Transition-Metal Free Mechanochemical Approach to Polyyne Substituted Pyrroles

Article abstract of DOI:10.1021/acs.joc.6b01732

In this contribution, the synthesis of long chain hexatriynyl- and octatetraynyl-substituted pyrroles in one step from 1-halopolyyne precursors is reported. The products were obtained via a mechanochemical approach by simple grinding of 1-haloalkynes with

Full text of DOI:10.1021/acs.joc.6b01732

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Article
Transition-Metal Free Mechanochemical
Approach to Polyyne Substituted Pyrroles
Bart#omiej Pigulski, Agata Arendt, Denis N. Tomilin, Lyubov
N. Sobenina, Boris A. Trofimov, and Slawomir Szafert
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01732 • Publication Date (Web): 26 Aug 2016
Downloaded from http://pubs.acs.org on August 30, 2016
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Transition-Metal Free Mechanochemical Approach to Polyyne Substituted Pyrroles
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Bartłomiej Pigulski,1 Agata Arendt,1 Denis N. Tomilin,2 Lyubov N. Sobenina2, Boris A.
Trofimov,2 Sławomir Szafert1*
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1Department of Chemistry, University of Wrocław, 14 F. JoliotꢀCurie, 50ꢀ383 Wrocław,
Poland.
2A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of
Sciences, 1 Favorsky, 664033, Irkutsk, Russian Federation.
corresponding author: slawomir.szafert@chem.uni.wroc.pl
ABSTRACT
In this contribution the synthesis of long chain hexatriynylꢀ and octatetraynylꢀ
substituted pyrroles in one step from 1ꢀhalopolyyne precursors is reported. The products were
obtained via a mechanochemical approach by simple grinding of 1ꢀhaloalkynes with Nꢀ
substituted pyrroles and potassium carbonate which played a role of heterogeneous catalyst
and this solventꢀ and transition metalꢀfree approach is unprecedent in the synthesis of new,
organic, long chain polyynes. Additionally, an extensive Xꢀray single crystal studies of
pyrrole endꢀcapped polyynes is presented. Such compounds are possible substrates for
different oligoheterocycles and have a significant application potential as for instance
molecular wires.
INTRODUCTION
Polyynes have been attracting a constant interest from a scientific community for more
than half a century and a variety of diverse compounds possessing such an unsaturated motif
has been synthesized to date.1 One of the major motivations for investigation of these linear
carbon rods is that they can be regarded as model compounds of yet unknown, hypothetical,
allotropic form of carbon ꢀ carbyne. Moreover polyynes possess considerable application
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potential. Such molecules have been explored as molecular wires and switches in
nanoelectronics,2 as materials for optoelectronics due to their strong, nonlinear optical
response,3 or as precursors for conducting polymers.4 It is also noteworthy that polyyne motifs
have been oftentimes recognized in the interstellar matter.5
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Polyynes which contain pyrrole endꢀgroups are a very scanty class of compounds. To
the best of our knowledge only butadiynes are known to date, among which there are
porphyrinoids with butadiyne chain incorporated into a macrocycle skeleton6 or modified
bilirubins.7 For instance Vogel6a and Panda6b published the synthesis of a very
physicochemically interesting 26πꢀβꢀoctasubstituted diacetyleneꢀcumulene porphycene from
butadiyneꢀbridged bipyrroledialdehydes. It is noteworthy that the precursor for this molecule
was obtained in seven synthetic steps.6c Another interesting example of diacetylene
porphyrinoids are dimeric and trimeric BODIPY based macrocycles obtained in CuCl
catalyzed homocoupling reaction shown by Shinokubo.6d Finally, a little different synthetic
approach to pyrrole butadiyne compounds was presented by Fiandanese where the target
molecule was obtained via heterocyclization from aminoaryl tetrayne.6e
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Despite synthetic inaccessibility of longer analogues, hexatriynylꢀ and octatetraynylꢀ
substituted pyrroles were investigated with the use of computational methods.8 Moreover,
such heterocyclicꢀlong conjugated systems may be used as very useful substrates for the
synthesis of oligoheterocycles.9
Recently, we have reported the crossꢀcoupling reaction between the conjugated 1ꢀ
halobutadiynes and substituted pyrroles.10 The reaction needed a short grinding of substrates
with K2CO3 in a mortar and was insensitive to moisture and air. The scope covered mostly
substrates with strongly electron withdrawing endꢀgroups directly attached to butadiyne
moiety what was in accordance with the earlier data that showed effective coupling of 1ꢀ
haloacetylenes possessing ester or keton endꢀgroups with substituted pyrroles.11 In our work
however, we have surprisingly noticed that aryl substituted 1ꢀhalobutadiynes also undergo
such coupling reaction. Reaction times were longer but it was possible to obtain products with
good yields. Encouraged by those findings we decided to expand the scope of this reaction to
longer arylꢀsubstituted polyynes and to use this convenient mechanochemical approach for the
synthesis of much longer pyrrole endꢀcapped carbon rods.
Herein we report the crossꢀcoupling reaction between 1ꢀhalopolyynes with carbon
chain up to octatatetrayne with a series of tetrahydroindoles giving a new class of pyrrole endꢀ
capped polyynes.
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RESULTS AND DISCUSSION
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Synthesis of polyynyl-substitited pyrroles
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In the initial thrust a series of 1ꢀhaloacetylenes 1ꢀ5ꢀC2Br was obtained as shown in
Scheme 1. Next, through C2 and C4 chain elongation protocols based on CadiotꢀChodkiewicz
crossꢀcoupling a group of hexatriynes 1ꢀ5ꢀC6TMS and two butadiynes 1ꢀ2ꢀC4TMS were
synthesized. All the compounds were transformed to the corresponding bromides via
desilylative halogenation and the 1ꢀ2ꢀC4Br were next used to obtain first 1ꢀ2ꢀC8TMS and then
target 1ꢀ2ꢀC8I. The synthesis of the presented 1ꢀiodooctatetraynes and 1ꢀbromohexatriyne 1ꢀ
C6Br were published in our earlier works.12 New 1ꢀbromohextariynes 2ꢀ4ꢀC6Br were obtained
in 66ꢀ96% yield and were reasonably stable (for days) in the solid state and when kept in
dark. Although, we have previously noticed that the coupling reaction of pyrroles with 1ꢀ
haloalkynes is much faster for bromides than for iodides, unfortunately, we also discovered
that longer 1ꢀbromoalkynes are much less stable that the iodo derivatives. Hence, for 1ꢀ
halooctatetraynes only iodo derivatives appeared available.
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Scheme 1. The synthesis of 1ꢀhalopolyynes.
All the new compounds were characterized by H and 13C NMR spectroscopy and
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gave the HRMS mass signals supporting appropriate molecular structures. The 13C NMR
spectra ꢀ although routine ꢀ revealed signals for all carbons from the polyyne chains. As usual
the signal of the carbon adjacent to a halogen atom were the most upfield shifted and
appeared between 42.9 and 45.1 ppm.
With all the starting materials in hand we performed initial test reactions using 4,5,6,7ꢀ
tetrahydroindoles and utilizing the known, mechanochemical procedure.10,13 Our choice of
alkylꢀsubstituted pyrroles eventuated from the fact that they are very convenient model
substrates due to their synthetic availability and moreover tetrahydroindoles were previously
used in similar couplings.
In order to optimize the reaction, we have first investigated a relation between a
carbon chain length and the reaction rate (see Scheme 2). As the test compounds we have
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selected the benzonitrile derivatives 1ꢀC2Br, 1ꢀC4Br, 1ꢀC6Br and Nꢀmethylꢀ4,5,6,7ꢀ
tetrahydroindole. The reaction with 1ꢀC2Br was very slow and after several days only traces
of product were observed in the 1H NMR spectrum. 1ꢀC4Br reacted faster but the reaction was
not completed even after few days. Surprisingly, the reaction for 1ꢀC6Br was already
completed after 3 h, which clearly shows that longer chain provided shorter reaction time.
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Scheme 2. Test reaction of 1ꢀCnX polyynes with Nꢀmethylꢀ4,5,6,7ꢀtetrahydroindole.
As said already, iodides are generally less reactive than bromides,10 but we have
decided anyway to check a difference in reaction times between 1ꢀC6I and 1ꢀC8I. The results
showed that the reaction between 1ꢀC6I and Nꢀmethylꢀ4,5,6,7ꢀtetrahydroindole was not
completed even after a few days unlike 1ꢀC8I which gave the desired product after 24 h. With
all that in mind we approached the syntheses of hexatriynylꢀsubstituted pyrroles using 1ꢀ
bromohexatriynes and octatetraynylꢀsubstituted pyrroles using 1ꢀiodooctatetraynes.
Reactions between 1ꢀbromohexatriynes 1ꢀ5ꢀC6Br and tetrahydroindoles were first
performed (see Scheme 3). The ones with Nꢀsubstituted tetrahydroindoles worked well and
the products were obtained with yields up to 96% (2ꢀC6THIꢀBn) and the reaction times were
between 3 and 24 h. Only the reaction of 4ꢀC6Br and 5ꢀC6Br with Nꢀvinylꢀsubstituted
tetrahydroindole gave the product with lower yield (19%). Generally, the reactions with
unsubstituted tetrahydroindole gave products with a little lower yields (8ꢀ52%) and also the
reaction times were longer (19ꢀ72 h). Nevertheless, we were able to isolate pure products for
all the five hexatriynes (20 examples). Importantly, the reaction scope includes electron
withdrawing substituents on a phenyl ring (1ꢀ4ꢀC6Br) as well as weakly electron donating ꢀ
OC(O)Me group (5ꢀC6Br). Additionally, we have tested two 1ꢀbromohexatriynes (1ꢀC6Br, 2ꢀ
C6Br) in the reaction with 2ꢀphenylpyrrole, but we were not able to isolate any coupling
products (only substrates were retrieved). We are fully aware that the scope on the pyrrole
side is a little narrow, but in our opinion the finding itself (meaning, that a pyrrole may
undergo such unusual transformation with long 1ꢀhalopolyynes) is already a very important
result.
