Ruthenium-catalyzed synthesis of highly substituted pyrroles from 1-vinylpropargyl alcohols and amines

Article abstract of DOI:10.1002/ejoc.201300803

Ruthenium-catalyzed atom-economic transformations of 1-vinylpropargyl alcohols with amines leading to highly substituted pyrroles in a one-pot cascade process are reported. The allylation/cycloisomerization sequence is catalyzed by a single ruthenium(0) complex that contains a redox-coupled dienone ligand and can be extended by an additional [3,3] rearrangement. The environmentally benign reactions allow the metal-catalyzed conversion of inexpensive and readily accessible materials to highly functionalized pyrroles with water as the only waste product. Ruthenium-catalyzed atom-economic transformations of 1-vinylpropargyl alcohols with primary amines leading to highly substituted pyrroles in a one-pot cascade process are reported. The allylation/ cycloisomerization cascade reaction generates water as the only waste product and the sequence can be extended by an additional [3,3] rearrangement by using secondary allylamines. Copyright

Full text of DOI:10.1002/ejoc.201300803

FULL PAPER
DOI: 10.1002/ejoc.201300803
Ruthenium-Catalyzed Synthesis of Highly Substituted Pyrroles from
1-Vinylpropargyl Alcohols and Amines
Nora Thies,[a] Martin Gerlach,[a] and Edgar Haak*[a]
Keywords: Synthetic methods / Homogeneous catalysis / Ruthenium / Nitrogen heterocycles / Cooperative effects
Ruthenium-catalyzed atom-economic transformations of 1-
vinylpropargyl alcohols with amines leading to highly substi-
tuted pyrroles in a one-pot cascade process are reported. The
allylation/cycloisomerization sequence is catalyzed by a sin-
gle ruthenium(0) complex that contains a redox-coupled di-
enone ligand and can be extended by an additional [3,3] re-
arrangement. The environmentally benign reactions allow
the metal-catalyzed conversion of inexpensive and readily
accessible materials to highly functionalized pyrroles with
water as the only waste product.
Introduction
Results and Discussion
Recently we discovered that ruthenium cyclopenta-
dienone complexes like 1 catalyze the allylation/cyclo-
isomerization of heteroaromatics or 1,3-dicarbonyl com-
pounds with 1-en-4-yn-3-ols 2, readily available from α,β-
unsaturated ketones (Scheme 1).[9a,9b]
Clean and sustainable organic synthesis requires atom-
economic catalytic processes to obtain important core
structures from readily and widely accessible starting mate-
rials.[1] In this context, ruthenium-catalyzed transforma-
tions of various unsaturated compounds, in particular, have
been reported.[2] Because the pyrrole core is an important
heteroaromatic system found in many natural products,[3]
drugs[4] and functional materials,[5] several metal-catalyzed
methods have been developed for its synthesis.[6,7] These
catalytic processes include carbonylation reactions,[6d,6o] the
rearrangement of diazo compounds,[6e,6h] the activation of
C–H bonds,[6f,6i–6k] redox isomerization[6r] and cycloisomer-
ization processes[6a–6c,6g,6l–6n,6p,6q,6s–6x] or the “borrowing-
hydrogen” method.[7] Metal-free multi-component reactions
for flexible pyrrole synthesis from easily accessible sub-
strates have also been developed.[6c,8] The most effective
methods for the metal-catalyzed conversion of inexpensive
and readily accessible materials to highly functionalized
pyrroles in one pot are based on the “borrowing-hydrogen”
strategy,[7] many other synthetic protocols requiring mul-
tiple steps or pre-functionalized substrates. Nevertheless, al-
ternatives to these generally superior methods are required
in several cases. Herein, we report a ruthenium-catalyzed
synthesis of highly substituted pyrroles directly from aro-
matic or aliphatic amines and various 1-en-4-yn-3-ols as an
Scheme 1. Transformations of 1-en-4-yn-3-ols 2 catalyzed by com-
plex 1.
We envisioned that highly substituted pyrroles could be
extension of our previous work on ruthenium-catalyzed accessible in a related cascade transformation of 1-en-4-yn-
transformations of propargyl alcohols (Scheme 1).[9]
3-ols with primary amines (Scheme 1). The first attempts to
convert 3-methylpent-1-en-4-yn-3-ol (2a) with amines 3 into
pyrroles in the presence of catalyst 1 and a catalytic amount
of trifluoroacetic acid (TFA) as co-catalyst yielded only
traces of the desired pyrroles 4. At 100 °C, aniline barely
reacted, whereas the more nucleophilic benzylamine formed
the corresponding imine by Markovnikov addition as the
major product (Scheme 2).
[a] Institut für Chemie, Otto-von-Guericke-Universität
Magdeburg,
Universitätsplatz 2, 39106 Magdeburg, Germany
E-mail: edgar.haak@ovgu.de
www.ich.ovgu.de
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300803.
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Eur. J. Org. Chem. 2013, 7354–7365

Substituted Pyrroles from 1-Vinylpropargyl Alcohols and Amines
Scheme 2. Conversion of 2a with aniline or benzylamine.
Moderate yields of substituted pyrroles 4 were obtained
from amines 3 containing an additional coordinating group
or at higher temperatures under microwave conditions
(Scheme 3). The pyrroles were accompanied by unconverted
starting materials and small amounts of the corresponding
imines (see Scheme 2) as the sole detectable byproducts.
