In(III)-Catalyzed Direct Regioselective Syntheses of 1-Naphthaldehyde Derivatives via a Hidden Aldehyde 1,3-Translocation and Disjointed CO2Extrusion

Article abstract of DOI:10.1021/acscatal.1c00629

A highly regioselective annulation of 3-formylchromones with alkynes in the presence of indium triflate leads to the direct construction of diverse 1-naphthaldehyde derivatives. This one-pot de novo protocol features an unusual aldehyde 1,3-translocation and disjointed CO2 extrusion. This methodology is effective for the construction of structurally diverse 1-naphthaldehydes bearing chiral moieties and polyaromatics. These naphthaldehydes can be further easily elaborated into a wide variety of functional groups. Density functional theory computations show that this In(III)-catalyzed reaction appears to proceed via a stepwise dearomative cyclization, lactonization, ring contraction, and, finally, extrusion of CO2. Most interestingly, the aldehyde translocation occurs not by the transposition of the aldehyde but rather by the skeletal rearrangement of the substrate arene.

Full text of DOI:10.1021/acscatal.1c00629

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Research Article
In(III)-Catalyzed Direct Regioselective Syntheses of
1
‑Naphthaldehyde Derivatives via a Hidden Aldehyde 1,3-
Translocation and Disjointed CO Extrusion
2
Sabera Sultana, Gisela A. González-Montiel, Samjhana Pradhan, Hari Datta Khanal, Sagar D. Nale,
Paul Ha-Yeon Cheong,* and Yong Rok Lee*
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sı Supporting Information
ABSTRACT: A highly regioselective annulation of 3-formylchromones
with alkynes in the presence of indium triflate leads to the direct
construction of diverse 1-naphthaldehyde derivatives. This one-pot de
novo protocol features an unusual aldehyde 1,3-translocation and
disjointed CO2 extrusion. This methodology is effective for the
construction of structurally diverse 1-naphthaldehydes bearing chiral
moieties and polyaromatics. These naphthaldehydes can be further easily
elaborated into a wide variety of functional groups. Density functional
theory computations show that this In(III)-catalyzed reaction appears to proceed via a stepwise dearomative cyclization,
lactonization, ring contraction, and, finally, extrusion of CO . Most interestingly, the aldehyde translocation occurs not by the
2
transposition of the aldehyde but rather by the skeletal rearrangement of the substrate arene.
KEYWORDS: In(III)-catalyzed, regiocontrolled, 1-napthaldehydes, annulation, alkynes
aphthalenes are important structural elements found in
all the starting materials are readily accessible, and this
methodology opens a new, reliable, and simple way to
synthesize complex polyaromatic hydrocarbons.
N
many functional materials, pharmaceuticals, and natural
1
products with numerous applications in academia and
2
industry. They are also widely used as valuable building
Our investigation commenced with the reaction of 3-
formylchromone (1a) and phenylacetylene (2a) (Table 1).
The initial attempts with Brønsted acids such as p-TsOH and
TFA and Lewis acids such as AgOTf, Cu(OTf) , and AlCl in
3
blocks for the construction of more complex polyaromatics.
Conversions of naphthalenes to 1- or 2-naphthaldehydes via
4
simple oxidation of alcohols or coupling reaction of functional
2
3
5
groups on the naphthalene ring are known. However, direct
toluene at 80 °C for 12 h resulted in recovered starting
construction of naphthaldehydes from simple starting materials
is rare. The Loh group has reported the synthesis of 1-
naphthaldehydes using Rh(III)-catalyzed C−H bond function-
materials (entries 1−5, Table 1). However, with Sc(OTf) ,
3
product 3a was isolated in a 79% yield (entry 6). Interestingly,
a significantly improved yield was observed with In(OTf) as a
3
6
alization of enaminones with vinyl esters (Scheme 1a). 2-
catalyst (entries 7−11). Notably, this product appears to arise
from a complex sequence of events that involves the
incorporation of the incoming alkyne, loss of CO and O,
Naphthaldehydes are accessible through platinum-catalyzed
rearrangement of epoxyalkynylbenzenes by the Liu group
7
(
Scheme 1b) and Rh(III)-catalyzed reaction of enaminones
most likely through extrusion of CO , and 1,3-translocation of
2
8
with alkynes by the Zhu group (Scheme 1c). However, the
development of an efficient and facile approach to highly
functionalized naphthaldehydes from readily available starting
materials is still a significant challenge with potential to greatly
broaden access to these privileged building blocks.
the aldehyde. In all these cases, the possible regioisomer 3a′
was not obtained. The best yield (84%) was obtained with 5
mol % In(OTf) in chlorobenzene at 80 °C for 1 h (entry 8).
