Access to 3-Oxindoles from Allylic Alcohols and Indoles

Article abstract of DOI:10.1002/chem.201800348

The site-selective and regioselective allylation of 2-substituted indoles was performed by using a ruthenium(IV) precatalyst containing a phosphine–sulfonate chelate. Mono-, di-, and triallylated indoles were selectively obtained depending on the reaction

Full text of DOI:10.1002/chem.201800348

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Accepted Article
Title: Access to 3-oxindoles from Allylic Alcohols and Indoles
Authors: Mathieu Jérôme Achard, Hortense Lauwick, Yang Sun, Huriye
Akdas-Kilig, and Sylvie Derien
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Access to 3-oxindoles from Allylic Alcohols and Indoles
Hortense Lauwick,[a] Yang Sun,[a] Huriye Akdas-Kilig,[a] Sylvie Dérien[a]* and Mathieu Achard[a]*
Dedication ((optional))
Abstract: The site and regioselective allylation reaction of 2-
substituted indoles was carried out by using a ruthenium(IV)
precatalyst containing phosphine-sulfonate chelate. Mono-, di- and
tri-allylated indoles could be selectively obtained according to
reaction conditions and gave only water as byproduct. The
preparation of 3-oxindole derivatives was then successfully
performed owing to the oxidation under air of the corresponding
allylated indoles. Diallylated pseudoindoxyls were proved to be good
synthons to perform cyclization through Ring Closing Metathesis
affording the corresponding tricyclic adducts. Photophysical
properties of 3-oxindoles have been measured, some compounds
showing a strong fluorescence in water.
Therefore the development of sustainable transformations to
access 3-oxindole derivatives minimizing the steps and waste is
highly desirable.
Transition metal complexes-catalyzed allylic substitution become
a method of choice for the formation of various Carbon-Carbon
and Carbon-Heteroatom bonds.[10] In these transformations, the
use of dissymmetric allylic substrate raises the control of
regioselectivity and several ruthenium precatalysts have shown
excellent activities for the formation of branched products.[11]
Interestingly, recent developments toward the introduction of an
allylic or an alkyl fragment were developed via transition metal-
catalyzed allylic substitution, borrowing hydrogen methodology
or more recently hydroelementation starting from simple allylic or
aliphatic alcohols[12-17] and alkynes or allenes[18] providing an
useful atom economical toolbox to access to allylated or
alkylated indoles. Recently, some of us reported the synthesis of
an allylation ruthenium precatalyst by designing an allylic
ruthenium(IV) complex featuring phosphine-sulfonate chelate
which proven efficiency in regio- and chemo-selective allylation
from various allylic alcohols.[16j,19]
Introduction
Pseudoindoxyl derivatives containing the indolin-3-one core
structure and a quaternary stereogenic center at the 2-position is
an attractive class of compounds with highly interesting
photophysical or biological properties (Figure 1).[1,2] They are
found in various biomolecules such as the spirocyclic
Aristotelone,[1a]
Brevianamides,[1b]
Mytragynine
pseudoindoxyl[1c,d] as well as in the Isatisine A,[1e] Duocarmycin
A,C [1f,g] and Fluorocurine.[1h] Following the seminal observations
of Perkin and Plant[3] that 10,11-dihydroxyhexahydrocarbazoles
are unstable under basic conditions, reexamination by Witkop
demonstrated the formation of the key 3-hydroxyindolenines
which undergo a semi-pinacolic rearrangement to afford the
corresponding 3-oxindoles.[4] Various oxidative approaches have
been described in the literature to access 3-hydroxyindolenines
involving the use of strong oxidants such as dimethyldioxirane,[5]
meta chloro perbenzoic acid[6] and others.[7] Alternative pathways
involve photo-oxygenation of the substituted indoles and the
transient formation of hydroperoxides.[8] Alternative approaches
to 3-oxindoles are also reported in the literature.[9]
Due to the presence of a rigid conjugated electron-donor
acceptor fragment Restricting Intramolecular Rotation (RIR),
several pseudoindoxyls exhibit fluorescent properties. In 1983,
during the isolation of various alkaloids of Aspidosperma
oblongum, Potier and al. isolated pseudoindoxyl derivatives as
“Produit jaune, amorphe, très fluorescent à l'uv”.[1c] Recently, 3-
oxindoles have been used as fluorophores (Figure 1).[2] Among
them, Lipid green® has been used for the fluorescent labelling of
lipid droplets.[2b,c] Other reports highlight their facile post-
functionalization to tune their photophysical properties.[2a]
Figure 1. Examples of biorelevant or synthetic pseudoindoxyls and
applications.