Scheme 4. Formation of pyrroles from higher substituted enynols.
[a] The reaction was stopped after 6 h, unconverted starting materi-
als were recovered.
activated enynols or more basic amines. In general, no
transformation was observed in the absence of catalyst 1,
whereas lower yields were obtained in the absence of the
co-catalyst TFA.
Extension of the catalytic cascade transformation by a
[3,3] rearrangement allowed the functionalization of the 2-
methyl group of the initially formed pyrroles (Scheme 7).
This sequence is limited to basic secondary allylamines.
Pyrroles formed from primary allylamines did not re-
arrange (see 6p, Scheme 5) and pyrrole formation from N-
allylanilines was not observed. A related gold-catalyzed
conversion has previously been published.[6p]
In contrast, the allylation of secondary allylamines with
acyclic biallylic propargyl alcohols like 2e was followed by
a [4+2] cycloaddition rather than by a cycloisomerization
process (Scheme 8). The coupling constants in the NMR
spectra of products 10a and 10b indicate that syn cycload-
Scheme 3. Formation of pyrroles from the reaction of 2a with vari-
ous amines. [a] The reaction was stopped after 6 h, unconverted
starting materials were recovered. [b] The reaction time was 48 h
with full conversion of 2a. [c] The amine was generated in situ from
RNH3Cl and Et3N. [d] Racemization took place during the reac-
tion. [e] The reaction was carried out at 200 °C in 5 min by using
microwave irradiation.
A phenyl substituent at the distal end of the double bond dition occurs from the less hindered side with respect to the
led to a slight increase in the reactivity of the alcohol. Con- phenyl substituent at C-1 with the endo isomer formed as
sidering the amine, increasing yields were obtained in the the major product. The assignments were made by com-
3
order anilineϽ p-Ͻ m-Ͻ o-pyrrolylaniline (5aϽ 5gϽ 5dϽ parison of the J(H,H) coupling constants with the corre-
5b). This shows that the reactivity of the amine depends on sponding dihedral H–C–C–H angles generated from en-
coordinative rather than electronic effects (Scheme 4).
ergy-minimized models (MM2 force field) and were con-
Enhanced yields were obtained with biallylic substrates firmed by NOESY experiments (see the Supporting Infor-
2e,f derived from dibenzylidene ketones due to their in- mation).
creased electrophilicity (Scheme 5).
Similar cycloaddition products were obtained from N-
In the case of aniline as the amine component, smaller propargylanilines or sterically hindered primary proparg-
amounts of pyrroles were obtained from substrates 2e or ylamines. In contrast, N-propargylbenzylamine led to pyr-
2f in the absence of the ruthenium catalyst under acidic role 6j and N,N-dipropargylbenzylamine by propargyl sub-
conditions. In this case, the pyrroles were accompanied by stitution (Scheme 9).
ortho- and para-allylated anilines, which were not formed in
Tertiary enynols containing internal alkyne moieties all-
the presence of the catalyst (Scheme 6). This spontaneous ylated the nucleophile and led selectively to (Z)-enynes
allylation/cyclization reaction was not observed with less (Scheme 10). Subsequent cycloisomerization was not ob-
Eur. J. Org. Chem. 2013, 7354–7365
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N. Thies, M. Gerlach, E. Haak
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Scheme 6. Spontaneous allylation/cyclization reaction.
Scheme 7. Allylation/cyclization/rearrangement sequence. [a] The
reaction was stopped after 6 h, unconverted starting materials were
recovered. [b] Side-product, see Scheme 8.
Scheme 8. Allylation/cycloaddition sequence of biallylic propargyl
alcohol 2e with allylamines.
served under standard conditions. As a consequence, all ac-
cessible pyrroles are methyl-substituted at C-2 with the ex-
ception of the rearranged products 9. Secondary enynols
were not transformed at 100 °C. At higher temperatures
under microwave conditions enynes 11 were formed ac-
companied by small amounts of pyrroles from enynols con-
taining an internal alkyne moiety. In addition, secondary
substrates propargylated the nucleophile, whereas tertiary
derivatives formed Diels–Alder adducts after initial dehy-
dration (Scheme 10).
Scheme 5. Formation of pyrroles from biallylic substrates. [a] The
reaction was stopped after 6 h, unconverted starting materials were
recovered. [b] Side-product. [c] The reaction was carried out at
200 °C for 5 min under microwave irradiation. [d] The amine was
generated in situ from RNH3Cl and Et3N. [e] Racemization took
place during the reaction.
This reported pyrrole formation was not observed by
using different ruthenium catalysts such as [Ru3(CO)12],
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Eur. J. Org. Chem. 2013, 7354–7365

Substituted Pyrroles from 1-Vinylpropargyl Alcohols and Amines
enynes (Scheme 11). Related gold-catalyzed conversions of
1-en-4-yn-3-ols have previously been published.[6n,11a,11b]
Internal substrates are not further converted under stan-
dard conditions. The chelating substrate coordination in A,
which involves the basic coordination site of the electroni-
cally coupled ligand, is crucial for this initial transforma-
tion. Derivatives containing weaker hydrogen-bond ac-
ceptors like 14a–c remain inactive. In the case of terminal
substrates, the resulting π complex B is in equilibrium with
alkynyl species C and vinylidene complex D. Similar equi-
libria have been reported previously.[2,9b,11c] The subsequent
cyclization leads to alkenyl complex E and may be derived
from π complex B or from alkynyl species C by intramolec-
ular protonation of the triple bond. A formal 1,5-hydrogen
shift followed by reductive elimination of the product from
complex F regenerated the active catalytic species. The anal-
ogous transformation of secondary allylamines leads to
zwitterionic complex EЈ, which forms FЈ in a formal [3,3]
rearrangement sequence. Enyne complex BЈ, derived from
alcohol 2e and secondary allyl- or propargylamines, forms
Scheme 9. Allylation/cycloaddition sequence with propargylamines.
