[IY[OU]

DOI: 10.1002/slct.201901141 Full Papers

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2 z Organic & Supramolecular Chemistry
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Kinetics, Thermodynamics, and Theoretical Studies in a
6 Diels-Alder Dimerization Process of 3-Vinylindole
7
8 Derivative of the 3-Indoleacetic Acid: An Auxin.
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10 Jonathan Román Valdez-Camacho,[a] Karen Paola Cortés-Guzmán,[a] Héctor Torres-Gómez,[b]
11 Roberto Flores,[c] Marco A. Leyva,[d] and Jaime Escalante*[a]
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14 In this work we present a kinetics, thermodynamics and kinetics analysis show that here DAR was a second order, one-
15 theoretical studies of the Diels-Alder Reaction (DAR) of methyl step process, which indicates an associative mechanism where
16 ester of a 3-vinylindole in a solvent-free process for the the s-cis and s-trans conformations produce a single activated
17 synthesis of tetrahydrocarbazole. The results of the reaction complex.
18
19 Introduction
et al.[10] determined the activation energy (Ea) for the DAR to be
20
Tetrahydrocarbazoles are precursors or intermediates in the in the range of 8–15.2 kcal/mol. Sauer and Sustmann[11] found
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synthesis of carbazoles which are widely used because of their the value of Ea of cyclopentadiene and some α,β-unsaturated
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multiples biological activities,[1] applications in technology and olefins to be 9.2–16.6 kcal/mol.
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medicine.[2] For this reason, efficient synthesis of fused five- Recently, Jasiński et al.[12–13] have suggested that the
24
membered heterocyclic compounds such as carbazoles or thermodynamic values of ΔH! and ΔS! as better candidate for
25
tetrahydrocarbazoles have been developed, including the tradi- the prediction of the mechanistic trajectory of a DAR. They
26
tional routes of transition metals catalysis.[3] Noland et al. have reported that values of ΔH! and ΔS! in the range of (10.9) –
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proposed a Diels-Alder Reaction[4] approach using substituted (17.7) kcal/mol and (-24.5) – (-39.4) cal/mol⋅K, respectively, are
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2-vinylindoles[5] or 3-vinylindoles[6] as dienes for the preparation typical for a concerted [4 + 2] cycloaddition reactions.
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of tetrahydrocarbazoles; methods that use Brönsted-Lowry In the present work, we developed a DAR strategy for the
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acids as catalysts were also reported.[7] synthesis of tetrahydrocarbazole in a 3-vinylindole derivative
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DAR has been studied from a kinetic point of view by without a catalyst. The reaction occurred in a solvent-free
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Wasserman[8] as early as 1935 and more recently by Silvestri process, which increased reaction rate significantly as opposed
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et al. in 1989. They found that DAR should be considered as a to the reaction in solution. Thus it can be said that the strategy
34
second order reaction. Thus, the reaction rate expression could presented here meets four of the twelve principles of green
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be represented according to:[9] chemistry: Prevention, atom economy of 100%, safer solvents
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and auxiliaries, and reduction of derivatives.[14]
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d½diene" We also explored the kinetics of the process, determining
38 v¼! ¼ k½diene"½dienophile" (1)
dt the rate constants (k) and Ea at different temperatures. Kinetic
39
parameters and stereochemistry of the reaction was studied
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On the other hand, in their kinetic studies of various from a theoretical point of view using DFT calculations.
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anthracene and maleic anhydride derivatives, in 1955 Andrews
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43
Results and Discussion
44 [a] J. R. Valdez-Camacho, K. P. Cortés-Guzmán, Prof. J. Escalante
45 Centro de Investigaciones Químicas-IICBA, Universidad Autónoma del Synthesis
46 Estado de Morelos, Cuernavaca, Av. Universidad 1001, C.P. 62210 México
E-mail: jaime@uaem.mx For this study, acrylate 4 was prepared from 3-indoleacetic acid
47
[b] Dr. H. Torres-Gómez 1, which was converted into its methyl ester 2 by treatment
48 Institut für Pharmazeutische und Medizinische Chemie, Heinrich-Heine- with methanol in the presence of TMSCl. Compound 3 was
49 Universität Düsseldorf, Universitätsstraße 40225 Düsseldorf, Germany
synthesized through of the addition of (Boc)2O and 4-DMAP as
50 [c] Dr. R. Flores
Facultad de Ciencias Químicas e Ingeniería, Universidad Autónoma del a catalyst in a mixture of Toluene/AcCN 9:1 as solvent at reflux.
51
Estado de Morelos Finally, the desired acrylate 4 was obtained by treatment with
52 [d] M. A. Leyva paraformaldehyde and NaH using THF as solvent (Scheme 1).[15]
53 CINVESTAV!I.P.N., Chemistry Department, Av. Instituto Politécnico Nacio-
If compound 4 is subjected to heat, it presents a Diels-Alder
54 nal 2508, Col. San Pedro Zacatenco, C.P. 07000, Ciudad de México,
Mexico type dimerization between s-cis and s-trans conformations
55
Supporting information for this article is available on the WWW under yielding a tetrahydrocarbazole derivative endo-5, as it is shown
56
https://doi.org/10.1002/slct.201901141 in Scheme 2.
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 Full Papers

