 and 21).
We then proceeded to investigate the scope of
reaction under the optimized conditions using a slight
excess of 1.1 equivalents of Fe and 2.5 equivalents of
CBrCl3 or CBr4 as the polyhalomethane for the
synthesis of 1-chloro- and 1-bromonaphthalenes,
respectively (Table 2). With CBrCl3 and allylbenzene,
excellent yields of 3a were obtained after 2 hours.
Furthermore, CCl4 could also be used instead of
CBrCl3, although the synthesis of 3a required much
longer reaction times and the use of DMF as solvent.
2- and 4-Allyltoluenes couple well with CBrCl3 and
CBr4, giving excellent yields of 5- and 7-methyl
substituted 1-halonaphthalenes, respectively (Table 2,
4a, 4b, 5a and 5b). On the other hand, 3-allyltoluenes
gave mixtures of 6-methyl and 8-methyl substituted 1-
3
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10.1002/adsc.202001249
Advanced Synthesis & Catalysis
Figure 1. Proposed Mechanism
The subsequent steps are similar to the traditional
intramolecular Friedel-Crafts alkylation,[27] namely
generation of a carbocation catalysed by FeIII to form
intermediate C and its nucleophilic attack by the
delocalized π-system to give intermediate D. Next,
deprotonation of the carbocation by Br- from the
[FeIII]- complex takes place, restoring the aromaticity
of the naphthyl ring with simultaneous extrusion of
HBr and release of the [FeIII] complex to form
intermediate E. Dehydrohalogenation assisted by CBr4
then yields the desired 1-halonaphthalene product
together with another equivalent of HBr. This
Scheme 2. Mechanistic studies.
mechanism explains the requirement for
a
addition of CCl4 to olefins.[25] Radical trapping
experiments were also conducted, where allylbenzene
and the Kharasch intermediate 24 were reacted at their
respective optimized conditions with addition of 2.0
stoichiometric amount of iron because it forms the
catalytically active FeII species that adds the
halomethane to the allylbenzene but is non-
regenerable as it is further oxidized to FeIII during the
subsequent cyclization step. The mechanism also
explains the need for over-stoichiometric amounts of
CBr4 which, in addition to being a coupling partner of
allylbenzene 1, also acts as an oxidant to generate the
FeII active species in situ.
In summary, we have developed a protocol for the
facile synthesis of a wide array of polysubstituted 1-
bromo and 1-chloronaphthalenes from the coupling of
allylbenzenes with the polyhalomethanes, CBr4 and
CBrCl3, respectively. The reaction is mediated by iron
metal and visible light and proceeds via a Kharasch
addition of polyhalomethanes to the allylbenzenes,
followed by a benzannulation reaction, forming two
Csp2-Csp2 bonds in the process. This protocol gives
access to 1-halonaphthalenes with substituent(s) at C-
5 to 8 that are challenging to synthesize otherwise. A
plausible mechanism is proposed whereby Fe metal is
oxidized to the active species FeII in situ prior to the
Kharasch addition, followed by the involvement of
FeIII in the electrophilic substitution reaction towards
formation of the desired product.
equivalents of the radical scavenger
2,2,6,6-
tetramethylpiperidin-1-yl oxyl (TEMPO) (Scheme 2,
d and e). With allylbenzene, no 3b was formed at all
but a trace amount of the Kharasch intermediate 24
was found in the reaction mixture. However, starting
from 24, product 3b could be detected in small
amounts. In addition, the bromo-TEMPO adduct could
be observed for both reactions via ESI-MS.[26] These
results confirm that the reaction proceeds via a radical
pathway and also that •Br and •CBr3 are not only
involved in the Kharasch addition but also play a role
in the subsequent benzannulation. This explains why
an excess of polyhalomethane has to be used in the
reaction.
Based on the above results, a plausible reaction
mechanism is proposed (Figure 1). Under visible light,
the homolytic cleavage of the C-Br bond forms •Br and
•CBr3 radicals which react with the Fe metal to form a
FeII-polyhalomethane complex [BrFeIICBr3] (denoted
as [FeII]. This complex activates CBr4 for the Kharasch
addition to the allylbenzene, and intermediate A is
formed. Elimination of H and Br leads to the
intermediate B, with oxidation of the [FeII] species and
release of bromoform or HBr in the process. The
presence of bromoform in the reaction mixture was
detected by GC and confirmed by GC-MS.
4
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10.1002/adsc.202001249
Advanced Synthesis & Catalysis
Experimental Section
Nishina, K. Takami, Green Chem. 2012, 14, 2380-2383;
c) M. Kodomari, H. Satoh, S. Yoshitomi, J. Org. Chem.
1988, 53, 2093-2094.
General Procedure for the Synthesis of 1-
halonaphthalenes
[5] a) J. G. Lee, H. T. Cha, Tett. Lett. 1992, 33, 3167-3168;
b)W. Baik, W. Luan, H. J. Lee, C. H. Yoon, S. Koo, B.
H. Kim, Can. J. Chem. 2005, 83, 213-219; c) G. A.
Molander, L. N. Cavalcanti, J. Org. Chem. 2011, 76,
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Org. Lett. 2017, 19, 4142-4145.
A test tube was charged with allylbenzene 1a (132 µL, 1.0
mmol), CBrCl3 2a (246 µL, 2.5 mmol) and iron powder (61
mg, 1.1 mmol) in 1 mL of ethanol. The test tube was placed
in an 8-port sample holder of the photoreactor (Figure S1).
The reaction mixture was stirred in open air under
irradiation from a 9.5 W white LED lamp at room
temperature. Upon completion, the reaction mixture was
diluted with ethyl acetate and washed with saturated
aqueous sodium bicarbonate followed by brine and
subsequently dried with anhydrous Na2SO4. After filtration,
the solvent was removed by rotary evaporation and the
residue was purified by column chromatography using
hexane as eluent to afford 3a as a colourless oil in 90 % yield.
[6] a) Y.-L. Ren, B. Wang, X.-Z. Tian, S. Zhao, J. Wang,
Tett. Lett. 2015, 6, 6452-6455; b) A. L. S. Thompson, G.
W. Kabalka, M. R. Akula, J. W. Huffman, Synthesis
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R. Fochi, J. Org. Chem. 1999, 64, 3448-3453; d) S. C.
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Hopkins, A. A. Lignieres, A. K. Pitzel, A. A. Lamar,
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Acknowledgements
Financial support from Ministry of Education (Singapore) Tier 1
Grants R-143-000-B07-114 and R-143-000-A46-114 is gratefully
acknowledged. I. I. Roslan thanks the Faculty of Science, NUS for
the award of a RSB-funded research fellowship.
[7] a) K. Ohkubo, K. Mizushima, R. Iwata, S. Fukuzumi,
Chem. Sci. 2011, 2, 715-722; b) D. A. Rogers, R. G.
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LeBlanc, A. A. Lamar, ACS Omega 2018, 3, 12868-
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M. Miura, J. Am. Chem. Soc. 2020, 142, 1621-1629; d)
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Advanced Synthesis & Catalysis
COMMUNICATION
A Visible Light and Iron-mediated Carbocationic
Route to Polysubstituted 1-Halonaphthalenes by
Benzannulation using Allylbenzenes and
Polyhalomethanes
Adv. Synth. Catal. Year, Volume, Page – Page
Irwan Iskandar Roslan,a Hongwei Zhang,a Kian-
Hong Ng,a Stephan Jaenickea and Gaik-Khuan
Chuaha*
7
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