the
corresponding
Diels–Alder
product
instead
(Scheme 11). The use of an acidic additive is not crucial but
accelerates the reaction. This effect may result from proton-
Scheme 10. Conversion of internal substrates. [a] The reaction was
stopped after 6 h, unconverted starting materials were recovered.
[b] The rreaction was carried out at 200 °C for 5 min by using mi-
crowave irradiation.
[CpRuCl(PPh3)2], [RuCl2(PPh3)3], the tetracyclone complex
14a,[9e,10a] its methyl derivative 14b[9e] or the ethylated com-
plex 14c[10b] (Figure 1).
Figure 1. Inactive complex derivatives 14a–c.
In agreement with our previously reported studies,[9a,9b]
we assumed that the initially formed π complex A leads to
the allylation of the nucleophile to yield the corresponding Scheme 11. Proposed mechanisms.
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N. Thies, M. Gerlach, E. Haak
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921 (m), 870 (m), 828 (m), 764 (m), 727 (s), 703 (s), 659 (m), 636
(s) cm–1. HRMS: calcd. for C16H16N2 236.1313 [M]+; found
236.1314.
ation of the ligand’s carbonyl group in A, thereby increasing
the electrophilicity of the ruthenium centre and promoting
the dehydration step.
Methyl 2-(2,3-Dimethyl-1H-pyrrol-1-yl)benzoate (4b): 1H NMR
(600 MHz, CDCl3): δ = 1.94 (s, 3 H), 2.10 (s, 3 H), 3.71 (s, 3 H),
6.08 (d, J = 2.4 Hz, 1 H), 6.56 (d, J = 2.4 Hz, 1 H), 7.32 (dd, J =
8.4, 0.9 Hz, 1 H), 7.46 (td, J = 7.8, 1.2 Hz, 1 H), 7.58 (td, J =
7.2, 1.8 Hz, 1 H), 7.90 (dd, J = 7.8, 1.2 Hz, 1 H) ppm. 13C NMR
(150 MHz, CDCl3): δ = 10.0 (CH3), 11.6 (CH3), 52.4 (CH3), 109.9
(CH), 115.3 (C), 120.2 (CH), 126.3 (C), 127.7 (CH), 129.3 (CH),
129.8 (C), 130.6 (CH), 132.3 (CH), 140.1 (C), 166.8 (C) ppm. MS
(EI): m/z (%) = 229 (100) [M]+, 228 (62), 214 (28), 170 (25), 154
(26). HRMS: calcd. for C14H15NO2 229.1103 [M]+; found
229.1104.
Conclusions
We have described the ruthenium-catalyzed reactions of
1-en-4-yn-3-ols with primary amines to yield substituted
pyrroles in an allylation/cycloisomerization cascade process
with water as the only waste product. The sequence can
be extended by a [3,3] rearrangement by using secondary
allylamines. A different reaction pathway takes place with
acyclic biallylic propargyl alcohols and propargyl or sec-
ondary allylamines. In this case, Diels–Alder adducts are
obtained from the initially formed 1,3-dienes. The presented
transformations depend on the basic coordination site of
the electronically coupled cyclopentadienone ligand in 1.
Analogous ruthenium complexes containing weaker hydro-
gen-bond acceptors were catalytically inactive in this trans-
formation. Further investigations with particular regard to
detailed reaction mechanisms and applications in drug syn-
thesis are currently under investigation.
[2-(2,3-Dimethyl-1H-pyrrol-1-yl)phenyl]methanol (4c): 1H NMR
(400 MHz, CDCl3): δ = 1.83 (s, 3 H), 2.01 (s, 3 H), 4.32 (s, 2 H),
6.02 (d, J = 2.8 Hz, 1 H), 6.49 (d, J = 2.8 Hz, 1 H), 7.13 (dd, J =
7.6, 1.2 Hz, 1 H), 7.29 (td, J = 7.6, 1.6 Hz, 1 H), 7.36 (td, J =
7.6, 1.6 Hz, 1 H), 7.49 (dd, J = 7.6, 1.2 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 10.0 (CH3), 11.6 (CH3), 61.6 (CH2), 109.9
(CH), 115.4 (C), 120.2 (CH), 126.2 (C), 128.3 (CH), 128.5 (CH),
128.6 (CH), 128.7 (CH), 138.7 (C), 138.8 (C) ppm. IR: ν = 3366
˜
(s), 3067 (m), 3009 (m), 2925 (s), 2858 (s), 1680 (s), 1606 (s), 1590
(s), 1495 (s), 1458 (s), 1378 (s), 1349 (s), 1314 (m), 1260 (m), 947
(w), 928 (w), 849 (w), 755 (s), 667 (m), 639 (m) cm–1. MS (EI): m/z
(%) = 201 (80) [M]+, 200 (60), 184 (76), 169 (100), 168 (61). HRMS:
calcd. for C13H15NO 201.1154 [M]+; found 201.1152.