3
Polar solvents such as acetonitrile and DMF led to no reaction
(
entries 12 and 13). Moreover, the reactions using InCl and
3
We have been engaged in the development of novel
methodologies for the synthesis of diverse aromatics and
heteroaromatics using Lewis acid catalysts such as indium salts
InBr in chlorobenzene at 80 °C for 12 h did not afford
3
9
Received: February 9, 2021
Revised: April 20, 2021
Published: May 18, 2021
and BF ·OEt . In continuation of our studies on Lewis acid-
3
2
catalyzed reactions for the development of new methodologies,
here, we report an In(OTf) -catalyzed regiocontrolled direct
3
construction of diverse and polyfunctionalized 1-naphthalde-
hydes through annulation of 3-formylchromones with sym-
metrical or unsymmetrical alkynes (Scheme 1d). Most notably,
©
2021 American Chemical Society
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Scheme 1. (a−d) Strategies for Direct Construction of 1-
and 2-Naphthaldehydes via Cyclization
Scheme 2. Substrate Scope of Terminal Alkynes 2b−2s
a
Table 1. Optimization Studies
b
entry catalyst (mol %)
solvent
temp. (°C) time (h) yield (%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
p-TsOH (5)
TFA (5)
AgOTf (5)
toluene
toluene
toluene
toluene
toluene
toluene
toluene
PhCl
80
80
80
80
80
80
80
80
80
80
130
80
80
80
80
12
12
12
12
12
1
1
1
1
1
0
0
0
0
Cu(OTf) (5)
2
AlCl (5)
0
3
Sc(OTf) (5)
79
81
84
75
84
71
0
0
0
0
3
In(OTf) (5)
3
In(OTf) (5)
3
In(OTf) (2)
PhCl
PhCl
PhCl
3
0
1
2
3
4
5
In(OTf) (10)
3
In(OTf) (5)
1
3
In(OTf) (5)
CH CN
12
12
12
12
3
3
8
3
7, and 75% yields, respectively. In addition, a combination of
-formylchromones 1b−1e bearing electron-donating and
In(OTf) (5)
DMF
PhCl
PhCl
3
InCl (5)
3
electron-withdrawing groups with alkynes 2e−2h was well-
tolerated and provided the corresponding products 3e−3h in
80−84% yields. Satisfactorily, terminal alkynes 2i−2m bearing
polycyclic arenes and heteroaromatics such as biphenyl, 1-
naphthalenyl, 2-naphthalenyl, 9-phenanthranyl, and 3-thieno-
phenyl moieties were also tolerated under the standard
conditions to give the desired products 3i−3n in 78−88%
yields. Moreover, alkynes 2n−2s bearing vinyl, alkyl, and
cycloalkyl groups gave the desired products 3o−3t in 60−79%
isolated yields.
Having seen the generality of diverse terminal alkynes
tolerated by the reaction, we then explored the use of internal
alkynes 4a−4k (Scheme 3). Reaction of 1a or 1b with
diphenylacetylene (4a) generated the desired 5a and 5b in 71
and 69% yields, respectively. With the symmetric diaryl-
InBr (5)
3
a
Reaction conditions: 1a (0.5 mmol), 2a (0.5 mmol), and solvent (1
mL). Isolated yield.
b
product 3a (entries 14 and 15). The structure and
regiochemistry of 3a were confirmed by H NMR. We were
1
also intrigued by the possibility of using 3-acetylchromone
instead of 3-formylchromone. However, the reaction of 3-
acetyl-4H-chromen-4-one with 2a under standard reaction
conditions did not afford any product.
We examined the scope and generality using terminal
alkynes (Scheme 2). Treatment of 1a with terminal arylalkynes
2
b−2d bearing electron-donating and electron-withdrawing
groups on benzene provided desired products 3b−3d in 78,
6
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Scheme 3. Substrate Scope of Internal Alkynes 4a−4k
Scheme 4. Substrate Scope of Active and Chiral Internal
Alkynes 6a−6l
substituted alkynes 4b and 4c bearing electron-donating and
electron-withdrawing groups, 5c and 5d were isolated in 67
and 63% yields. Dialkyl-substituted alkynes 4d and 4e were
also feasible and gave the corresponding products 5e and 5f in
and, instead, resulted in an intractable mixture. Furthermore,
reactions using electron-deficient internal alkynes 6j−6l
bearing chiral ester and amide groups led to the products
7j−7l in 73, 70, and 41% yields, respectively. It is also
interesting to note that there appears to be no significant
electronic effects of electron-donating or electron-withdrawing
groups on the aromatic ring of either the 3-formylchromones
or the alkynes for the formation of the products. However,
these results also showed that electron-donating and electron-
withdrawing groups directly conjugated to the triple bond of
alkynes were critical in controlling the regiochemistry.