Herein we disclose a facile access to various substituted
indole derivatives starting from allylic alcohols via a ruthenium-
catalyzed regio- and site-selective allylation followed by a solid-
state oxidation on the resulted allylated indoles to afford the
corresponding indoxyls generating water as the sole byproduct
of the overall reaction sequence.
Results and Discussion
[a]
Univ Rennes, ISCR (Institut des Sciences Chimiques de Rennes) –
UMR 6226, F-35000 Rennes, France
The allylation of 2-methyl indole 1a in the presence of
catalytic amount of our previously described Ru-1
{[Ru(Cp*)(H2CCHCH2)(dppbs)]PF6} was first evaluated (Table
1).[16j] During the stoichiometric treatment of 1a with allyl alcohol
2a, selective C(3)-allylation occurred in dichloromethane in less
than three hours reaction time providing 3aa with almost
E-mail: mathieu.achard@univ-rennes1.fr
sylvie.derien@univ-rennes1.fr
Supporting information for this article is given via a link at the end of
the document. ((Please delete this text if not appropriate))
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complete conversion (entry 1). Increasing the amount of allyl
alcohol 2a to 2 equivalents, resulted in the selective N- and
C(3)-allylation to afford the product 4aa (entry 2). Higher amount
of allyl alcohol along with the catalyst loading had a crucial
influence on the selectivity and favored the formation of the
diallylated compound 4aa (entry 2). 2-methylindoles are useful
scaffolds for the generation of 2-vinylindolines and o-
quinodimethanes.[20] However, alkylation of 2-methylindole
usually require harsh reaction conditions or the use of strong
base such as organolithium reagent or KHMDS to ensure
conversion.[20] Astonishingly, this catalytic system was not limited
to the N- or C(3) allylation and for the first time, the base free
allylation of the methylene moiety was achieved leading to the
tri-allylated product 5aa accompanied with traces of the tetra-
allylated side product (entry 3). It is important to note that this
last transformation was very sensitive to the reaction conditions
and lower selectivity and conversion were observed with lower
catalyst loading and/or insufficiently deaerated solvent. Finally,
almost complete formation of the tri-allylated indole 5aa was
obtained in the presence of 7 mol% of Ru-1 (entries 4 and 5).
Having established our best reaction conditions toward selective
allylation, we next examined the scope of the transformation with
2-methylindole 1a and 2-phenyl indole 1b (Scheme 1). As
expected, indoles 1a and 1b react smoothly with allyl alcohol 1a
leading to the selective formation of mono-allylated products 3aa
and 3ba in up to 90% isolated yields. In the case of
unsymmetrical allylic alcohols, the allylation afforded the
branched indoles with complete regioselectivity toward the
branched compounds between 70 and 96% isolated yields.
Interestingly, reverse prenylation was also observed starting
from 2-Methyl-3-buten-2-ol 2f affording allylated indole 3af in up
to 93% isolated yield.[21] The reaction of 1a with linear allylic
alcohol 2g and 2h provided the access to the branched indoles
3ab and 3ad in up to 97:3 ratio. In the light of the selective
formation of branched products, the diallylation reaction
provided the access to the dibranched indoles 4 with isolated
yields ranging from 86 and 99% without diastereoselectivity.