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K2CO3
3
R1
grinding
R1
Br
N
N
R2
R2
4
5
6
7
8
N
N
N
N
N
N
N
N
H
1-C6THI-Me 82%, 3h
1-C6THI-Vin 40%, 24h
1-C6THI-H 52%, 24h
1-C6THI-Bn 88%, 3h
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O2
N
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O2
N
O2
N
O2N
N
N
H
N
N
2-C6THI-H 42%, 72h
2-C6THI-Bn 97%, 24h
2-C6THI-Me 58%, 24h
2-C6THI-Vin 81%, 24h
N
N
H
N
N
O
O
O
O
3-C6THI-Bn 78%, 24h
3-C6THI-H 8%, 22h
3-C6THI-Me 39%, 3h
3-C6THI-Vin 96%, 20h
Et
O
Et
O
Et
O
Et
O
N
N
N
N
O
O
O
O
H
4-C6THI-Me 74%, 20h
4-C6THI-Vin 19%, 23h
4-C6THI-Bn 57%, 4h
4-C6THI-H 25%, 19h
O
O
O
O
O
O
O
O
N
N
H
N
N
5-C6THI-H 11%, 24h
5-C6THI-Me 74%, 24h
5-C6THI-Vin 19%, 24h
5-C6THI-Bn 42%, 20h
Scheme 3. Synthesis of hexatriynylꢀsubstituted tetrahydroindoles.
Reaction with 1ꢀiodotetraynes presented a greater challenge. Reaction times were
longer (24ꢀ48 h) than those for the corresponding 1ꢀbromohexatriynes (3ꢀ24 h), however
products were obtained with yields ranging from 34% up to 97% (see Scheme 4).
Unfortunately, reactions with unsubstituted tetrahydroindole were too slow and we were
unable to obtain the expected products.
Scheme 4. Synthesis of octatetraynylꢀsubstituted tetrahydroindoles.
Looking at the previously obtained arylꢀsubstituted butadiynes10 it should be noticed
that the yields obtained for the reaction of analogous tetrahydroindoles with 4ꢀ
CO2EtC6H4C≡CC≡CBr (36ꢀ58%) were in general lower and the reaction times (24 h to 5
days) much longer. This implies that the use of longer conjugate systems C6 and C8
contributes to a better reaction performance.
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A reaction mechanism for this inverse Sonogashira coupling has already been
proposed14 and the ESR studies confirmed that the first step is the formation of ionꢀradicals
pair via a single electron transfer. A fine grinding of the reactants is intended to mix the
substrates as evenly and finely as possible what corresponds to a distribution of substrates in a
solvent. In this case, the crystalline lattice plays a role of a highly ionized medium,
resembling an ionic liquid. The NMR monitoring unambiguously proves that during “the
resting delay” the reaction proceeds and the given reaction time is experimentally determined.
Thus, it is also an experimental fact, that during “the resting delay” (actually, the reaction
time) the reaction proceeds. It is clear that migration/diffusion of the reactants in the solid
state should be very slow. Apparently, the reactants contact each other already in the process
of grinding to form charge transfer complexes and then ion radical pairs and their further
transformation to the final products is not immediate and takes some time. It is understood
that the detailed mechanism of this reaction is still far from being entirely clarified and
deserves an inꢀdepth investigation, in particular, we should not ignore the mechanochemical
contribution (formation of crystalline lattice defects) to the triggering of the coupling reaction.
Based on that we may conclude that longer chain gives better stabilization at the initial
step (the formation of ionꢀradical pair) spawning the better yield and shorter reaction time as
shown in Scheme 5. Moreover, less electronꢀrich bromides probably are more likely to form
cationꢀradical at the first step than more electronꢀrich iodides.
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Scheme 5. Proposed mechanism of long chain stabilization of a radical intermediate product.
Coupling products presented in this contribution are new and exceptional from the
structural point of view. To our best knowledge, pyrroles with ꢀ(C≡C)3R or ꢀ(C≡C)4R
substituents are not known in the literature. Polyynes with heteroaromatic endꢀgroup are
generally rare and to date only symmetric octatetraynes with thiophene,15 quinoline16 and
pyridine17 groups have been described.
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X-Ray Crystallography
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Single crystals appropriate for Xꢀray analysis were in most cases obtained by liquid
phase diffusion (CH2Cl2/nꢀhexane) or by slow evaporation of a solvent at low temperature.
Coupling products crystallized rather well and six Xꢀray solid state structures were solved
which are shown in Figure 1. The presented compounds are the first examples of hexatriynylꢀ
and octatetraynylꢀsubstituted pyrroles to date.
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Figure 1. Molecular structures of coupling products. Thermal ellipsoids are given at 50%
4
5
probability level. For 1ꢀC6THIꢀMe and 4ꢀC6THIꢀBn disorder is omitted for clarity.
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In all cases, a tetrahydroindole moiety, a polyyne chain and a phenyl ring are coplanar
except for 4-C6THIꢀBn where the planes of pyrrole and phenyl rings are twisted by 81° most
probably due to packing forces. The carbonꢀcarbon chain bond lengths are given in the Table
1 and it can be noticed that the triple bonds are usually slightly longer while the single bonds
are slightly longer than typical values for polyynes with carbon chain of that length.18
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Table 1. Bond lengths in the polyyne chains [Å].
Cpy-C1
C1-C2
C2-C3
C3-C4
C4-C5
C5-C6
C6-C7
C7-C8
CX-CPh
1ꢀC6THIꢀMe
2ꢀC6THIꢀVin
2ꢀC6THIꢀBn
3ꢀC6THIꢀVin
4ꢀC6THIꢀBn
2ꢀC8THIꢀVin
1.381(4)
1.424(5)
1.419(2)
1.405(7)
1.404(2)
1.428(4)
1.235(5)
1.207(5)
1.231(2)
1.208(7)
1.218(2)
1.201(4)
1.311(4)
1.368(5)
1.386(2)
1.381(8)
1.354(2)
1.359(4)
1.212(2)
1.209(5)
1.231(2)
1.208(7)
1.215(2)
1.219(4)
1.361(3)
1.368(5)
1.398(2)
1.360(8)
1.357(2)
1.351(4)
1.207(3)
1.205(5)
1.233(2)
1.212(8)
1.207(2)
1.218(4)
ꢀ
ꢀ
1.430(3)
1.431(5)
1.458(2)
1.436(8)
1.430(2)
1.428(4)
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1.361(4)
1.212(4)
Contraction coefficients of polyyne chains are given in the Table 2. Compounds
C6THIꢀVin, ꢀC6THIꢀVin and ꢀC8THIꢀVin are nearly linear with very low contraction
coefficients (C1ꢀCn = 0.00ꢀ0.04%, Cpy CPh = 0.00ꢀ0.03%).
2ꢀ
3
2
-
Table 2. Contraction coefficients for polyyne chains.
1ꢀC6THIꢀMe
0.21%
2ꢀC6THIꢀVin
0.00%
2ꢀC6THIꢀBn
0.12%
3ꢀC6THIꢀVin
0.05%
4ꢀC6THIꢀBn
0.16%
2ꢀC8THIꢀVin
0.04%
C1-Cna
b
Cpy-CPh
0.26%
0.00%
0.22%
0.03%
0.34%
0.03%
aContraction C1ꢀC
n = (sum of C1ꢀCn bond lengths − C1ꢀCn distance)/sum of C1ꢀCn bond
b
lengths × 100ꢁ%; Contraction CpyꢀCAr = (sum of CpyꢀCAr bond lengths − CpyꢀCAr distance)/
sum of CpyꢀCAr bond lengths × 100ꢁ%.
Since polyynes hold a great potential for 1,
analyzed packing arrangements of the polyynylꢀsubstituted pyrroles. In four cases (
Me, ꢀC6THIꢀVin, ꢀC6THIꢀVin, ꢀC8THIꢀVin) molecules form in the solid state ‘headꢀtoꢀ
n
ꢀtopochemical polymerization4,19 we have
ꢀC6THIꢀ
1
2
3
2
tail” chains with strong π···π interactions between carbon chains what makes them good
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candidates for topochemical process. Next, the closest chainꢀchain separation was analyzed,
which is understood as the closest carbonꢀcarbon distance from two neighboring carbon
chains. As revealed by thorough analysis the closest distances between two carbon atoms of
parallel chains are: 3.702 Å for 1ꢀC6THIꢀMe, 3.509 Å for 2ꢀC6THIꢀVin, 3.565 Å for 3ꢀC6THIꢀ
Vin, and 3.422 Å for 2ꢀC8THIꢀVin, what is slightly above the sum of the van der Waals radii
(3.4 Å).20 Example of packing diagram for 2ꢀC8THIꢀVin is given in the Figure 2.
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Figure 2. Packing motif for 2ꢀC8THIꢀVin. The closest intermolecular CꢀC distances [Å]: C2ꢀ
C8(i)=C8(i)ꢀC2(ii) 3.448, C3ꢀC7(i)=C7(i)ꢀC3(ii) 3.422, C4ꢀC6(i)=C6(i)ꢀC4(ii) 3.445, C5ꢀ
C5(i)=C5(i)ꢀC5(ii) 3.466. Symmetry operations for related atoms are: (i) ꢀx, ꢀ1 + x, z; (ii) –x,
ꢀ1/2 + y, 1/2 –x.
CONCLUSION
In summary, we have shown an effective and convenient way to novel pyrrole endꢀ
capped polyynes. For the first time, hexatriynylꢀ and ocatatetraynylꢀpyrroles were obtained in
reasonable to high yields and the coupling reaction required only simple grinding of substrates
with potassium carbonate under solventꢀ and transition metalꢀfree conditions. Products were
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characterized using H and 13C NMR and ESIꢀMS techniques. Further, the first solid state
structures of long polyynylꢀsubstituded pyrroles were obtained and their packing analysis
revealed that four of them are promising candidates for 1,nꢀtopochemical polymerization. We
believe, that such simple mechanochemical approach may lead to new synthetic protocols for
novel carbon rods.
EXPERIMENTAL SECTION
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General: All moistureꢀ and airꢀsensitive reactions were conducted under N2 with the use of
standard Schlenk techniques. Inverse Sonogashira coupling reactions were carried out in the
presence of air and moisture. Glassware was preꢀdried at 120 °C. Solvents were treated as
follows: THF was distilled from Na/benzophenone, CH3CN (HPLC grade), hexane (HPLC
grade), DCM (pure per analysis), diethyl ether (pure per analysis) were used as received. CuI
(99%), Nꢀbromosuccinimide (99%), NH(iꢀPr)2 (99.5%), Pd(PPh3)2Cl2 (99.5%), K2CO3 (pure
per analysis) were used as received. 1ꢀC6Br, 1ꢀC8I, 2ꢀC6TMS, 2ꢀC8I, 3ꢀC2Br, 4ꢀC2Br, 5ꢀC2Br,
butadiynyltrimethylsilane and all pyrroles were obtained according to the known
procedures.12c,d,21
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1H and 13C{1H}NMR spectra were recorded on a 300 and 500 MHz spectrometers
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with an inverse broadband probe. For the H NMR spectra, chemical shifts in chloroformꢀd
were reported in the scale relative to the solvent residual peak (7.26 ppm for CDCl3). For the
13C NMR spectra, chemical shifts were reported in the scale relative to CDCl3 (77.16 ppm).