Having confirmed the generality of this transformation for
monoalkynes, we turned our attention to various diynes
(Scheme 5). Delightfully, the reactions of 1a with 1,4-
diethynylbenzene (8a), 1,4-bis(phenylethynyl)benzene (8b),
1,4-diphenylbuta-1,3-diyne (8c), and 9,10-bis(phenylethynyl)-
anthracene (8d) provided the products 9a−9d in 77, 67, 69,
and 51% yields, respectively.
6
2 and 64% yields, respectively. Moreover, the reactions with
unsymmetrical ethynylbenzene 4f−4k bearing methyl, ethyl, n-
butyl, n-heptyl, benzyl, and cyclohexyl groups on the ethynyl
moiety also afforded the corresponding products 5g−5t in 70−
8
6% yields. The structure and regiochemistry of 5a-5t were
confirmed by juxtaposition of the spectral data to compound
m, which was verified by single-crystal X-ray diffraction
analysis.
Next, the scope of this annulation was explored by using
5
electron-deficient or electron-rich alkynes as well as chiral
internal alkynes 6a−6l (Scheme 4). Electron-deficient alkynes
6
a−6h bearing formyl, ketone, ester, amide, sulfinyl, sulfonyl,
bromo, and chloro groups were also tolerated and provided
a−7h in 64−75% yields. Interestingly, phenyl-
phenylethynyl)sulfane (6i) gave product 7i in a 71% yield.
7
(
The regiochemistry of 7i was additionally confirmed by X-ray
crystallography. However, the reaction of 1a with
In addition, to show the practical applicability of the
protocol, the product aromatic aldehyde can be easily further
derivatized. In particular, we were delighted to obtain the
(
phenoxyethynyl)benzene failed to afford the desired product
6
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Scheme 5. Substrate Scope of Dialkynes 8a−8d
Scheme 7. Proposed Catalytic Cycle and Quantum
Mechanically Computed Energies for the Formation of 5g
with Respect to the 1a′ Complex and 4f
process is the rate- and regio-determining step of this reaction.
The unusual stability of vinyl cation intermediate I appears to
arise from the substantial hyperconjugative and conjugative
1
0
capricious phenalenyl-fused pyrylium product (see the
Supporting Information, Scheme S1).
17
To elucidate the mechanism, a crossover experiment was
performed using equimolar 1a and dideuterated formychro-
mone 1a-D to give products 3a/3a-D (Scheme 6). This
stabilization of the reactive vinyl cation. Addition to this vinyl
cation completes the transannular cyclization with a barrier of
18.1 kcal/mol. This formal [4+2] process affords the bridged
bicyclic adduct II (ΔG = 4.9 kcal/mol), and subsequent C−O
‡
Scheme 6. Control Experiment for 3a-D and 3a/3a-D
bond cleavage (ΔG = 13.3 kcal/mol) and rearomatization of
‡
the spiro intermediate III (ΔG = 9.0 kcal/mol) give rise to
the acylium arene IV (ΔG = 0.5 kcal/mol). The surprising
relative energetic stability of acylium arene IV stems from the
stability gained by aromatization of the newly formed arene.
Juxtaposition of saturated analogues of III and IV reveals that
indeed, the aromatization energy mitigates the penalty of
forming the reactive acylium (ΔG = 15.2 kcal/mol, in
comparison to ΔG = −3.6 kcal/mol from III to IV, see the
Supporting Information, Section 14). Lactonization of the
‡
acylium arene (ΔG = 6.6 kcal/mol) furnishes the unsaturated,
experiment suggested that the aldehyde 1,3-translocation
occurs exclusively intramolecularly and not intermolecularly
between two substrates. Based on these observations, we
explored the mechanism of this reaction for the formation of
naphthaldehyde 5g using the density functional theory
eight-membered lactone V (ΔG = −5.5 kcal/mol). Transfer of
In(OTf) to another 3-formylchromone starting material
3
‡
followed by 6π-electrocyclic ring contraction (ΔG = 12.5
kcal/mol) gives β-lactone VI (ΔG = −2.4 kcal/mol). Finally,
elimination of CO affords the observed naphthaldehyde
2
11
12
13
(
(
DFT)−ωB97XD /6-31G* and LANL2DZ basis sets
product 5g (ΔG = −70.7 kcal/mol).