Experimental Section
1-Benzhydryl-2,3-dimethyl-1H-pyrrole (4d): 1H NMR (600 MHz,
CDCl3): δ = 2.08 (s, 6 H), 5.96 (br. s, 1 H), 6.20 (br. s, 1 H), 6.43
(br. s, 1 H), 7.05 (d, J = 7.4 Hz, 4 H), 7.31 (t, J = 7.2 Hz, 2 H), 7.34
(t, J = 7.2 Hz, 4 H) ppm. 13C NMR (150 MHz, DEPT, CDCl3): δ
= 9.9 (CH3), 11.6 (CH3), 64.0 (CH), 108.3 (CH), 115.4 (C), 118.3
(CH), 125.7 (C), 127.7 (CH), 128.5 (CH), 128.6 (CH), 140.7
General: All reactions were carried out under dry argon using stan-
dard Schlenk techniques. Chemicals were dried and purified ac-
cording to common procedures. Products were identified by spec-
troscopic analysis (1H and 13C NMR, IR, MS, HRMS). Multi-
plicity was determined by DEPT spectra for all compounds. Corre-
lations and assignments were determined by 1H-1H COSY, HSQC,
HMBC and 1H-1H NOESY spectra if necessary. IR spectra were
obtained with a Perkin–Elmer FT-IR 2000 spectrometer. NMR
spectra were recorded with a Bruker DPX 400 or Avance 600 spec-
trometer. MS and HRMS data were obtained with a Finnigan
MAT 95 spectrometer. Reactions using microwave irradiation were
performed in an Anton Paar Monowave 300 reactor. Catalyst 1 has
previously been published in ref.[9e] and its crystal structure in
ref.[9b]
(C) ppm. IR: ν = 3088 (w), 3063 (m), 3029 (m), 2991 (m), 2919 (s),
˜
2861 (m), 1705 (w), 1603 (m), 1585 (w), 1528 (w), 1496 (s), 1481
(m), 1450 (s), 1387 (m), 1314 (s), 1279 (w), 1216 (s), 869 (w), 833
(w), 753 (s), 734 (s), 699 (s), 667 (m) cm–1. MS (EI): m/z (%) = 261
(30) [M]+, 167 (100), 165 (27), 152 (16). HRMS: calcd. for C19H19N
261.1517 [M]+; found 261.1518.
Methyl 2-(2,3-Dimethyl-1H-pyrrol-1-yl)propanoate (4e): The amine
was generated in situ from l-alanine methyl ester and Et3N
(1 equiv.). Polarimetric analysis and 1H NMR experiments in the
presence of a chiral shift reagent (Eu[tfc]3, 1.1 equiv.) revealed that
the product was racemic. 1H NMR (400 MHz, CDCl3): δ = 1.33
(d, J = 7.3 Hz, 3 H), 1.66 (s, 3 H), 1.74 (s, 3 H), 3.38 (s, 3 H), 4.40
(q, J = 7.3 Hz, 1 H), 5.61 (d, J = 2.9 Hz, 1 H), 6.28 (d, J = 2.9 Hz,
1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 8.9 (CH3), 10.9
(CH3), 17.4 (CH3), 52.0 (CH), 53.0 (CH3), 108.6 (CH), 114.2 (C),
115.2 (CH), 124.2 (C), 171.5 (C) ppm. HRMS: calcd. for
C10H15NO2 181.1103 [M]+; found 181.1103.
General Catalytic Procedure: Catalyst 1 (0.02 mmol) was dissolved
in toluene (1 mL) and TFA diluted in toluene (0.02 mmol, 1 m), the
propargyl alcohol (1 mmol) and amine (1 mmol) were subsequently
added. The mixture was stirred at 100 °C for 6 h under argon (stan-
dard conditions) or heated at 200 °C for 5 min by using microwave
irradiation (microwave conditions). Evaporation of the solvent and
flash chromatography on silica gel furnished the purified products
as colourless or yellow oils or foams.
Characterization Data of Catalysis Products
2,3-Dimethyl-1-phenyl-1H-pyrrole (4f): 1H NMR (400 MHz,
CDCl3): δ = 2.00 (s, 3 H), 2.02 (s, 3 H), 5.99 (d, J = 2.8 Hz, 1
H), 6.60 (d, J = 2.8 Hz, 1 H), 7.17–7.34 (m, 5 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 10.6 (CH3), 11.5 (CH3), 109.8 (CH), 116.2
(C), 119.8 (CH), 125.2 (C), 125.6 (CH), 126.5 (CH), 129.0 (CH),
140.7 (C) ppm. HRMS: calcd. for C12H13N 171.1048 [M]+; found
171.1048.