HMBC and HMQC techniques were used for peak assignment. HRMS spectra were recorded
using spectrometer with TOF mass analyzer and ESI ion source. IR spectra were recorded
with the use of FTIR spectrometer and the samples were measured as fluorinated oil mulls.
UVꢀVis spectra were recorded with the use of oneꢀbeam spectrophometer.
Synthesis of new trimethylsilyl-protected hexatriynes
(3-C6TMS) 1-(4-((Trimethylsilyl)hexatriynyl)phenyl)ethanone
A general procedure for Cadiot-Chodkiewicz cross-coupling: 3ꢀC2Br (1.01 g, 4.53 mmol),
butadiynyltrimethylsilane (0.667 g, 5.46 mmol), Pd(PPh3)2Cl2 (0.064 g, 0.091 mmol) and CuI
(0.035 g, 0.18 mmol) were dissolved in THF (20 mL) under N2 atmosphere. Mixture was
degassed three times with the use of freezeꢀpumpꢀthaw technique and next NH(iꢀPr)2 (1.61
mL, 11.5 mmol) was added. After 24 h solvent was removed under reduced pressure and
product was purified by flash silica gel column chromatography (eluent: DCM/hexane, v/v,
1/3) to give 0.502 g (1.90 mmol) of yellow solid. Yield: 42%. 1H NMR (500 MHz, CDCl3) δ
7.92ꢀ7.90 (m, 2H, C6H4), 7.62ꢀ7.58 (m, 2H, C6H4), 2.60 (s, 3H, CH3), 0.23 (s, 9H, SiMe3).
13C{1H}NMR (126 MHz, CDCl3) δ 197.2 (C=O), 137.4 (CArC=O), 133.3 (CH from C6H4),
128.4 (CH from C6H4), 125.8 (CArC≡C), 90.3 (SiC≡C), 87.9 (C≡C), 77.4 (C6H4C≡C), 75.7
(C≡C), 68.5 (C≡C), 61.2 (C≡C), 26.8 (CH3), ꢀ0.4 (Si(CH3)3). HRMS (ESI): m/z calcd for
C17H17OSi: 265.1043 [M+H+]; found: 265.1050.
(4-C6TMS) Ethyl 4-((trimethylsilyl)hexatriynyl)benzoate
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According to the general procedure for CadiotꢀChodkiewicz crossꢀcoupling 4ꢀC2Br (0.265 g,
1.05 mmol), butadiynyltrimethylsilane (0.155 g, 1.27 mmol), Pd(PPh3)2Cl2 (0.037 g, 0.053
mmol), CuI (0.010 g, 0.053 mmol), NH(iꢀPr)2 (0.34 mL, 2.4 mmol) and THF (15 mL) were
used. Time: 4.5 h, purification: silica gel chromatography (hexane/DCM, v/v, 1/1), beige
solid, yield: 33% (0.102 g, 0.346 mmol). 1H NMR (500 MHz, CDCl3) δ 7.98 (d, JHH = 8.6 Hz,
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2H, C6H4), 7.55 (d, JHH = 8.6 Hz, 2H, C6H4), 4.37 (q, JHH = 7.1 Hz, 2H, OCH2), 1.38 (t, JHH
=
7.1 Hz, 3H, CH3), 0.22 (s, 9H, SiMe3). 13C{1H}NMR (126 MHz, CDCl3) δ 165.8 (C=O),
133.0 (CH from C6H4), 131.3 (CArC=O), 129.6 (CH from C6H4), 125.4 (CArC≡C), 90.1
(SiC≡C), 87.9 (C≡C), 76.9 (C6H4C≡C), 75.8 (C≡C), 68.2 (C≡C), 61.4 (OCH2), 61.2 (C≡C),
14.4 (CH3), ꢀ0.4 (Si(CH3)3). HRMS(ESI): m/z calcd for C18H18O2SiNa: 317.0968 [M+Na+];
found: 317.0963.
(5-C6TMS) 4-((Trimethylsilyl)hexatriynyl)phenyl acetate
According to the general procedure for CadiotꢀChodkiewicz crossꢀcoupling 5ꢀC2Br (0.197 g,
0.824 mmol), butadiynyltrimethylsilane (0.121 g, 0.990 mmol), Pd(PPh3)4 (0.029 g, 0.041
mmol), CuI (0.0078 g, 0.041 mmol), NH(iꢀPr)2 (0.29 mL, 2.1 mmol) and THF (15 mL) were
used. Time: 4.5 h, purification: silica gel chromatography (hexane/DCM, v/v, 1/1), beige
solid, yield: 47% (0.108 g. 0.385 mmol). 1H NMR (500 MHz, CDCl3) δ 7.53 (d, JHH = 8.8 Hz,
2H, C6H4), 7.07 (d, JHH = 8.8 Hz, 2H, C6H4), 2.30 (s, 3H, CH3), 0.22 (s, 9H, SiMe3).
13C{1H}NMR (126 MHz, CDCl3) δ 169.0 (C=O), 151.8 (CArO), 134.5 (CH from C6H4), 122.1
(CH from C6H4), 118.6 (CArC≡C), 89.3 (SiC≡C), 88.1 (C≡C), 76.1 (C6H4C≡C), 74.6 (C≡C),
67.1 (C≡C), 61.6 (C≡C), 21.3 (CH3), ꢀ0.4 (Si(CH3)3). HRMS(ESI): m/z calcd for
C17H16O2SiNa: 303.0812 [M+Na+]; found: 303.0813.
Sythesis of a new 1-bromohexatriynes
(2-C6Br) 4-(Bromohexatriynyl)nitrobenzene
A general procedure for bromination of trimethylsilyl-protected polyynes: 2ꢀC6TMS (0.124 g,
0.464 mmol) was dissolved in acetonitrile (10 mL). Next Nꢀbromosuccinimide (0.100 g, 0.562
mmol), AgF (0.060 g, 0.47 mmol) and H2O (17 ꢂL) were added. The flask was wrapped with
aluminum foil and the mixture was stirred for 22 h. Next the solvent was removed under
reduced pressure and a product was purified by passing through short silica gel plug
(DCM/hexane, v/v, 1/2) to give 0.122 g (0.445 mmol) of yellow, quickly darkening crystals.
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Yield: 96%. H NMR (500 MHz, CDCl3) δ 8.23ꢀ8.18 (m, 2H, CHAr), 7.70ꢀ7.64 (m, 2H,
CHAr). 13C{1H}NMR (126 MHz, CDCl3) δ 148.0 (CNO2), 134.0 (CHAr), 127.8 (CPhC≡C),
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123.9 (CHAr), 79.0 (C≡C), 73.2 (C≡C), 69.8 (C≡C), 65.9 (C≡C), 58.2 (C≡C), 45.1 (C≡CBr).
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HRMS(ESI): m/z calcd for C12H5BrNO2Na: 273.9498 [M+Na+]; found: 273.9493.
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(3-C6Br) 1-(4-(Bromohexatriynyl)phenyl)ethanone
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According to the general procedure for bromination of trimethylsilylꢀprotected polyynes 3ꢀ
C6TMS (0.077 g, 0.29 mmol), Nꢀbromosuccinimide (0.062 g, 0.35 mmol), AgNO3 (0.049 g,
0.29 mmol), KF (0.017 g, 0.29 mmol), H2O (10 ꢂL) and acetonitrile (10 mL) were used.
Time: 6 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid (which
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quickly changed to dark green or brown), yield: 79% (0.062 g, 0.23 mmol). H NMR (500
MHz, CDCl3) δ 7.93ꢀ7.90 (m, 2H, C6H4), 7.62ꢀ7.59 (m, 2H, C6H4), 2.60 (s, 3H, CH3).
13C{1H}NMR (126 MHz, CDCl3) δ 197.1 (C=O), 137.5 (CArC=O), 133.4 (CH from C6H4),
128.4 (CH from C6H4), 125.6 (CArC≡C), 77.2 (C6H4C≡C), 74.7 (C≡C), 68.7 (C≡C), 66.1
(C≡C), 58.6 (C≡C), 44.1 (C≡CBr), 26.8 (CH3). HRMS(ESI): m/z calcd for C14H8BrO:
270.9753 [M+H+]; found: 270.9753.
(4-C6Br) Ethyl 4-(bromohexatriynyl)benzoate
According to the general procedure for bromination of trimethylsilylꢀprotected polyynes 4ꢀ
C6TMS (0.102 g, 0.35 mmol), Nꢀbromosuccinimide (0.074 g, 0.42 mmol), AgNO3 (0.059 g,
0.346 mmol), KF (0.020 g, 0.35 mmol), H2O (13 ꢂL) and acetonitrile (10 mL) were used.
Time: 2.5 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid (which
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quickly changed to dark green or brown), yield: 86% (0.092 g. 0.30 mmol). H NMR (500
MHz, CDCl3) δ 8.01ꢀ7.98 (m, 2H, C6H4), 7.58ꢀ7.55 (m, 2H, C6H4), 4.38 (q, JHH= 7.1 Hz, 2H,
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OCH2), 1.39 (t, JHH = 7.1 Hz, CH3). C{1H}NMR (126 MHz, CDCl3) δ 165.8 (C=O), 133.1
(CH from C6H4), 131.4 (CArC=O), 129.7 (CH from C6H4), 125.3 (CArC≡C), 76.8 (C6H4C≡C),
74.8 (C≡C), 68.5 (C≡C), 66.1 (C≡C), 61.5 (OCH2), 58.7 (C≡C), 44.0 (C≡CBr), 14.4 (CH3).
HRMS(ESI): m/z calcd for C15H9BrO2Na: 322.9678 [M+Na+]; found: 322.9682.
(5-C6Br) 4-(Bromohexatriynyl)phenyl acetate
According to the general procedure for bromination of trimethylsilylꢀprotected polyynes 5ꢀ
C6TMS (0.108 g, 0.357 mmol), Nꢀbromosuccinimide (0.082 g, 0.46 mmol), AgNO3 (0.065 g,
0.38 mmol), KF (0.022 g, 0.38 mmol), H2O (14 ꢂL) and acetonitrile (10 mL) were used.