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16 Scheme 1. Synthesis for the monomer 4 in the DAR.
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24 Figure 1. Solid-state structure of 9-(tert-butyl)-1,4-dimethyl-1-(1-(tert-butoxy-
Scheme 2. Diels-Alder reaction of s-cis and s-trans conformations of 3-
carbonyl)-1H-indol-3-yl)-1,2,3,9a-tetrahydro-9H-carbazole-1,4,9-tricarboxylate
25 vinylindole 4.
endo-5. For clarity, part of the hydrogens atoms were omitted.[16]
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27
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Although two regioisomeric compounds were expected as
29
products of the reaction, only the endo-adduct was isolated,
30
which reflects the high stereoselective of the process. The
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tetrahydrocarbazole derivative endo-5 was characterized by
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single-crystal X-ray diffraction analysis and is shown in Figure 1.
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323.15 (50 °C) and 363.15 K (90 °C) with 10 K intervals were
For the kinetics measurements, temperatures between
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35
considered. Measurements for each temperature were repeated
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twice in order to ensure reproducibility and make results as
37

spectra of the kinetics of 4 at 363.15 K (90 °C) at different time

uniform as possible. For example, Figure 2 shows the 1H NMR
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39
intervals. Most notable here is the intensity of the signal HC
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(δ = 5.23 ppm) of the product endo-5 as compared to the
41
signals HB and HA (δ = 5.98 and 6.38 ppm, respectively) of the
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vinyl protons of 4. One observes that HA and HB are decreasing
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with time, which almost disappeared after 60 minutes of
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reaction time. Concentrations of 4 were determined using the
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363.15 K (90 °C) of 4 at different reaction times; HA, HB, and HC: characteristic
proportions between the characteristic signals HA, HB and HC in Figure 2. Partial 1H NMR spectra at 500 MHz resulting from the heating at
46
the 1H NMR spectra from compounds 4 and endo-5 (Figure 2)
47 signals in 1H NMR of 4 and endo-5 respectively.
with chloroform-d as solvent. The rate constants for each
48
temperature were determined and adjusted to a second order
49
rate equation, and the dependence on temperature was related v ¼ !d½A"=dt ¼ k½A"½B"
50 (2)
to the Eyring-Polanyi equation (5).
51
52
where both can be considered as monomer of the reaction.
53 Kinetics and Thermodynamics Studies.
With this, expression (2) can be rewritten as the rate law of a
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In a dimerization process both dienophile (A) and a diene (B) dimerization process:
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are involved in the transition state
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1 v ¼ !d½A"=dt ¼ k½A"2 (3) DG6¼ ¼ DH6¼ ! T # DS6¼ (6)

2
3
Further integration of (3) yields the concentration of A: equation (5) can be written as follows:
4
5
½ A"t ¼ 1=ðkt þ 1 =½ A"0 Þ (4) k ¼ ðk # kB # T=hÞ # expðDS6¼ =RÞ # expð!DH6¼ =RTÞ (7)
6
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Nonlinear regression was performed on the results at Thermodynamic parameters of the DAR were estimated
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different temperatures using the program PolymathTM. Table 1 using the PolymathTM program. The results were:
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DS6¼ ¼ !4:89 $ 2:32 ðcal=mol # KÞ (8)
11 Table 1. Kinetics constants at different temperatures of the DAR.