Interestingly, as a reminiscence of the Potier statements, during
the isolation by column chromatography on silica gel of the
colourless indole 3aa, we observed its partial decomposition
highlighted by the apparition of a yellow band.[1c] Analysis of the
side product demonstrated the formation of the fluorescent
pseudoindoxyl 6aa. The latter arose from the oxidation of the
indole 3aa involving the transient formation of hydroperoxides
followed by a semi pinacolic rearrangement.[8,22] Thus, having
prepared our set of substituted indoles, we next examined their
reactivity toward oxidation. To achieve this task, solvent less
oxidation of the suspended indole 3ac on SiO2 was chosen to
prevent the formation of undesired side products arising
intermolecular side reactions (Table 2).[8] To our delight, 20% of
conversion was observed after one hour under sun light (entry 1).
It is important to note that shorter reaction time, highlighted the
transient formation of the putative hydroxyindolenine
intermediates as
a diastereoisomeric mixture which were
detected by GC/MS and 1H NMR.[8d,23] Longer reaction time
improved the conversion and almost exclusive formation of the
3-oxindole 6ac was obtained after three-day reaction time (entry
4). Reaction time can be shortened and
Table 1. Ruthenium-catalyzed site-selective allylation of 2-methylindole 1a with
allyl alcohol 2a.
Ru-1
ratio
T (°C), t
(h)
Ratio
3aa/4aa/5aa[c]
Entry[a]
conv. (%)[b]
(mol%)
1a/2a
1
2
3
4
5
6
3 mol%
5 mol%
5 mol%
7 mol%
7mol%
7 mol%
1:1
1:2
30°C, 3h
30°C, 1h
99%(3aa:90%)
99%(4aa:95%)
99%
100:0:0
0:100:0
0:68:32
0:0:100[d]
0:0:100[d]
0:7:93
1:4
20°C, 16h
20°C, 16h
20°C, 16h
30 °C, 21h
1:4
99%
1:5
99%(5aa:88%)
99%
1:3.5
[a] Experimental conditions: all reactions were performed under an inert
atmosphere of argon and carried out with allyl alcohol 2a (0.4-2 mmol), 2-
methylindole 1a (0.4 mmol), metallic precursor Ru-1 in a closed Schlenk tube in
degassed dichloromethane CH2Cl2 (0.5 mL). [b] Conversions were determined
by GC and numbers in parentheses correspond to the isolated yield of the major
product after column chromatography. [c] ratio was determined by GC analysis
on the crude reaction mixture. [d] traces of tetra-allylated product was detected.
Scheme 1. Regio- and Site-selective allylation of 2-substituted indoles 1.
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when similar reaction was performed under UV irradiation (λ=
312 nm) product 6ac was obtained in less than five hours with
up to 71% of isolated yield (entry 7). The reaction rate was
greatly affected by the presence of the N-H moiety. Using similar
protocol, the N-substituted indole 4aa provided less than 10% of
the corresponding oxindoles after one-week reaction time.[9f] As
expected, owing to their higher oxidation potential, 2-
phenylindoles 3b(a,b,e) did not undergo oxidation under these
conditions.[8] The semi pinacolic rearrangement was also
examined with branched indoles 3ab, 3ac and 3ae (Scheme 2).
As a result, no or very low diastereoselectivities were observed
with oxindoles 6ab and 6ac.
Table 2. Solid state oxidation of C(3)-allylated indole 3ac.