Time: 6 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid (which
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quickly changed to dark green or brown), yield: 67% (0.070 g, 0.24 mmol). H NMR (500
MHz, CDCl3) δ 7.55ꢀ7.52 (m, 2H, C6H4), 7.09ꢀ7.06 (m, 2H, C6H4), 2.30 (s, 3H, CH3).
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13C{1H}NMR (126 MHz, CDCl3) δ 168.8 (C=O), 151.7 (CArO), 134.4 (CH from C6H4), 122.0
(CH from C6H4), 118.2 (CArC≡C), 74.9 (C6H4C≡C), 74.3 (C≡C), 67.2 (C≡C), 66.0 (C≡C),
58.9 (C≡C), 42.9 (C≡CBr), 21.1 (CH3). HRMS(ESI): m/z calcd for C14H7BrO2Na: 308.9522
[M+Na+]; found: 308.9514.
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Synthesis of polyynyl-substituted pyrroles
(1-C6THI-H), 4-((4,5,6,7-Tetrahydro-1H-indol-2-yl)hexatriynyl)benzonitrile
A general procedure for inverse Sonogashira coupling: 1ꢀC6Br (0.0080 g, 0.031 mmol),
4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0080 g, 0.062 mmol) and K2CO3 (0.160 g) were placed in a
mortar and grinded for 10 minutes. After this time the mixture was placed in a vial and left for
24 h. After this time the mixture was placed at the top of silica gel column and the product
was eluted with the mixture of hexane and dichloromethane (v/v; 1/1). Pure product was
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obtained as yellow solid (0.0047 g, 0.016 mmol), yield: 52%. H NMR (500 MHz, CDCl3) δ
8.05 (bs, 1H, NH), 7.64ꢀ7.56 (m, 4H, C6H4), 6.47 (d, JHH = 2.3 Hz, 1H, pyrrole), 2.57 (t, JHH
=
6.2 Hz, 2H, CH2), 2.47 (t, JHH = 6.0 Hz, 2H, CH2), 1.84ꢀ1.78 (m, 2H, CH2), 1.78ꢀ1.69 (m, 2H,
CH2). 13C{1H}NMR (126 MHz, CDCl3) δ 133.3 (NCCH2, pyrrole), 132.5 (CH, C6H4CN),
132.2 (CH, C6H4CN), 126.6 (CArC≡C), 119.4 (CTHIC≡C), 119.3 (C≡N), 112.6 (CC≡N), 108.7
(HCCH2, pyrrole), 79.0 (C≡C), 77.9 (C≡C), 77.8 (C≡C), 74.2 (C≡C), 69.7 (C≡C), 68.5 (C≡C),
23.5 (CH2), 23.2 (CH2), 23.0 (CH2), 22.8 (CH2). IR (fluorinated oil mull) 2224 (N≡C), 2140
(C≡C), 2092 (C≡C) cm−1. HRMS(ESI): m/z calcd for C21H14N2: 295.1230 [M+H+]; found:
295.1230.
(1-C6THI-Me), 4-((1-Methyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)benzonitrile
According to the general procedure for inverse Sonogashira coupling 1ꢀC6Br (0.0084 g, 0.033
mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0089 g, 0.066 mmol) and K2CO3 (0.170 g)
were used. Time: 3 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
(0.0083 g, 0.027 mmol), yield: 82%. 1H NMR (500 MHz, CDCl3) δ 7.63ꢀ7.57 (m, 4H, C6H4),
6.46 (s, 1H, CH, pyrrole), 3.51 (s, 3H, CH3), 2.52 (t, JHH = 6.3 Hz, 2H, CH2), 2.46 (t, JHH
=
6.1 Hz, 2H, CH2), 1.86ꢀ1.80 (m, 2H, CH2), 1.74ꢀ1.69 (m, 2H, CH2). 13C NMR (126 MHz,
CDCl3) δ 134.3 (NCCH2, pyrrole), 133.3 (CH, C6H4CN), 132.2 (CH, C6H4CN), 126.7
(CArC≡C), 118.8 (CTHIC≡C), 118.4 (C≡N), 118.2 (CH, pyrrole), 112.6 (CC≡N), 111.8
(CHCCH2, pyrrole), 80.5 (C≡C), 79.1 (C≡C), 78.3 (C≡C), 73.9 (C≡C), 69.9 (C≡C), 69.3
(C≡C), 31.2 (CH3), 23.4 (CH2), 23.0 (CH2), 23.0 (CH2), 22.6 (CH2). IR (fluorinated oil mull)
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2222 (N≡C), 2147 (C≡C), 2095 (C≡C) cm−1. HRMS(ESI): m/z calcd for C22H17N2: 309.1386
[M+H+]; found: 309.1364.
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According to the general procedure for inverse Sonogashira coupling 1ꢀC6Br (0.010 g, 0.040
mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.012 g, 0.080 mmol) and K2CO3 (0.220 g)
were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0051 g, 0.016 mmol), yield: 40%. H NMR (500 MHz, CDCl3) δ 7.63ꢀ7.56 (m, 4H,
C6H4CN), 6.89 (dd, JHH = 16.0, 9.3 Hz, 1H, CH=CH2), 6.55 (s, 1H, pyrrole), 5.39 (dd, JHH
=
16.0, 1.2 Hz, 1H, CH=CH2), 4.93 (dd, JHH = 9.3, 1.2 Hz, 1H, CH=CH2), 2.64 (t, JHH = 6.2 Hz,
2H, CH2), 2.47 (t, J = 6.1 Hz, 2H, CH2), 1.86ꢀ1.79 (m, 2H, CH2), 1.76ꢀ1.69 (m, 2H, CH2). 13C
NMR (126 MHz, CDCl3) δ 133.5 (NCCH2, pyrrole), 133.3 (CH from C6H4CN), 132.2 (CH
from C6H4CN), 130.0 (CH=CH2), 126.5 (CArC≡C), 121.1 (CH, pyrrole), 120.6 (CTHIC≡C),
118.3 (C≡N), 112.7 (CC≡N), 111.2 (CHCCH2, pyrrole), 103.8 (CH=CH2), 80.6 (C≡C), 78.9
(C≡C), 78.3 (C≡C), 73.4 (C≡C), 69.6 (C≡C), 69.3 (C≡C), 24.2 (CH2), 23.1 (CH2), 23.0 (CH2),
23.0 (CH2). IR (fluorinated oil mull) 2223 (N≡C), 2151 (C≡C), 2097 (C≡C) cm−1.
HRMS(ESI): m/z calcd for C23H16N2: 321.1386 [M+H+]; found: 321.1387.
(1-C6THI-Bn), 4-((1-Benzyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)benzonitrile
According to the general procedure for inverse Sonogashira coupling 1ꢀC6Br (0.0060 g, 0.024
mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.010 g, 0.048 mmol) and K2CO3 (0.160 g)
were used. Time: 3 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0079 g, 0.021 mmol), yield: 88%. H NMR (500 MHz, CDCl3) δ 7.62ꢀ7.54 (m, 4H,
C6H4C≡N), 7.34ꢀ7.30 (m, 2H, C6H5), 7.29ꢀ7.24 (m, 1H, C6H5), 7.08ꢀ7.03 (m, 2H, C6H5), 6.54
(s, 1H, CH, pyrrole), 5.10 (s, 2H, CH2Ph), 2.48 (t, JHH = 6.0 Hz, 2H, CH2), 2.40 (t, JHH = 6.2
Hz, 2H, CH2), 1.79ꢀ1.73 (m, 2H, CH2), 1.73ꢀ1.65 (m, 2H, CH2). 13C NMR (126 MHz, CDCl3)
δ 137.6 (ipso from C6H5), 134.2 (NCCH2, pyrrole), 133.2 (CH from C5H4CN), 132.2 (CH
from C5H4CN), 128.9 (CH, C6H5), 127.6 (CH, ortho from C6H5), 126.8 (CH, C6H5), 126.6
(CPhC≡C), 119.4 (CH, pyrrole), 118.7 (CTHIC≡C), 118.3 (C≡N), 112.6 (CC≡N), 112.0
(CHCCH2, pyrrole), 80.5 (C≡C), 79.0 (C≡C), 78.3 (C≡C), 73.8 (C≡C), 69.9 (C≡C), 69.3
(C≡C), 48.4 (CH2Ph), 23.3 (CH2), 23.1 (CH2), 22.9 (CH2), 22.8 (CH2). IR (fluorinated oil
mull) 2226 (N≡C), 2140 (C≡C), 2091 (C≡C) cm−1. HRMS(ESI): m/z calcd for C28H21N2:
385.1699 [M+H+]; found: 385.1699.
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According to the general procedure for inverse Sonogashira coupling 2ꢀC6Br (0.0090 g, 0.033
mmol), 4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0080 g, 0.066 mmol) and K2CO3 (0.170 g) were used.
Time: 3 d, purification: short silica gel plug (hexane/DCM, v/v, 1/1), red solid (0.0047 g,
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0.014 mmol), yield: 42%. H NMR (500 MHz, CDCl3) δ 8.15ꢀ8.07 (m, 2H, C6H4NO2), 7.97
(s, 1H, NH), 7.61ꢀ7.54 (m, 2H, C6H4NO2), 6.41 (d, JHH = 2.3 Hz, 1H, CH, pyrrole), 2.50 (t,
JHH = 6.1 Hz, 2H, CH2), 2.40 (t, JHH = 6.0 Hz, 2H, CH2), 1.78ꢀ1.71 (m, 2H, CH2), 1.70ꢀ1.63
(m, 2H, CH2). 13C NMR (126 MHz, CDCl3) δ 147.7 (CNO2), 133.6 (NCCH2, pyrrole), 132.6
(CH from C6H4), 128.6 (CPhC≡C), 123.9 (CH from C6H4), 119.4 (CH, pyrrole), 108.7
(CHCCH2, pyrrole), 79.9 (C≡C), 77.8 (C≡C), 77.7 (C≡C), 74.5 (C≡C), 70.2 (C≡C), 68.5
(C≡C), 23.5 (CH2), 23.2 (CH2), 23.0 (CH2), 22.8 (CH2). IR (fluorinated oil mull) 2145 (C≡C),
2093 (C≡C) cm−1.HRMS(ESI): m/z calcd for C24H17N2: 315.1128 [M+H+]; found: 315.1130.