Temperature (°C)
12 DH6¼ ¼ 16:49 $ 0:83 ðkcal=molÞ
k (L mol-1 h-1) 95% confidence R2adj (9)
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14 50 4.197 0.1034 0.999 R2 adj ¼ 0:999 (10)
60 9.879 0.4929 0.999
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70 18.195 0.5920 0.999
16 80 39.260 4.3910 0.999 The obtained value for ΔH! and ΔS! suggest that the
17 90 76.694 5.4567 0.999
dimerization of 4 to endo-5 corresponds a one-step cyclo-
18
addition [4 + 2] process.[12–13] Negative values for ΔS! show a
19
decrease of entropy upon forming the transition state, which
20
summarizes the calculations, and Figure 3 displays the fitting of often indicates an associative mechanism in which two reaction
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the reaction rate equation with the experimental data. partners form a single activated complex. Table 2 displays the
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24 Table 2. Gibbs energy of activation at different temperatures of the DAR.

Temperature (°C)
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ΔG! (kcal/mol)
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27 50 18.07 $ 1.58
60 18.12 $ 1.60
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70 18.17 $ 1.63
29 80 18.22 $ 1.65
30 90 18.27 $ 1.67
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Figure 3. Relationship between the DAR and the rate law of a dimerization
39
process.
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For the thermodynamic analysis, the Eyring-Polanyi equa-
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tion was used to describe the variance of the reaction rate with
44
temperature:
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k ¼ ðk # kB # T=hÞ # expð!DG6¼ =RTÞ (5)
47
48
where k is the transmission coefficient; kB is the Boltzmann’s
49
constant (1.3806 × 10!23 J K!1); h is the Planck’s constant Figure 4. Relationship between the kinetic constant of the DAR and the
50
(6.6261 × 10!34 J⋅s); and ΔG! is the Gibbs energy of activation. Eyring-Polanyi equation.
51
The transmission coefficient is often assumed to be unity as it
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reflects what fraction of the flux through the transition state
53
proceeds to the product without recrossing the transition state.
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Using the definition of the Gibbs free energy: Gibbs energy of activation at different temperatures. Figure 4
55
shows the adjustment of the experimental kinetics constants
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with the Eyring-Polanyi equation.
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Theoretical Studies.
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2
As we know, from a mechanistic point of view, the correct
3
conformation for the diene in DAR is the s-cis geometry.
4
However, this is not the more stable one. In order to verify
5
which is the energy cost for the conversion of s-cis to s-trans
6
geometry for compound 4 (monomer), DFT calculations using
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the B3LYP hybrid-functional were carried out, and the s-trans
8
conformer was shown to be more stable by - 4.6 kcal/mol,
9
(Figure 5). By the fact of having bulky groups rather than just
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12
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14 Figure 7. Optimized geometry for the TS for the endo-adduct showing the
15 centroid length between indole moities.
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21 Figure 5. Gibbs free energy difference between s-cis and s-trans conforma-
22 tions of 4 calculated at the B3LYP/6-31G** level of theory.
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24
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hydrogen in the system, the allylic repulsion is probably
26
increased, and a more negative value is observed if it is
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compared with the 1,3-butadiene conversion energy (- 3 kcal/ Figure 8. (a) Optimized geometry for the TS for the exo-adduct showing the
28
mol).[17] asynchronicity and non the π-π aryl-aryl Secondary Orbital Interaction (SOI)
29 between the indole rings and (b) the less probably repulsion interactions by
X-ray structure analysis confirms that the endo-adduct was
30 using van der Waals spheres view.