2,3-Dimethyl-1-[2-(1H-pyrrol-1-yl)phenyl]-1H-pyrrole
(4a):
1H
NMR (400 MHz, CDCl3): δ = 1.68 (s, 3 H), 2.02 (s, 3 H), 6.09 (d,
J = 2.6 Hz, 1 H), 6.19 (t, J = 1.9 Hz, 2 H), 6.48 (t, J = 1.9 Hz, 2
H), 6.52 (d, J = 2.7 Hz, 1 H), 7.35–7.37 (m, 2 H), 7.45–7.47 (m, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 9.1 (CH3), 11.4 (CH3),
110.0 (CH), 110.6 (CH), 115.5 (C), 119.4 (CH), 120.4 (CH), 124.9
(CH), 126.3 (C), 126.4 (CH), 128.6 (CH), 129.6 (CH), 133.3 (C),
137.6 (C) ppm. IR: ν = 3102 (m), 3070 (m), 2921 (s), 2860 (s), 1737
2,3-Dimethyl-1-(4-nitrophenyl)-1H-pyrrole
(4g):
1H
NMR
˜
(m), 1602 (s), 1587 (m), 1511 (s), 1483 (s), 1387 (m), 1351 (s), 1333 (400 MHz, CDCl3): δ = 2.02 (s, 3 H), 2.13 (s, 3 H), 6.09 (d, J =
(s), 1265 (m), 1245 (m), 1229 (m), 1180 (s), 1160 (m), 1142 (m), 2.9 Hz, 1 H), 6.67 (d, J = 2.9 Hz, 1 H), 7.35 (d, J = 9.1 Hz, 2 H),
1125 (m), 1105 (s), 1069 (s), 1044 (m), 1015 (s), 986 (m), 946 (m), 8.23 (d, J = 9.1 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
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Substituted Pyrroles from 1-Vinylpropargyl Alcohols and Amines
10.9 (CH3), 11.4 (CH3), 111.9 (CH), 118.6 (C), 119.6 (CH), 124.8
(CH), 128.4 (CH), 128.7 (CH), 129.1 (CH), 133.1 (C), 139.5
(CH), 124.8 (CH), 124.8 (C), 145.3 (C), 145.9 (C) ppm. HRMS: (C) ppm. IR: ν = 3060 (m), 3034 (m), 2923 (s), 2853 (m), 2834 (m),
˜
calcd. for C12H12N2O2 216.0899 [M]+; found 216.0898.
2,3-Dimethyl-1,5-diphenyl-1H-pyrrole
(5a):[12a] 1H
1689 (m), 1657 (m), 1598 (s), 1523 (m), 1497 (s), 1442 (s), 1427 (m),
1372 (s), 1341 (m), 1329 (m), 1242 (m), 1156 (m), 1075 (m), 1029
(m), 910 (m), 756 (s), 731 (m), 699 (s), 646 (m) cm–1. HRMS: calcd.
for C21H21N 287.1674 [M]+; found 287.1674.
NMR
(400 MHz, CDCl3): δ = 1.98 (s, 3 H), 2.06 (s, 3 H), 6.19 (s, 1 H),
6.97–7.27 (m, 10 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.9
(CH3), 11.3 (CH3), 110.6 (CH), 115.6 (C), 125.4 (CH), 126.0 (C), 1-Benzyl-2,3-dimethyl-5-phenyl-1H-pyrrole
126.5 (CH), 127.6 (CH), 127.9 (CH), 128.4 (CH), 128.9 (CH), 131.7 (400 MHz, CDCl3): δ = 2.02 (s, 3 H), 2.08 (s, 3 H), 5.08 (s, 2 H),
(C), 133.4 (C), 139.7 (C) ppm. IR: ν = 3059 (m), 3026 (m), 2925 6.10 (s, 1 H), 6.92 (d, J = 7.5 Hz, 2 H), 7.20–7.29 (m, 8 H) ppm.
(s), 2856 (m), 1667 (m), 1599 (s), 1495 (s), 1379 (m), 1369 (m), 1261 13C NMR (100 MHz, CDCl3): δ = 10.1 (CH3), 11.3 (CH3), 47.8
(5f):
1H
NMR
˜
(m), 1155 (m), 1073 (m), 1029 (m), 968 (w), 757 (s), 697 (s) cm–1.
MS (EI): m/z (%) = 247 (100) [M]+, 246 (52), 205 (19), 154 (20),
144 (29), 129 (54), 128 (35), 105 (30). HRMS: calcd. for C18H17N
247.1361 [M]+; found 247.1361.
(CH2), 109.7 (CH), 115.3 (C), 125.7 (CH), 126.4 (CH), 126.6 (C),
126.9 (CH), 128.3 (CH), 128.5 (CH), 128.7 (CH), 133.3 (C), 133.7
(C), 139.2 (C) ppm. IR: ν = 3059 (m), 3031 (m), 2914 (s), 2862 (s),
˜
1768 (m), 1734 (m), 1649 (m), 1599 (s), 1510 (s), 1495 (s), 1471 (s),
1452 (s), 1395 (s), 1342 (s), 1180 (m), 1158 (m), 1073 (m), 1027 (m),
968 (m), 803 (m), 814 (m), 762 (s), 744 (s), 721 (s), 700 (s) cm–1.
MS (EI): m/z (%) = 261 (83) [M]+, 170 (100), 128 (7). HRMS:
calcd. for C19H19N 261.1517 [M]+; found 261.1517.