(2-C6THI-Me), 1-Methyl-2-((4-nitrophenyl)hexatriynyl)-4,5,6,7-tetrahydro-1H-indole
According to the general procedure for inverse Sonogashira coupling 2ꢀC6Br (0.0176 g, 0.064
mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0174 g, 0.064 mmol) and K2CO3 (0.170 g)
were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/2), red solid
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(0.0122 g, 0.037 mmol), yield: 58%. H NMR (500 MHz, CDCl3) δ 8.22ꢀ8.18 (m, 2H,
C6H4NO2), 7.67ꢀ7.63 (m, 2H, C6H4NO2), 6.47 (s, 1H, pyrrole), 3.52 (s, 3H, CH3), 2.52 (t, JHH
= 6.3 Hz, 2H, CH2), 2.46 (t, JHH = 6.1 Hz, 2H, CH2), 1.87ꢀ1.80 (m, 2H, CH2), 1.75ꢀ1.69 (m,
2H, CH2). 13C NMR (126 MHz, CDCl3) δ 147.6 (CNO2), 134.4 (NCCH2, pyrrole), 133.6 (CH
from C6H4), 128.7 (CPhC≡C), 123.8 (CH from C6H4), 118.9 (CTHIC≡C), 118.3 (CH, pyrrole),
111.8 (CHCCH2, pyrrole), 80.6 (C≡C), 79.9 (C≡C), 78.1 (C≡C), 74.2 (C≡C), 70.4 (C≡C),
69.4 (C≡C), 31.3 (CH3), 23.4 (CH2), 23.1 (CH2), 23.0 (CH2), 22.6 (CH2). IR (fluorinated oil
mull) 2144 (C≡C), 2096 (C≡C) cm−1. HRMS(ESI): m/z calcd for C21H16N2O2Na: 351.1103
[M+Na+]; found: 351.1107.
(2-C6THI-Vin), 2-((4-Nitrophenyl)hexatriynyl)-1-vinyl-4,5,6,7-tetrahydro-1H-indole
According to the general procedure for inverse Sonogashira coupling 2ꢀC6Br (0.0115 g, 0.042
mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0124 g, 0.084 mmol) and K2CO3 (0.240 g)
were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/2), red solid
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(0.0116 g, 0.034 mmol), yield: 81%. H NMR (500 MHz, CDCl3) δ 8.22ꢀ8.17 (m, 2H,
C6H4NO2), 7.67ꢀ7.62 (m, 2H, C6H4NO2), 6.89 (dd, JHH = 16.0, 9.3 Hz, 1H, CH=CH2), 6.56 (s,
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1H, pyrrole), 5.40 (dd, JHH = 16.0, 1.2 Hz, 1H, CH=CH2), 4.93 (dd, JHH = 9.3, 1.2 Hz, 1H,
CH=CH2), 2.64 (t, JHH = 6.2 Hz, 2H, CH2), 2.47 (t, JHH = 6.1 Hz, 2H, CH2), 1.86ꢀ1.80 (m, 2H,
CH2), 1.76ꢀ1.70 (m, 2H, CH2). 13C NMR (126 MHz, CDCl3) δ 147.7 (CNO2), 133.6 (CH from
C6H4), 130.0 (CArC≡C), 128.4 (CH from C6H4), 123.8 (CH of C6H4), 121.2 (CH, pyrrole),
120.6 (CTHIC≡C), 111.2 (CHCCH2, pyrrole), 103.9 (HC=CH2), 80.7 (C≡C), 79.8 (C≡C), 78.0
(C≡C), 73.7 (C≡C), 70.1 (C≡C), 69.3 (C≡C), 24.2 (CH2), 23.1 (CH2), 23.0 (CH2), 23.0 (CH2).
IR (fluorinated oil mull) 2147 (C≡C), 2096 (C≡C) cm−1. HRMS(ESI): m/z calcd for
C22H17N2O2: 341.1286 [M+H+]; found: 341.1293.
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(2-C6THI-Bn) 1-Benzyl-2-((4-nitrophenyl)hexatriynyl)-4,5,6,7-tetrahydro-1H-indole
According to the general procedure for inverse Sonogashira coupling 2ꢀC6Br (0.0155 g,
0.0566 mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.024 g, 0.132 mmol) and K2CO3
(0.390 g) were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1),
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red solid (0.0224 g, 0.055 mmol), yield: 97%. H NMR (500 MHz, CDCl3) δ 8.21ꢀ8.17 (m,
2H, C6H4), 7.65ꢀ7.60 (m, 2H, C6H4), 7.35ꢀ7.30 (m, 2H, C6H5), 7.29ꢀ7.25 (m, 1H, C6H5), 7.08ꢀ
7.04 (m, 2H, C6H5), 6.55 (s, 1H, CH, pyrrole), 5.10 (s, 2H, CH2Ph), 2.48 (t, JHH = 5.9 Hz, 2H,
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CH2), 2.40 (t, JHH = 6.1 Hz, 2H, CH2), 1.79ꢀ1.73 (m, 2H, CH2), 1.72ꢀ1.66 (m, 2H, CH2). C
NMR (126 MHz, CDCl3) δ 147.6 (CNO2), 137.6 (ipso from C6H5), 134.3 (NCCH2, pyrrole),
133.6 (CH from C6H4), 128.9 (CH, C6H5), 128.6 (CArC≡C), 127.6 (CH, ortho from C6H5),
126.8 (CH, C6H5), 123.8 (CH from C6H4), 119.5 (CTHIC≡C), 118.9 (CH, pyrrole), 112.0
(CHCCH2, pyrrole), 79.9 (C≡C), 78.1 (C≡C), 74.2 (C≡C), 70.4 (C≡C), 69.4 (C≡C), 48.5
(CH3), 23.3 (CH2), 23.1 (CH2), 22.9 (CH2), 22.8 (CH2). HRMS(ESI): m/z calcd for
C27H21N2O2: 405.1598 [M+H+]; found: 405.1596.
(3-C6THI-H), 1-(4-((4,5,6,7-Tetrahydro-1H-indol-2-yl)hexatriynyl)phenyl)ethanone
According to the general procedure for inverse Sonogashira coupling 3ꢀC6Br (0.0140 g,
0.0516 mmol), 4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0125 g, 0.104 mmol) and K2CO3 (0.265 g)
were used. Time: 22 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0013 g, 0.0042 mmol), yield: 8%. H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H, NH), 7.93ꢀ
7.89 (m, 2H, C6H4), 7.61ꢀ7.57 (m, 2H, C6H4), 6.46 (d, J HH = 2.4 Hz, 1H, pyrrole), 2.60 (s,
3H, C(O)CH3), 2.57 (t, J HH = 6.2 Hz, 2H, CH2), 2.47 (t, J HH = 6.0 Hz, 2H, CH2), 1.84ꢀ1.78
(m, 2H, CH2), 1.76ꢀ1.71 (m, 2H, CH2). 13C NMR (75 MHz, CDCl3) δ 197.2 (C=O), 137.1
(NCCH2, pyrrole), 133.1 (CH from C6H4), 132.3 (CArC=O), 128.4 (CH from C6H4), 126.4
(CArC≡C), 119.3 (CH, pyrrole), 119.1 (CTHIC≡C), 108.8 (CHCCH2, pyrrole), 78.9 (C≡C), 77.4
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(C≡C), 73.7 (C≡C), 69.0 (C≡C), 68.8 (C≡C), 26.8 (C(O)CH3), 23.5 (CH2), 23.2 (CH2), 23.1
(CH2), 22.8 (CH2), one acetylene signal under solvent. HRMS(ESI): m/z calcd for C22H16NO:
310.1237 [MꢀHꢀ]; found: 310.1243.
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(3-C6THI-Me), 1-(4-((1-Methyl-4,5,6,7-tetrahydro-1
hanone
H-indol-2-yl)hexatriynyl)phenyl)et-
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According to the general procedure for inverse Sonogashira coupling 3ꢀC6Br (0.0550 g, 0.203
mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.025 g, 0.185 mmol) and K2CO3 (0.800 g)
were used. Time: 3 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
(0.026 g, 0.080 mmol), yield: 39%. 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J HH = 8.6 Hz, 2H,
C6H4), 7.59 (d, JHH = 8.6 Hz, 2H, C6H4), 6.45 (s, 1H, pyrrole), 3.51 (s, 3H, NCH3), 2.60 (s,
3H, C(O)CH3), 2.52 (t, JHH = 6.3 Hz, 2H, CH2), 2.46 (t, JHH = 6.1 Hz, 2H, CH2), 1.86ꢀ1.80
(m, 2H, CH2), 1.74ꢀ1.69 (m, 2H, CH2). 13C NMR (126 MHz, CDCl3) δ 197.2 (C=O), 137.1
(NCCH2, pyrrole), 133.4 (CArC=O), 133.0 (CH from C6H4), 128.4 (CH from C6H4), 126.5
(CArC≡C), 118.7 (CTHIC≡C), 117.9 (CH, pyrrole), 111.9 (CHCCH2, pyrrole), 80.5 (C≡C), 79.4
(C≡C), 78.0 (C≡C), 73.3 (C≡C), 69.6 (C≡C), 69.2 (C≡C), 31.2 (NCH3), 26.8 (C(O)CH3), 23.4
(CH2), 23.05 (CH2), 23.0 (CH2), 22.6 (CH2). IR (fluorinated oil mull) 2145 (C≡C), 2095
(C≡C) cm−1. HRMS(ESI): m/z calcd for C23H20NO: 326.1539 [M+H+]; found: 326.1535.