1
4
for In) in SMD (toluene) solvation at 80 °C as
It is interesting to note that the aldehyde 1,3-translocation
occurs not by the direct transposition of the aldehyde itself but
by the skeletal rearrangement of the arene moiety. The formal
[4+2] destroys the aromaticity of the arene, and the
subsequent acylium ion formation and lactonization process
rearranges the carbon skeleton connectivity. Ring contraction
15
implemented in Gaussian 16. The applicability of DFT
methods for studying In-catalyzed reactions has been
16
demonstrated by other groups. Alternative reaction pathways
were also considered with DFT computations (see the
Supporting Information, Section 15). The complete catalytic
cycle and the energies are shown in Scheme 7.
and CO extrusion restore the arene structure and aromaticity,
2
The cycle begins with a stepwise dearomative cyclization
leading to an apparent aldehyde 1,3-translocation.
involving the In(OTf) and 3-formylchromone complex 1a′
The regioselectivity of naphthaldehyde 5g was also
investigated by computing the major and minor transition
structures of nucleophilic 1,4-conjugate alkyne (4f) addition to
the In complex of formylchromone (1a′) (Scheme 8). DFT
3
and alkyne 4f. The nucleophilic 1,4-conjugate addition of
‡
alkyne 4f (ΔG = 24.3 kcal/mol) results in the formation of
the vinyl cation intermediate I (ΔG = 14.4 kcal/mol). This
6
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Scheme 8. Alkyne Addition Transition Structures and
Computed Energies with Respect to the 1a′ Complex and 4f
Detailed experimental procedures, characterization data,
1
detailed computational studies, and copies of H NMR
1
3
and C NMR spectra (PDF)
FAIR data, including the primary NMR FID files, for all
synthesized compounds (RTF)
Accession Codes
CCDC 2051230, 2051235, 2051239, 2051264 contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif, by emailing data_request@ccdc.cam.ac.uk,
or by contacting The Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
Paul Ha-Yeon Cheong − Department of Chemistry, Oregon
State University, Corvallis, Oregon 97331, United States;
orcid.org/0000-0001-6705-2962; Email: paulc@
science.oregonstate.edu
Yong Rok Lee − School of Chemical Engineering, Yeungnam
University, Gyeongsan 38541, Republic of Korea;
orcid.org/0000-0002-4048-8341; Email: yrlee@yu.ac.kr
shows that there is substantial preference for the observed
regiocontrol by 5.8 kcal/mol. The major alkyne addition-TS
results in the formation of a more stable benzylic cation (ΔG
Authors
Sabera Sultana − School of Chemical Engineering, Yeungnam
University, Gyeongsan 38541, Republic of Korea
Gisela A. González-Montiel − Department of Chemistry,
Oregon State University, Corvallis, Oregon 97331, United
States
Samjhana Pradhan − School of Chemical Engineering,
Yeungnam University, Gyeongsan 38541, Republic of Korea;
orcid.org/0000-0002-3934-9248
Hari Datta Khanal − School of Chemical Engineering,
Yeungnam University, Gyeongsan 38541, Republic of Korea;
orcid.org/0000-0001-9955-1256
Sagar D. Nale − School of Chemical Engineering, Yeungnam
University, Gyeongsan 38541, Republic of Korea;
orcid.org/0000-0002-6326-3188
‡
=
24.3 kcal/mol). In contrast, the disfavored minor TS results
in the formation of a less stable homobenzylic cation that is
hyperconjugated to the methyl group (see the Supporting
Information, Section 14).
These computational and experimental results indicate that
the observed high regioselectivities are determined by the
electronic nature of the alkyne π-system in the initial
1
8
nucleophilic addition (Scheme 2). For example, with
terminal alkynes 2a−2s bearing electron-donating or elec-
tron-rich substituents such as aryls, heteroaryl, vinyl, and alkyl
groups, compounds 3a−3t are exclusively produced via an
addition transition state where the developing positive charge
of the vinyl cation is positioned alpha to the stabilizing
substituent. In the case of unsymmetrical internal alkynes
bearing alkyls and electron-withdrawing groups such as CHO,
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.1c00629
COMe, COOEt, CONMe , SOMe, Ts, Br, and Cl, products
2
Author Contributions
All authors have given approval to the final version of the
5g−5t and 7a−7h are selectively formed by addition transition
states where the forming cation is in the more stabilizing
benzylic position. Surprisingly, with alkyne 6i bearing an
electron-donating SPh group, 7i was isolated, arguably due to
better stabilization of the cation via the sulfur lone pairs.
In summary, we have developed an In(III)-catalyzed
regioselective addition of terminal or internal alkynes to 3-
formylchromones for the formation of diverse 1-napthaldehyde
derivatives. The reaction proceeds via a complex sequence of
events that features a hidden aldehyde translocation and
manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Research
Foundation of Korea (NRF) grant funded by the Korea
government (MSIT) (2018R1A2B2004432 and
2
021R1A2B5B02002436). P.H.-Y.C. is the Bert and Emelyn
disjointed CO extrusion. The methodology is compatible with
2
Christensen professor of OSU and gratefully acknowledges
financial support from the Vicki & Patrick F. Stone family, the
National Science Foundation (NSF, CHE-1352663).
a wide range of functional groups opening a new and simple
way to synthesize complex polyaromatic molecules and their
precursors.
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ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.1c00629.
■
■
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