2,3-Dimethyl-5-phenyl-1-[2-(1H-pyrrol-1-yl)phenyl]-1H-pyrrole (5b):
1H NMR (400 MHz, CDCl3): δ = 1.93 (s, 3 H), 2.13 (s, 3 H), 6.13
(t, J = 2.1 Hz, 2 H), 6.23 (s, 1 H), 6.28 (t, J = 2.1 Hz, 2 H), 6.88–
6.90 (m, 2 H), 7.06–7.10 (m, 3 H), 7.33 (ddd, J = 7.9, 6.7, 1.5 Hz,
1 H), 7.36–7.40 (m, 2 H), 7.46 (ddd, J = 8.1, 6.8, 2.0 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 10.1 (CH3), 11.3 (CH3), 109.8
2,3-Dimethyl-5-phenyl-1-[4-(1H-pyrrol-1-yl)phenyl]-1H-pyrrole (5g):
1H NMR (400 MHz, CDCl3): δ = 2.11 (s, 3 H), 2.17 (s, 3 H), 6.29
(CH), 110.8 (CH), 116.2 (C), 120.2 (CH), 124.9 (CH), 125.6 (CH), (br. s, 1 H), 6.38 (t, J = 2.2 Hz, 2 H), 7.08–7.22 (m, 9 H), 7.39 (d,
126.3 (CH), 127.1 (CH), 127.4 (C), 127.7 (CH), 128.9 (CH), 131.2
(CH), 132.1 (C), 132.6 (C), 132.7 (C), 138.3 (C) ppm. IR: ν = 3062
J = 8.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.6
(CH3), 11.0 (CH3), 109.1 (CH), 110.6 (CH), 115.6 (C), 118.9 (CH),
˜
(s), 3028 (s), 2920 (s), 2860 (s), 1706 (m), 1603 (s), 1505 (s), 1478 120.1 (CH), 125.0 (C), 125.4 (CH), 127.5 (CH), 127.7 (CH), 129.3
(s), 1455 (s), 1379 (s), 1368 (s), 1333 (s), 1284 (s), 1264 (s), 1182 (s), (CH), 132.7 (C), 133.0 (C), 136.7 (C), 139.1 (C) ppm. IR: ν = 3059
1159 (s), 1107 (s), 1070 (s), 1070 (s), 1045 (s), 1028 (s), 1016 (s), (m), 3028 (m), 2922 (s), 2854 (m), 1712 (s), 1602 (s), 1519 (s), 1494
1000 (s), 966 (s), 946 (s), 921 (s), 909 (s), 871 (m), 794 (s), 760 (s), (s), 1450 (s), 1402 (m), 1380 (s), 1327 (s), 1291 (m), 1259 (m), 1181
˜
726 (s), 696 (s), 649 (s), 635 (s) cm–1. HRMS: calcd. for C22H20N2 (m), 1157 (m), 1118 (m), 1071 (s), 1021 (m), 964 (m), 921 (s), 909
312.1626 [M]+; found 312.1626.
(s), 844 (s), 760 (s), 729 (s), 699 (s) cm–1. HRMS: calcd. for
C22H20N2 312.1626 [M]+; found 312.1626.
3-Ethyl-2,5-dimethyl-1-[2-(1H-pyrrol-1-yl)phenyl]-1H-pyrrole
1
(5c): H NMR (400 MHz, CDCl3): δ = 1.12 (t, J = 7.6 Hz, 3 H), 2-(2,3-Dimethyl-5-phenyl-1H-pyrrol-1-yl)pyridine (5h): 1H NMR
1.74 (s, 3 H), 1.83 (s, 3 H), 2.37 (q, J = 7.6 Hz, 2 H), 5.81 (s, 1 H),
(600 MHz, CDCl3): δ = 2.04 (s, 3 H), 2.07 (s, 3 H), 6.16 (s, 1 H),
6.16 (t, J = 2.1 Hz, 2 H), 6.40 (t, J = 2.1 Hz, 2 H), 7.32–7.34 (m, 6.82 (d, J = 7.8 Hz, 1 H), 6.93 (d, J = 7.4 Hz, 2 H), 7.00 (t, J =
2 H), 7.46–7.48 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 7.2 Hz, 1 H), 7.05 (t, J = 7.4 Hz, 2 H), 7.14 (ddd, J = 7.2, 4.8,
9.8 (CH3), 12.1 (CH3), 15.7 (CH3), 19.3 (CH2), 106.7 (CH), 110.1 1.2 Hz, 1 H), 7.51 (td, J = 7.8, 1.8 Hz, 1 H), 8.51 (dd, J = 4.8,
(CH), 120.3 (CH), 121.8 (C), 123.9 (C), 124.4 (CH), 126.1 (CH), 1.8 Hz, 1 H) ppm. 13C NMR (150 MHz, CDCl3): δ = 11.0 (CH3),
127.3 (C), 129.0 (CH), 131.0 (CH), 138.7 (C), 139.2 (C) ppm. IR:
ν = 3104 (s), 2824 (s), 2854 (s), 1739 (s), 1712 (s), 1605 (s), 1508
˜
11.3 (CH3), 111.9 (CH), 116.5 (C), 122.2 (CH), 123.3 (CH), 125.8
(C), 127.8 (CH), 128.1 (CH), 129.1 (CH), 132.6 (C), 133.6 (C),
(s), 1462 (s), 1377 (s), 1334 (s), 1162 (s), 1107 (s), 1069 (s), 1045 (s),
137.8 (CH), 149.2 (CH), 152.9 (C) ppm. IR: ν = 3059 (m), 3029
˜
1015 (s), 967 (s), 922 (s), 887 (m), 861 (m), 760 (s), 726 (s), 704 (s), (m), 2981 (m), 2926 (m), 1714 (s), 1658 (s), 1635 (s), 1604 (s), 1491
635 (s) cm–1. HRMS: calcd. for C18H20N2 264.1626 [M]+; found
264.1626.