(3-C6THI-Vin), 1-(4-((1-Vinyl-4,5,6,7-tetrahydro-1
none
H-indol-2-yl)hexatriynyl)phenyl)etha-
According to the general procedure for inverse Sonogashira coupling 3ꢀC6Br (0.0130 g,
0.0480 mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0141 g, 0.0958 mmol) and K2CO3
(0.271 g) were used. Time: 20 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1),
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yellow solid (0.0155 g, 0.0459 mmol), yield: 96%. H NMR (500 MHz, CDCl3) δ 7.93ꢀ7.90
(m, 2H, C6H4), 7.62ꢀ7.57 (m, 2H, C6H4), 6.90 (dd, JHH = 16.0, 9.3 Hz, 1H, CH=CH2), 6.53 (s,
1H, pyrrole), 5.39 (dd, JHH = 16.0, 1.2 Hz, 1H, CH=CH2), 4.92 (dd, JHH = 9.3, 1.1 Hz, 1H,
CH=CH2), 2.64 (t, JHH = 6.2 Hz, 2H, CH2), 2.60 (s, 3H, C(O)CH3), 2.47 (t, J HH= 6.1 Hz, 2H,
CH2), 1.82 (ddd, JHH = 8.4, 7.7, 4.2 Hz, 2H, CH2), 1.75ꢀ1.69 (m, 2H, CH2). 13C NMR (126
MHz, CDCl3) δ 197.2 (C=O), 137.1 (NCCH2, pyrrole), 133.3 (CArC=O), 133.1 (CH from
C6H4), 130.1 (CH=CH2), 128.4 (CH from C6H4), 126.3 (CArC≡C), 120.9 (CH, pyrrole), 120.5
(CTHIC≡C), 111.4 (CHCCH2, pyrrole), 103.7 (CH=CH2), 80.7 (C≡C), 79.3 (C≡C), 77.8
(C6H4C≡C), 72.9 (CTHIC≡C), 69.6 (C≡C), 68.9 (C≡C), 26.8 (C(O)CH3), 24.2 (CH2), 23.2
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(CH2), 23.0 (CH2), 23.0 (CH2). HRMS(ESI): m/z calcd for C24H20NO: 338.1539 [M+H+];
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(3-C6THI-Bn), 1-(4-((1-Benzyl-4,5,6,7-tetrahydro-1
anone
H-indol-2-yl)hexatriynyl)phenyl)eth-
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According to the general procedure for inverse Sonogashira coupling 3ꢀC6Br (0.0088 g, 0.032
mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0137 g, 0.064 mmol) and K2CO3 (0.225 g)
were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
(0.0100 g, 0.025 mmol), yield: 78%. 1H NMR (500 MHz, CDCl3) δ 7.92ꢀ7.89 (m, 2H, C6H4),
7.59ꢀ7.56 (m, 2H, C6H4), 7.35ꢀ7.30 (m, 2H, C6H5), 7.27 (d, JHH = 1.2 Hz, 1H, C6H5), 7.06 (dd,
JHH = 9.4, 2.4 Hz, 2H, C6H5), 6.53 (s, 1H, CH, pyrrole), 5.10 (s, 2H, CH2Ph), 2.60 (s, 3H,
C(O)CH3), 2.48 (t, JHH = 5.9 Hz, 2H, CH2), 2.40 (t, JHH = 6.1 Hz, 2H, CH2), 1.80ꢀ1.71 (m,
2H, CH2), 1.72ꢀ1.66 (m, 2H, CH2). 13C NMR (75 MHz, CDCl3) δ 197.2 (C=O), 137.6 (ipso
from C6H5), 137.0 (CPhC=O), 134.0 (NCCH2, pyrrole), 133.0 (CH from C6H4), 128.9 (CH,
ortho from C6H5), 128.4 (CH from C6H4), 127.6 (CH from C6H5), 126.8 (CH from C6H5),
126.4 (CArC≡C), 119.4 (CTHIC≡C), 118.5 (CH, pyrrole), 112.1 (CHCCH2, pyrrole), 80.5
(C≡C), 79.4 (C≡C), 77.9 (C6H4C≡C), 73.3 (CTHIC≡C), 69.6 (C≡C), 69.1 (C≡C), 48.4
(CH2Ph), 26.8 (C(O)CH3), 23.3 (CH2), 23.1 (CH2), 22.9 (CH2), 22.8 (CH2). HRMS(ESI): m/z
calcd for C29H24NO: 402.1852 [M+H+]; found: 402.1854.
(4-C6THI-H), Ethyl 4-((4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)benzoate
According to the general procedure for inverse Sonogashira coupling 4ꢀC6Br (0.0130 g,
0.0432 mmol), 4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0105 g, 0.0873 mmol) and K2CO3 (0.235 g)
were used. Time: 19 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0038 g, 0.011 mmol), yield: 25%. H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H, NH), 8.02ꢀ
7.98 (m, 2H, C6H4), 7.59ꢀ7.55 (m, 2H, C6H4), 6.45 (d, JHH = 2.3 Hz, 1H, pyrrole), 4.38 (q, JHH
= 7.1 Hz, 2H, OCH2), 2.57 (t, JHH= 6.2 Hz, 2H, CH2), 2.47 (t, JHH = 6.0 Hz, 2H, CH2), 1.40 (t,
JHH = 7.1 Hz, 3H, CH3). 13C NMR (126 MHz, CDCl3) δ 165.9 (C=O), 132.8 (CH from C6H4),
132.2 (NCCH2, pyrrole), 131.0 (CArC=O), 129.7 (CH from C6H4), 126.1 (CArC≡C), 119.3
(CH, pyrrole), 119.0 (CTHIC≡C), 108.9 (CHCCH2, pyrrole), 79.1 (C≡C), 77.8 (C≡C), 77.5
(C6H4C≡C), 73.5 (C≡C), 68.8 (C≡C), 68.7 (C≡C), 61.4 (OCH2), 23.6 (CH2), 23.2 (CH2), 23.1
(CH2), 22.8 (CH2), 14.4 (CH3). HRMS(ESI): m/z calcd for C23H18NO2: 340.1343 [MꢀHꢀ];
found: 340.1350.
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(4-C6THI-Me), Ethyl 4-((1-methyl-4,5,6,7-tetrahydro-1
ate
H-indol-2-yl)hexatriynyl)benzo-
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According to the general procedure for inverse Sonogashira coupling 4ꢀC6Br (0.0106 g, 0.035
mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0095 g, 0.070 mmol) and K2CO3 (0.201 g)
were used. Time: 20 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
(0.0094 g, 0.026 mmol), yield: 74%. 1H NMR (500 MHz, CDCl3) δ 8.02ꢀ7.98 (m, 2H, C6H4),
7.58ꢀ7.55 (m, 2H, C6H4), 6.44 (s, 1H, pyrrole), 4.38 (q, J HH= 7.1 Hz, 2H, OCH2), 3.51 (s, 3H,
CH3), 2.52 (t, JHH = 6.3 Hz, 2H, CH2), 2.46 (t, JHH = 6.1 Hz, 2H, CH2), 1.86ꢀ1.80 (m, 2H,
CH2), 1.74ꢀ1.69 (m, 2H, CH2), 1.40 (t, JHH = 7.1 Hz, 3H, CH3). 13C NMR (126 MHz, CDCl3)
δ 165.9 (C=O), 134.0 (NCCH2, pyrrole), 132.8 (CH from C6H4), 131.0 (CArC=O), 129.6 (CH
from C6H4), 126.2 (CArC≡C), 118.9 (CTHIC≡C), 117.9 (2C, CH, pyrrole, CHCCH2, pyrrole),
80.5 (C≡C), 79.5 (C≡C), 77.6 (C6H4C≡C), 73.2 (C≡C), 69.6 (C≡C), 68.9 (C≡C), 61.4
(OCH2), 31.2 (CH3), 23.4 (CH2), 23.1 (CH2), 23.0 (CH2), 22.6 (CH2), 14.4 (CH3). IR
(fluorinated oil mull) 2148 (C≡C), 2096 (C≡C) cm−1. HRMS(ESI): m/z calcd for C24H22NO2:
356.1645 [M+H+]; found: 356.1645.
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(4-C6THI-Vin), Ethyl 4-((1-vinyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)benzoate
According to the general procedure for inverse Sonogashira coupling 4ꢀC6Br (0.0095 g, 0.032
mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0093 g, 0.063 mmol) and K2CO3 (0.188 g)
were used. Time: 23 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0022 g, 0.0060 mmol), yield: 19%. H NMR (500 MHz, CDCl3) δ 8.02ꢀ7.99 (m, 2H,
C6H4), 7.58ꢀ7.55 (m, 2H, C6H4), 6.90 (dd, JHH = 16.0, 9.3 Hz, 1H, CH=CH2), 6.53 (s, 1H,
pyrrole), 5.39 (dd, JHH = 16.0, 1.2 Hz, 1H, CH=CH2), 4.92 (dd, JHH = 9.3, 1.2 Hz, 1H,
CH=CH2), 4.38 (q, JHH = 7.1 Hz, 2H, OCH2), 2.64 (t, JHH = 6.2 Hz, 2H, CH2), 2.47 (t, JHH
=
6., 1 Hz, 2H, CH2), 1.86ꢀ1.80 (m, 2H, CH2), 1.76ꢀ1.70 (m, 2H, CH2), 1.40(t, JHH = 7.1 3H,
CH3). 13C NMR (126 MHz, CDCl3) δ 165.9 (C=O), 133.3 (NCCH2, pyrrole), 132.8 (CH from
C6H4), 131.0 (CArC=O), 130.1 CH=CH2), 129.7 (CH from C6H4), 126.0 (CArC≡C), 120.8
(CH, pyrrole), 120.5 (CTHIC≡C), 111.4 (CHCCH2, pyrrole), 103.6 (CH=CH2), 80.7 (C≡C),
79.4 (C≡C), 72.7 (C≡C), 69.6 (C≡C), 68.6 (C≡C), 61.4 (OCH2), 24.2 (CH2), 23.2 (CH2, 23.0
(CH2), 23.0 (CH2), 14.4 (CH3), one acetylene signal under solvent. HRMS(ESI): m/z calcd for
C25H22NO2: 368.1645 [M+H+]; found: 368.1644.
(4-C6THI-Bn), Ethyl 4-((1-benzyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)benzoate
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According to the general procedure for inverse Sonogashira coupling 4ꢀC6Br (0.0190 g,
0.0631 mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0200 g, 0.095 mmol) and K2CO3
(0.390 g) were used. Time: 4 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1),
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yellow solid (0.0156 g, 0.0362 mmol), yield: 57%. H NMR (500 MHz, CDCl3) δ 8.02ꢀ7.97
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(m, 2H, C6H4), 7.56ꢀ7.53 (m, 2H, C6H4), 7.38ꢀ7.27 (m, 3H, C6H5), 7.09ꢀ7.05 (m, 2H, C6H5),
6.53 (s, 1H, CH, pyrrole), 5.10 (s, 2H, CH2Ph), 4.38 (q, JHH = 7.1 Hz, 2H, OCH2), 2.48 (t, JHH
= 5.9 Hz, 2H, CH2), 2.40 (t, JHH = 6.1 Hz, 2H, CH2), 1.78ꢀ1.73 (m, 2H, CH2), 1.72ꢀ1.67 (m,
2H, CH2), 1.40 (t, JHH = 7.1 Hz, 3H, CH3). 13C NMR (126 MHz, CDCl3) δ 165.9 (C=O),
137.6 (ipso from C6H5), 133.9 (NCCH2, pyrrole), 132.7 (CH from C6H4), 130.9 (CArC=O),
129.6 (CH from C6H4), 128.9 (CH, ortho from C6H5), 127.6 (CH from C6H5), 126.8 (CH from
C6H5), 126.1 (CArC≡C), 119.3 (CTHIC≡C), 118.4 (CH, pyrrole), 112.1 (CTHIC≡C), 80.5 (C≡C),
79.5 (C≡C), 77.5 C6H4C≡C), 73.1 (C≡C), 69.6 (C≡C), 68.9 (C≡C), 61.4 (OCH2), 48.4
(CH2Ph), 23.3 (CH2), 23.1 (CH2), 22.9 (CH2), 22.8 (CH2), 14.4 (CH3). HRMS(ESI): m/z calcd
for C30H26NO2: 432.1958 [M+H+]; found: 432.1956.