Scheme 2. Solid-state oxidation of the C(3)-allylated indoles 3 over SiO2. X-ray
structure of the major diastereoisomer of 6ae. CCDC 1533366 contains the
supplementary crystallographic data for 6ae
Keeping in mind, the low reactivity of the disubstituted
indoles 4 towards solid state oxidation allowed us to next
investigate the possibility of introducing a different second allylic
substituent on the nitrogen atom to further perform cyclization
through Ring Closing Metathesis (RCM) on the resulting
compounds (Scheme 3). As expected, the use of our allylation
catalyst Ru-1 led to the expected formation of the corresponding
diallylated pseudoindoxyls 7 in 55-98% isolated yields (Scheme
3). A rapid screening of the reaction conditions demonstrated
that Hoveyda-Grubbs II precatalyst allowed the formation of the
tricyclic adducts in up to 84% isolated yields.[9m,25] Owing to the
rigid structure of the tricyclic adducts, diastereoisomers of
8ab,ac,ae were easily separated after isolation by column
chromatography.
6ac/SiO2
Entry
Conds.[a]
t (h)
Conv. [b]
(mmol/g SiO2)
1
2
3
4
5
6
7
A
A
A
A
B
C
D
0.6
0.3
0.3
0.3
0.3
0.3
0.3
1
20%
22%
1
27
72
27
4.5
4.5
66%
91%(73%)
38%
84%
98(71%)
[a] A: Compound 3ac was suspended on SiO2 and the reaction mixture was
placed in air at room temperature without stirring. B: Compound 3ac was
suspended on SiO2 and the reaction mixture was placed in air at room
temperature in the dark without stirring. C: Compound 3ac was suspended on
SiO2 and the reaction mixture was placed in air at room temperature under UV
irradiation without stirring. D: Compound 3ac was suspended on SiO2 and the
reaction mixture was placed in air at room temperature under UV irradiation
under stirring. [b] Conversions were determined by 1H NMR. Numbers in
parentheses correspond to the isolated yield of the oxindole 6ac after column
chromatography.
In contrast, substituted indole 3ae allowed up to 40% of
diastereoisomeric excess. Interestingly, configuration of the
major diastereoisomer was unambiguously confirmed by X-ray
studies. It is noteworthy that intermolecular H-bonding
interactions prevail in solid state and no noticeable π-π stacking
interactions were detected.[24] Oxidation of indole 3aa occurred
at faster rate and under a modified procedure, pseudoindoxyl
6aa was obtained in up to 84% yield. Taking together, the nature
of the allylic substituent had
a profound impact on the
Scheme 3. Allylation/Metathesis sequence on oxindoles 6.
transformation rate and the overall reactivity follows the
decreasing order 3aa>3ab=3ac>3af>3ae.
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solution at 298 K, with fluorescence quantum yield up to 59%.
Solvatochromic and fluorosolvatochromic effects were observed
by using two different solvents (Table 3). Interestingly, they
exhibit positive fluorosolvatochromism: increasing the polarity of
the solvent leads to a red shift (Stock shift ≈ 45 nm) of the
emission band (for 7aa: em(CH2Cl2) = 455 nm; em (H2O) = 498
nm), consistent with
a more pronounced charge-transfer
character due to hydrogen bonding interactions with the oxindole
and the molecules of water.[2b,23,28] Unlike the absorption spectra,
we can notice a shoulder is present at longer wavelength on all
the emission spectra in dichloromethane and water for both
compounds meaning that the shape of the emission is not
affected by the solvent. The effect of the allylic substituent had a
minimal incidence of the absorption and emission properties on
the resulting tricyclic adducts whereas the quantum yield was
reduced by the introduction of the phenyl moiety presumably
due to higher vibrational degrees of freedom.
Table 3. Photophysical properties of 7aa, 8aa, 8ab, and 8ae in H2O and CH2Cl2.