(s), 1470 (s), 1436 (s), 1388 (s), 1359 (s), 1327 (m), 1254 (s), 1182
(m), 1150 (m), 1096 (m), 1073 (m), 1027 (m), 970 (m), 922 (m), 756
(s), 699 (s), 637 (m) cm–1. MS (EI): m/z (%) = 248 (38) [M]+, 221
(20), 157 (59), 146 (75), 145 (60), 131 (100). HRMS: calcd. for
C17H16N2 248.1313 [M]+; found 248.1315.
2,3-Dimethyl-5-phenyl-1-[3-(1H-pyrrol-1-yl)phenyl]-1H-pyrrole (5d):
1H NMR (400 MHz, CDCl3): δ = 2.14 (s, 3 H), 2.18 (s, 3 H), 6.31
(s, 1 H), 6.35 (t, J = 2.2 Hz, 2 H), 6.98 (t, J = 2.2 Hz, 2 H), 7.10–
7.44 (m, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.7 (CH3),
2,3-Dimethyl-5-phenyl-1-[2-(1H-pyrrol-1-yl)benzyl]-1H-pyrrole (5i):
11.0 (CH3), 110.6 (CH), 110.7 (CH), 115.8 (C), 118.8 (CH), 120.0 1H NMR (400 MHz, CDCl3): δ = 1.99 (s, 3 H), 2.11 (s, 3 H), 4.92
(CH), 125.0 (CH), 125.1 (CH), 125.5 (CH), 127.5 (C), 127.5 (CH), (s, 2 H), 6.14 (s, 1 H), 6.33 (t, J = 2.1 Hz, 2 H), 6.71 (t, J = 2.1 Hz,
127.8 (CH), 129.6 (CH), 132.7 (C), 133.0 (C), 140.6 (C), 140.8 2 H), 7.24–7.34 (m, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
(C) ppm. IR: ν = 3059 (m), 3026 (s), 2921 (s), 2853 (s), 1702 (s),
9.6 (CH3), 11.0 (CH3), 43.6 (CH2), 109.1 (CH), 109.7 (CH), 115.2
˜
1604 (s), 1499 (s), 1451 (s), 1379 (s), 1341 (s), 1312 (s), 1258 (s), (C), 121.7 (CH), 126.2 (C), 126.3 (CH), 126.5 (CH), 126.7 (CH),
1167 (s), 1069 (s), 1029 (s), 966 (m), 928 (m), 873 (m), 799 (m), 752 127.3 (CH), 128.1 (CH), 128.2 (CH), 128.3 (CH), 133.1 (C), 133.3
(m), 726 (s), 698 (s) cm–1. HRMS: calcd. for C22H20N2 312.1626 (C), 135.4 (C), 138.3 (C) ppm. IR: ν = 3101 (m), 3062 (s), 3028 (s),
˜
[M]+; found 312.1627.
2921 (s), 2860 (s), 1713 (s), 1639 (s), 1602 (s), 1583 (s), 1500 (s),
1478 (s), 1453 (s), 1396 (s), 1273 (m), 1176 (s), 1158 (s), 1093 (s),
1071 (s), 1044 (m), 1029 (m), 1016 (s), 968 (m), 925 (s), 910 (s), 871
(m), 799 (m), 762 (s), 729 (s), 700 (s), 633 (s) cm–1. HRMS: calcd.
for C23H22N2 326.1783 [M]+; found 326.1782.
1-Methyl-2,3-diphenyl-4,5,6,7-tetrahydro-2H-isoindole (5e): 1H
NMR (600 MHz, CDCl3): δ = 1.88–1.91 (m, 2 H), 1.95–1.98 (m, 2
H), 2.18 (s, 3 H), 2.71 (t, J = 6.0 Hz, 2 H), 2.81 (t, J = 6.0 Hz, 2
H), 7.13 (d, J = 7.6 Hz, 2 H), 7.17 (t, J = 7.4 Hz, 1 H), 7.23 (d, J
= 7.8 Hz, 2 H), 7.26 (t, J = 7.8 Hz, 2 H), 7.36 (t, J = 7.4 Hz, 1 H), 2,3-Dimethyl-1-phenethyl-5-phenyl-1H-pyrrole (5j): 1H NMR
7.42 (t, J = 7.8 Hz, 2 H) ppm. 13C NMR (150 MHz, CDCl3): δ =
10.8 (CH3), 21.8 (CH2), 23.2 (CH2), 24.0 (CH2), 24.3 (CH2), 117.0
(400 MHz, CDCl3): δ = 1.97 (s, 3 H), 2.08 (s, 3 H), 2.65 (t, J =
8.0 Hz, 2 H), 3.94 (t, J = 8.0 Hz, 2 H), 5.90 (s, 1 H), 6.84 (d, J =
(C), 119.0 (C), 125.1 (CH), 125.3 (C), 126.6 (CH), 127.5 (C), 127.6 7.8 Hz, 2 H), 7.07–7.27 (m, 8 H) ppm. 13C NMR (100 MHz,
Eur. J. Org. Chem. 2013, 7354–7365
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7359

N. Thies, M. Gerlach, E. Haak
FULL PAPER
CDCl3): δ = 10.0 (CH3), 11.2 (CH3), 37.7 (CH2), 45.9 (CH2), 109.8 (32), 260 (16), 167 (13), 129 (58), 112 (18). HRMS: calcd. for
(CH), 114.9 (C), 125.9 (C), 126.4 (CH), 126.6 (CH), 128.3 (CH), C25H20BrN 413.0779 [M]+; found 413.0780.