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(5-C6THI-H), 4-((4,5,6,7-Tetrahydro-1H-indol-2-yl)hexatriynyl)phenyl acetate
According to the general procedure for inverse Sonogashira coupling 5ꢀC6Br (0.0112 g,
0.0390 mmol), 4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0095 g, 0.078 mmol) and K2CO3 (0.207 g)
were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0014 g, 0.0043 mmol), yield: 11%. H NMR (500 MHz, CDCl3) δ 7.99 (s, 1H, NH), 7.55ꢀ
7.50 (m, 2H, C6H4), 7.09ꢀ7.06 (m, 2H, C6H4), 6.44 (d, JHH = 2.4 Hz, 1H, pyrrole), 2.56 (t, JHH
= 6.2 Hz, 2H, CH2), 2.47 (t, JHH = 6.0 Hz, 2H, CH2), 2.30 (s, 3H, CH3), 1.84ꢀ1.78 (m, 2H,
CH2), 1.74 (dt, JHH = 5.0, 4.5 Hz, 2H, CH2). 13C NMR (75 MHz, CDCl3) δ 169.1 (C=O),
151.5 (CArO), 134.2 (CH from C6H4), 132.0 (NCCH2, pyrrole), 122.1 (CH from C6H4), 119.2
(CArC≡C), 119.1 (CTHIC≡C), 118.8 (CH, pyrrole), 109.0 (CHCCH2, pyrrole), 79.2 (C≡C), 77.4
(C6H4C≡C), 75.0 (C≡C), 72.7 (C≡C), 69.0 (C≡C), 67.4 (C≡C), 23.6 (CH2), 23.2 (CH2), 23.1
(CH2), 22.8 (CH2), 21.3 (CH3). HRMS(ESI): m/z calcd for C22H16NO2: 326.1186 [MꢀHꢀ];
found: 326.1187.
(5-C6THI-Me), 4-((1-Methyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)phenyl acetate
According to the general procedure for inverse Sonogashira coupling 5ꢀC6Br (0.0101 g,
0.0352 mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0095 g, 0.070 mmol) and K2CO3
(0.196 g) were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1),
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yellow solid (0.0090 g, 0.026 mmol), yield: 74%. H NMR (500 MHz, CDCl3) δ 7.54ꢀ7.51
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(m, 2H, C6H4), 7.09ꢀ7.05 (m, 2H, C6H4), 6.43 (s, 1H, pyrrole), 3.51 (s, 3H, CH3), 2.51 (t, JHH
= 6.3 Hz, 2H, CH2), 2.46 (t, JHH = 6.1 Hz, 2H, CH2), 2.30 (s, 3H, CH3), 1.82 (ddd, JHH = 8.6,
7.7, 4.3 Hz, 2H, CH2), 1.71 (ddd, JHH = 15.3, 7.5, 4.2 Hz, 2H, CH2). 13C NMR (75 MHz,
CDCl3) δ 169.1 (C=O), 151.5 (CArO), 134.2 (CH from C6H4), 133.7 (NCCH2, pyrrole), 122.1
(CH from C6H4), 119.2 (CArC≡C), 118.6 (CTHIC≡C), 117.6 (CH, pyrrole), 112.1 (CHCCH2,
pyrrole), 80.4 (C≡C), 79.6 (C≡C), 75.0 (C6H4C≡C), 72.3 (C≡C), 69.7 (C≡C), 67.5 (C≡C),
31.2 (CH3), 23.4 (CH2), 23.0 (CH2), 23.0 (CH2), 22.6 (CH2), 21.3 (CH3). HRMS(ESI): m/z
calcd for C23H20NO2: 342.1489 [M+H+]; found: 342.1487.
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(5-C6THI-Vin), 4-((1-Vinyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)phenyl acetate
According to the general procedure for inverse Sonogashira coupling 5ꢀC6Br (0.0169 g,
0.0589 mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0173 g, 0.118 mmol) and K2CO3
(0.342 g) were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1),
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yellow solid (0.0026 g, 0.011 mmol), yield: 19%. H NMR (500 MHz, CDCl3) δ 7.54ꢀ7.51
(m, 2H, C6H4), 7.09ꢀ7.06 (m, 2H, C6H4), 6.90 (dd, JHH = 16.0, 9.3 Hz, 1H, CH=CH2), 6.52 (s,
1H, pyrrole), 5.39 (dd, JHH = 16.0, 1.2 Hz, 1H, CH=CH2), 4.91 (dd, JHH = 9.3, 1.1 Hz, 1H),
2.64 (t, JHH = 6.2 Hz, 2H, CH2), 2.46 (t, JHH = 6.1 Hz, 2H, CH2), 2.30 (s, 3H, CH3), 1.82 (ddd,
J HH= 8.4, 7.7, 4.2 Hz, 2H, CH2), 1.72 (ddd, JHH = 12.5, 6.1, 2.7 Hz, 2H, CH2). 13C NMR (126
MHz, CDCl3) δ 169.1 (C=O), 151.6 (CArO), 134.2 (CH from C6H4), 133.0 (NCCH2, pyrrole),
130.1 (CH=CH2), 122.1 (CH from C6H4), 120.6 (CH, pyrrole), 120.4 (CTHIC≡C), 119.0
(CArC≡C), 111.5 (CHCCH2, pyrrole), 103.5 (CH=CH2), 80.7 (C≡C), 79.6 (C≡C), 74.9
(C6H4C≡C), 71.9 (C≡C), 69.8 (C≡C), 67.3 (C≡C), 24.2 (CH2), 23.2 (CH2), 23.0 (CH2), 23.0
(CH2), 21.3 (CH3). IR (fluorinated oil mull) 2147 (C≡C), 2104 (C≡C) cm−1. HRMS(ESI): m/z
calcd for C24H20NO2: 354.1486 [M+H+]; found: 354.1486.
(5-C6THI-Bn), 4-((1-Benzyl-4,5,6,7-tetrahydro-1H-indol-2-yl)hexatriynyl)phenyl acetate
According to the general procedure for inverse Sonogashira coupling 5ꢀC6Br (0.0123 g,
0.0428 mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0181 g, 0.0857 mmol) and K2CO3
(0.304 g) were used. Time: 20 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1),
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yellow solid (0.0074 g, 0.018 mmol), yield: 42%. H NMR (500 MHz, CDCl3) δ 7.53ꢀ7.48
(m, 2H, C6H4), 7.38ꢀ7.27 (m, 3H, C6H5), 7.09ꢀ7.04 (m, 2H from C6H4 and 2H from C6H5),
6.51 (s, 1H, CH, pyrrole), 5.10 (s, 2H, CH2Ph), 2.48 (t, JHH = 6.0 Hz, 2H, CH2), 2.40 (t, JHH
=
6.1 Hz, 2H, CH2), 2.30 (s, 3H, CH3), 1.78ꢀ1.74 (m, 2H, CH2), 1.71ꢀ1.67 (m, 2H, CH2). 13C
NMR (126 MHz, CDCl3) δ 169.1 (C=O), 151.5 (CArO), 137.7 (ipso from C6H5), 134.2 (CH
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from C6H4), 133.7 (NCCH2, pyrrole), 128.9 (CH, ortho from C6H5), 127.6 (CH from C6H5),
126.8 (CH from C6H5), 122.1 (CH from C6H4), 119.2 (CArC≡C), 119.1 (CTHIC≡C), 118.2
(CH, pyrrole), 112.3 (CHCCH2, pyrrole), 80.5 (C≡C), 79.6 (C≡C), 75.0 (C6H4C≡C), 72.3
(C≡C), 69.7 (C≡C), 67.5 (C≡C), 48.4 (CH2Ph), 23.4 (CH2), 23.1 (CH2), 23.0 (CH2), 22.8
(CH2), 21.3 (CH3). HRMS(ESI): m/z calcd for C29H24NO2: 418.1802 [M+H+]; found:
418.1800.
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(1-C8THI-Me), 4-((1-Methyl-4,5,6,7-tetrahydro-1H-indol-2-yl)octatetraynyl)benzonitrile
According to the general procedure for inverse Sonogashira coupling 1ꢀC8I (0.0105 g, 0.0323
mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0080 g, 0.064 mmol) and K2CO3 (0.140 g)
were used. Time: 24 h, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
(0.0041 g, 0.012 mmol), yield: 37%. 1H NMR (500 MHz, CDCl3) δ 7.64ꢀ7.58 (m, 4H, C6H4),
6.48 (s, 1H, pyrrole), 3.50 (s, 3H, CH3), 2.51 (t, JHH = 6.3 Hz, 2H, CH2), 2.45 (t, JHH = 6.1 Hz,
2H, CH2), 1.86ꢀ1.80 (m, 2H, CH2), 1.74ꢀ1.68 (m, 2H, CH2). 13C NMR (126 MHz, CDCl3) δ
134.7 (NCCH2, pyrrole), 133.6 (CH, C6H4CN), 132.3 (CH, C6H4CN), 126.1 (CArC≡C), 119.0
(CTHIC≡C), 118.9 (CH, pyrrole), 118.2 (C≡N), 113.0 (CC≡N), 111.6 (CHCCH2, pyrrole), 81.2
(C≡C), 78.8 (C≡C), 76.5 (C6H4C≡C), 72.5 (C≡C), 71.2 (C≡C), 70.0 (C≡C), 66.1 (C≡C), 65.3
(C≡C), 31.3 (CH3), 23.4 (CH2), 23.0 (CH2), 22.9 (CH2), 22.7 (CH2). IR (fluorinated oil mull)
2223 (N≡C), 2188 (C≡C), 2153 (C≡C), 2102 (C≡C) cm−1. HRMS(ESI): m/z calcd for
C24H17N2: 333.1386 [M+H+]; found: 333.1391.