[a]
[b]
Compound
Solvent
λabs/nm (εmax
)
λem/nm
Φem
Stokes shift/cm-1
7aa
7aa
CH2Cl2
H2O
407, 420 (sh) (4,2 ; 4)
455, 488 (sh)
498, 526 (sh)
45
59
2592
3175
430 (3,8)
8aa
CH2Cl2
H2O
410, 428 (sh) (3,3 ; 2,9)
431 (3,9)
458, 488 (sh)
500, 534 (sh)
457, 480 (sh)
497, 527 (sh)
460, 486 (sh)
500, 529 (sh)
496, 524 (sh)
501, 527 (sh)
47
42
59
40
56
35
35
29
2556
3201
2568
3368
2651
3041
3203
2871
8aa
8ab-d1
8ab-d1
8ab-d2
8ab-d2
8ae-d1
8ae-d2
CH2Cl2
H2O
409, 430 (sh) (2.6, 2.2)
425 (0.8)
Figure 2. Proposed overall mechanisms.
CH2Cl2
H2O
410, 430 (sh) (1.9, 1.8)
434 (1.1)
According to the previous independent reports of
Kitamura,[26] Pregosin[27] and us,[19] an overall plausible
mechanism for the allylation of indoles 1 is depicted in Figure 2.
It involves the activation of the allylic alcohol 2 by the protonated
sulfonate fragment on the ruthenium(II) intermediate I followed
by the oxidative addition and the release of a water molecule.
Outer sphere approach of the nucleophilic indole 1 on the π-
allylic ruthenium(IV) intermediate II followed by proton transfer
and ligand exchange on IV with allylic alcohol 2, release the
allylated indole 3. Concerning the pseudoindoxyls 6, according
to previous reports on 2,3-disubstituted indoles oxidation and
related compounds, formation of a hydroperoxide A tends to be
the key intermediate. [4,8b,c,28,29d] Homolysis of this latter followed
by reduction via comproportionation with 3, water or the surface
involving hydroxy radical might explain the formation of
hydroxyindolenine B.[29] Finally, the semi pinacol rearrangement
of B assisted by the acidic R3SiOH groups led to the formation of
the expected pseudoindoxyl 6.
H2O
428 (1.0)
H2O
438 (2.6)
[a] Units = 103 Mol-1 cm-1. [b] Fluorescence quantum yield (%) with ± 10% error versus quinine
sulphate.
Figure 3. Absorption and Emission spectra of 7aa in CH2Cl2 (red), in H2O
(blue) and of 8aa in CH2Cl2 (green), in H2O (black).
The photophysical properties of uncyclized and cyclized
pseudoindoxyl compounds 7aa and 8aa are given in Table 3,
and the absorption and emission spectra, measured in
dichloromethane and more interestingly in water of 7aa and 8aa
are presented in Figure 3. The UV-vis absorption spectra of 7aa
and 8aa in dichloromethane display a broad band at λ = 407 and
410 nm, respectively, presenting a shoulder which can be
ascribed to an intramolecular charge transfer (ICT) transition.
Compounds 7aa and 8aa are also strongly fluorescent in
Conclusions
In conclusion, through the use of a well-defined π-allylic
ruthenium(IV) precatalyst, we achieved the site and regio-
selective allylation of 2-substituted indoles. Sustainable solid
state oxidation under air of the corresponding indoles 3 in the
absence of photosensitizer gave the corresponding 3-oxindole
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derivatives. This reaction sequence releasing only water as side
product provides a promising alternative to the use of strong
oxidant. Finally, solid state oxidation in the presence of
photosensitizer would provide interesting results to reluctant
substrates.
Acknowledgements
H. L. thanks the MESRI-Ministère de l'Enseignement Supérieur,
de la Recherche et de l'Innovation for fellowship.
Keywords: ruthenium • allylation • oxidation • metathesis •
fluorescence
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Preparation of tricyclic pseudoindoxyls
was easily achieved from allylic
alcohols and indoles generating water
and ethylene as the only side
products.
Hortense Lauwick, Yang Sun, Huriye
Akdas-Kilig, Sylvie Dérien* and Mathieu
Achard*
Page No. – Page No.
Access to 3-oxindoles from Allylic
Alcohols and Indoles
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