isolated as expected. In fact, the reaction proceeds with
31
stereospecificity, probably by the π-π aryl-aryl Secondary
32
Orbital Interaction (SOI) between the indole rings.[18]
33
This idea was further supported by the analysis of the mol respectively). As commented earlier, the more favorable
34
transition state (TS, Figure 6) for the endo-adduct, where it was conformer is the s-trans, and for the exo-adduct TS, both the
35
diene and dienophile have an s-cis geometry, while for the
36
endo-adduct just the diene is under this condition. However,
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when free energy values were compared, we could only find a
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spontaneous process for the endo-adduct (- 1.74 kcal/mol),
39
while an unspontaneous process for the exo-adduct is expected
40
(7.35 kcal/mol, Figure 9) in agreement with experimental data.
41
However, stereospecificity alone is not enough to confirm
42
the one-step mechanism. Although in the present work a one-
43
step mechanism is proposed for the DAR, it is important to
44 Figure 6. (a) Optimized geometry for the TS for the endo-adduct showing the comment that at this moment several mechanisms should be
45 asynchronicity and the π-π aryl-aryl Secondary Orbital Interaction (SOI)
considered. Thus, DAR should be classified as non-polar (N-
46 between the indole rings and (b) greater repulsion interactions as viewed by
van der Waals spheres model. DAR), where synchronical, one-step or two-steps (which is less
47
common), biradical mechanism are possible. Polar (P-DAR) are
48
also possible where they are characterized as asynchronical,
49
stepwise, zwitterionic mechanism processes.[20–23] In order to
50
noted a tilted edge-to-face (T-EF) π-stacking with a centroid classify the DAR as N-DAR or P-DAR, the Global Electron Density
51
distance of 4.601 Å, which is lower than the reported value in Transfer (GEDT) values were used. Domingo[24] proposed that
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the literature for similar interaction (5.94-5.99 Å, Figure 7).[19] N-DAR corresponds with GEDT values below 0.2 e, while P-DAR
53
On the other hand, the exo-adduct shows an energetically exhibit GEDT values above 0.2 e. By the fact of the endo-adduct
54
unfavorable orientation for the π-π interaction (Figure 8). was the only product isolated, only its GEDT value was
55
Nevertheless, the activation energy (Ea) for the exo-adduct is determined. The 0.1 e of GEDT corresponds to a N-DAR, which
56
similar to that of the endo-adduct (24.6 kcal/mol and 24.7 kcal/
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FT-IR spectra, Elemental analysis, and HRMS (ESI). SI also
1
includes computational details.
2
3
4 Acknowledgements
5
We would like to thank CONACYT for financial support (Project
6
No. CB2015/256653). K.P. C.-G. and J.R. V.-C thanks CONACYT for
7
his graduate scholarship.
8
9
10 Conflict of Interest
11
The authors declare no conflict of interest.
12
13
Figure 9. Energy profile for paths A (reaction coordinate for the endo-adduct)
14 Keywords: Activation Energy · B3LYP functional · DFT
and B (reaction coordinate for the exo-adduct). Energies where calculated
15 relative to the reactive (R) and are given in kcal mol!1. Calculations · Diels-Alder · Tetrahydrocarbazoles
16
17 [1] V. Sridharan, M. A. Martín, J. C. Menéndez, Eur. J. Org. Chem. 2009, 27,
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19 [2] For more recently approximations: a) S. A. Jenekhe, L. Lu, M. M. Alam,
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20
By analyzing the exo- and endo-adduct TS, we note a higher J. Pielichowski, K. Pielichowski, Prog. Polym. Sci. 2003, 28, 1297–1353;
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27 Chem. Res. 2008, 41, 1110–1119; h) P. Kochapradist, N. Prachumrack, R.
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36
second order reaction, thus it can be considered as an Zhao, R. C. Larock, J. Org. Chem. 2006, 71, 5340–5348; i) R. B. Bedford, M.
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46 1668–1698.
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11 2019, 9, 10–22.
12 [16] Crystallographic data is deposited at Cambridge Crystallographic Data Submitted: March 27, 2019
13 Center CCDC: No. 1877663.
Accepted: July 15, 2019
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