(1-C8THI-Vin), 4-((1-Vinyl-4,5,6,7-tetrahydro-1H-indol-2-yl)octatetraynyl)benzonitrile
According to the general procedure for inverse Sonogashira coupling 1ꢀC8I (0.0114 g, 0.0351
mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0103 g, 0.070 mmol) and K2CO3 (0.210 g)
were used. Time: 2 d, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0047 g, 0.014 mmol), yield: 40%. H NMR (500 MHz, CDCl3) δ 7.64ꢀ7.58 (m, 4H,
C6H4CN), 6.88 (dd, JHH = 16.0, 9.3 Hz, 1H, CH=CH2), 6.57 (s, 1H, pyrrole), 5.39 (dd, JHH
=
16.0, 1.2 Hz, 1H, CH=CH2), 4.94 (dd, JHH = 9.3, 1.2 Hz, 1H, CH=CH2), 2.63 (t, JHH = 6.2 Hz,
2H, CH2), 2.46 (t, JHH = 6.1 Hz, 2H, CH2), 1.86ꢀ1.79 (m, 2H, CH2), 1.75ꢀ1.69 (m, 2H, CH2).
13C NMR (126 MHz, CDCl3) δ 134.0 (NCCH2, pyrrole), 133.6 (CH from C5H4CN), 132.3
(CH from C5H4CN), 130.0 (CH=CH2), 126.0 (CArC≡C), 121.9 (CH, pyrrole), 120.7
(CTHIC≡C), 118.2 (C≡N), 113.1 (CC≡N), 111.0 (CHCCH2, pyrrole), 104.1 (CH=CH2), 81.2
(C≡C), 78.8 (C≡C), 76.4 (C6H4C≡C), 71.2 (CTHIC≡C), 71.0 (C≡C), 69.8 (C≡C), 65.8 (C≡C),
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C25H17N2: 345.1386 [M+H+]; found: 345.1391.
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According to the general procedure for inverse Sonogashira coupling 1ꢀC8I (0.0140 g, 0.043
mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0182 g, 0.086 mmol) and K2CO3 (0.320 g)
were used. Time: 1 d, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0140 g, 0.034 mmol), yield: 79%. H NMR (500 MHz, CDCl3) δ 7.63ꢀ7.57 (m, 4H,
C6H4C≡N), 7.34ꢀ7.30 (m, H, 2H, C6H5), 7.28ꢀ7.24 (m, 1H, C6H5), 7.07ꢀ7.02 (m, H, 2H,
C6H5), 6.56 (s, 1H, CH, pyrrole), 5.09 (s, 2H, CH2Ph), 2.47 (t, JHH = 6.0 Hz, 2H, CH2), 2.39
(t, JHH = 6.2 Hz, 2H CH2), 1.78ꢀ1.72 (m, 2H CH2), 1.72ꢀ1.65 (m, 2H, CH2). 13C NMR (126
MHz, CDCl3) δ 137.5 (ipso from C6H5), 134.7 (NCCH2, pyrrole), 133.6 (CH from C5H4CN),
132.3 (CH from C5H4CN), 128.9 (CH, C6H5), 127.7 (CH, ortho from C6H5), 126.8 (CH,
C6H5), 126.1 (CArC≡C), 119.6 (CTHIC≡C), 119.5 (CH, pyrrole), 118.2 (C≡N), 113.0 (CC≡N),
111.9 (CHCCH2, pyrrole), 81.2 (C≡C), 78.8 (C≡C), 76.5 (C≡C), 72.4 (C≡C), 71.2 (C≡C),
69.9 (C≡C), 66.1 (C≡C), 65.3 (C≡C), 48.5 (CH2Ph), 23.3 (CH2), 23.1 (CH2), 22.9 (CH2), 22.8
(CH2). HRMS(ESI): m/z calcd for C30H21N2: 409.1699 [M+H+]; found: 409.1705.
(2-C8THI-Me), 1-Methyl-2-((4-nitrophenyl)octatetraynyl)-4,5,6,7-tetrahydro-1H-indole
According to the general procedure for inverse Sonogashira coupling 2ꢀC8I (0.0085 g, 0.025
mmol), 1ꢀmethylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0067 g, 0.050 mmol) and K2CO3 (0.150 g)
were used. Time: 1 d, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
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(0.0080 g, 0.023 mmol), yield: 92%. H NMR (500 MHz, CDCl3) δ 8.23ꢀ8.18 (m, 2H,
C6H4NO2), 7.69ꢀ7.64 (m, 2H, C6H4NO2), 6.49 (s, 1H, pyrrole), 3.51 (s, 3H, CH3), 2.52 (t, JHH
= 6.3 Hz, 2H), 2.46 (t, JHH = 6.1 Hz, 2H), 1.86ꢀ1.80 (m, 2H), 1.75ꢀ1.68 (m, 2H). 13C NMR
(126 MHz, CDCl3) δ 147.9 (CNO2), 134.8 (NCCH2, pyrrole), 133.9 (CH from C6H4), 128.1
(CArC≡C), 123.9 (CH from C6H4), 119.1 (CTHIC≡C), 119.0 (CH, pyrrole), 111.6 (CHCCH2,
pyrrole), 81.3 (C≡C), 79.6 (C≡C), 76.3 (C6H4C≡C), 72.7 (CTHIC≡C), 71.2 (C≡C), 70.4 (C≡C),
66.4 (C≡C), 65.3 (C≡C), 31.3 (CH3), 23.4 (CH2), 23.0 (CH2), 22.9 (CH2), 22.7 (CH2).
HRMS(ESI): m/z calcd for C23H17N2O2: 353.1285 [M+H+]; found: 353.1282.
(2-C8THI-Vin), 2-((4-Nitrophenyl)octatetraynyl)-1-vinyl-4,5,6,7-tetrahydro-1H-indole
According to the general procedure for inverse Sonogashira coupling 2ꢀC8I (0.0074 g, 0.021
mmol), 1ꢀvinylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.0063 g, 0.042 mmol) and K2CO3 (0.140 g)
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were used. Time: 1 d, purification: short silica gel plug (hexane/DCM, v/v, 1/1), yellow solid
(0.0026 g, 0.0071 mmol), yield: 34%. 1H NMR (500 MHz, CDCl3) δ 8.22ꢀ8.19 (m, 2H), 7.69ꢀ
7.65 (m, 2H), 6.88 (dd, JHH = 16.0, 9.3 Hz, 1H), 6.58 (s, 1H), 5.40 (dd, JHH = 16.0, 1.2 Hz,
1H), 4.94 (dd, JHH = 9.3, 1.2 Hz, 1H), 2.64 (t, JHH = 6.2 Hz, 2H), 2.47 (t, JHH = 6.1 Hz, 2H),
1.86ꢀ1.79 (m, 2H), 1.77ꢀ1.69 (m, 2H) 13C NMR (151 MHz, CDCl3) δ 147.9 (CNO2), 134.2
(NCCH2 of pyrrole), 133.9 (CH of C6H4), 130.0 (HC=CH2), 128.0 (CArC≡C), 123.9 (CH of
C6H4), 121.9 (CH of pyrrole), 120.7 (CC≡C of pyrrole), 111.0 (CHCCH2 of pyrrole), 104.1
(HC=CH2), 81.2 (C≡C), 79.5 (C≡C), 76.2 (C6H4C≡C), 72.2 (pyrroleC≡C), 71.0 (C≡C), 70.3
(C≡C), 66.1 (C≡C), 65.1 (C≡C), 24.2 (CH2), 23.1 (CH2), 23.0 (CH2), 23.0 (CH2).
HRMS(ESI): m/z calcd for C24H17N2O2: 365.1285 [M+H+]; found: 365.1279.
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(2-C8THI-Bn), 1-Benzyl-2-((4-nitrophenyl)octatetraynyl)-4,5,6,7-tetrahydro-1H-indole
According to the general procedure for inverse Sonogashira coupling 2ꢀC8I (0.0095 g, 0.028
mmol), 1ꢀbenzylꢀ4,5,6,7ꢀtetrahydroꢀ1Hꢀindole (0.012 g, 0.056 mmol) and K2CO3 (0.220 g)
were used. Time: 1 d, purification: short silica gel plug (hexane/DCM, v/v, 1/1), red solid
(0.0055 g, 0.013 mmol), yield: 46%. 1H NMR (500 MHz, CDCl3) δ 8.21ꢀ8.18 (m, 2H, C6H4),
7.67ꢀ7.64 (m, 2H, C6H4), 7.34ꢀ7.30 (m, 2H, C6H5), 7.29ꢀ7.24 (m, 1H, C6H5), 7.07ꢀ7.24 (m,
2H, C6H5), 6.57 (s, 1H, CH, pyrrole), 5.09 (s, 2H, CH2Ph), 2.48 (t, JHH = 6.0 Hz, 2H, CH2),
2.40 (t, JHH = 6.1 Hz, 2H, CH2), 1.78ꢀ1.72 (m, 2H, CH2), 1.72ꢀ1.65 (m, 2H, CH2). 13C NMR
(126 MHz, CDCl3) δ 147.9 (CNO2), 137.5 (ipso from C6H5), 134.8 (NCCH2, pyrrole), 133.9
(CH from C6H4), 128.9 (CH, C6H5), 128.1 (CArC≡C), 127.7 (CH, C6H5), 126.8 (CH, C6H5),
123.9 (CH from C6H4), 119.7 (CTHIC≡C), 119.6 (CH, pyrrole), 111.8 (CHCCH2, pyrrole),
81.2 (C≡C), 79.6 (C≡C), 76.3 (C6H4C≡C), 72.6 (CTHIC≡C), 71.2 (C≡C), 70.4 (C≡C), 66.3
(C≡C), 65.2 (C≡C), 48.5 (CH2Ph), 23.3 (CH2), 23.1 (CH2), 22.9 (CH2), 22.8 (CH2).
HRMS(ESI): m/z calcd for C29H21N2O2: 429.1598 [M+H+]; found: 429.1602.
AUTHOR INFORMATION
Corresponding Author: slawomir.szafert.@chem.uni.wroc.pl
ACKNOWLEDGMENTS
The work was supported by the National Science Centre Poland (UMOꢀ
2013/08/M/ST5/00942).
ASSOCIATED CONTENT
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The Supporting Information is available free of charge on the ACS. 1H and 13C NMR spectra
for all new compounds, UVꢀVis spectra and cif files for 1ꢀC6THIꢀMe, 2ꢀC6THIꢀVin, 2ꢀ
C6THIꢀBn, 3ꢀC6THIꢀVin, 4ꢀC6THIꢀBn and 2ꢀC8THIꢀVin.
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