128.4 (CH), 128.6 (CH), 129.0 (CH), 132.5 (C), 134.2 (C), 138.4
(E)-2-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)pyridine (6e): 1H
(C) ppm. IR: ν = 3062 (m), 3026 (s), 2919 (s), 2861 (s), 1649 (m),
˜
NMR (400 MHz, CDCl3): δ = 2.30 (s, 3 H), 6.67 (s, 1 H), 6.86 (d,
J = 16.2 Hz, 1 H), 6.90 (d, J = 8.0 Hz, 1 H), 7.06–7.23 (m, 8 H, 7-
H or 8-H), 7.31 (t, J = 7.6 Hz, 2 H), 7.48 (d, J = 7.9 Hz, 2 H), 7.58
(td, J = 7.8, 1.2 Hz, 1 H), 8.59 (dd, J = 4.9, 1.8 Hz, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 11.0 (CH3), 106.6 (CH), 120.3 (C),
121.0 (CH), 122.4 (CH), 123.1 (CH), 124.7 (CH), 125.7 (CH), 126.2
(CH), 126.4 (CH), 127.8 (CH), 128.1 (CH), 128.5 (CH), 130.8 (C),
132.9 (C), 134.4 (C), 137.8 (CH), 138.5 (C), 149.1 (CH), 152.1
1603 (s), 1515 (m), 1496 (m), 1453 (s), 1393 (m), 1344 (s), 1229 (m),
1176 (m), 1114 (w), 1072 (w), 1029 (w), 755 (s), 699 (s) cm–1. MS
(EI): m/z (%) = 275 (70) [M]+, 184 (100), 105 (18). HRMS: calcd.
for C20H21N 275.1674 [M]+; found 275.1674.
(E)-2-Methyl-1,5-diphenyl-3-styryl-1H-pyrrole (6a): 1H NMR
(600 MHz, CDCl3): δ = 2.11 (s, 3 H), 6.60 (s, 1 H), 6.78 (d, J =
16.1 Hz, 1 H), 6.99–7.11 (m, 9 H), 7.22–7.26 (m, 5 H), 7.40 (d, J
= 7.5 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 11.1 (CH3),
105.7 (CH), 119.7 (C), 121.3 (CH), 124.4 (CH), 125.7 (CH), 126.1
(CH), 126.3 (CH), 127.6 (CH), 127.9 (CH), 127.8 (CH), 128.4
(CH), 128.5 (CH), 128.9 (CH), 130.6 (C), 132.9 (C), 134.8 (C),
(C) ppm. IR: ν = 3052 (m), 3028 (m), 2922 (m), 2854 (m), 1633
˜
(m), 1596 (s), 1585 (s), 1471 (s), 1435 (s), 1376 (m), 1027 (m), 953
(m), 757 (s), 696 (s) cm–1. MS (EI): m/z (%) = 336 (100) [M]+, 278
(25). HRMS: calcd. for C24H20N2 336.1626 [M]+; found 336.1626.
(E)-3-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)pyridine (6f): 1H
NMR (600 MHz, CDCl3): δ = 2.14 (s, 3 H), 6.61 (s, 1 H), 6.80 (d,
J = 16.1 Hz, 1 H), 6.97–7.00 (m, 2 H), 7.04–7.15 (m, 5 H, 7-H or
8-H), 7.20 (ddd, J = 8.0, 4.8, 0.6 Hz, 1 H), 7.25 (t, J = 7.5 Hz, 2
H), 7.33 (ddd, J = 8.0, 2.4, 1.6 Hz, 1 H), 7.41 (d, J = 7.2 Hz, 2 H),
8.40 (d, J = 2.5 Hz, 1 H), 8.48 (dd, J = 4.8, 1.5 Hz, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 11.1 (CH3), 106.6 (CH), 120.5 (C),
120.8 (CH), 123.5 (CH), 125.2 (CH), 125.8 (CH), 126.5 (CH), 126.6
(CH), 128.2 (CH), 128.3 (CH), 128.6 (CH), 130.3 (C), 132.2 (C),
135.1 (C), 135.6 (C), 138.4 (C), 138.7 (CH), 148.5 (CH), 149.3
(CH) ppm. MS (EI): m/z (%) = 336 (100) [M]+, 276 (24), 262 (12),
233 (16). HRMS: calcd. for C24H20N2 336.1626 [M]+; found
336.1627.
138.6 (C), 138.9 (C) ppm. IR: ν = 3056 (m), 3025 (m), 2915 (m),
˜
1722 (w), 1635 (m), 1595 (s), 1497 (s), 1448 (m), 1419 (m), 1375
(m), 1181 (m), 1071 (m), 1028 (m), 951 (m), 767 (m), 756 (s), 694
(s) cm–1. MS (EI): m/z (%) = 335 (100) [M]+, 261 (15), 193 (12), 149
(12),105 (20). HRMS: calcd. for C25H21N 335.1674 [M]+; found
335.1675.
(E)-2-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)phenol (6b): 1H
NMR (600 MHz, CDCl3): δ = 2.04 (s, 3 H), 5.26 (br. s, 1 H, OH),
6.67 (s, 1 H), 6.78–6.84 (m, 2 H), 6.92–6.99 (m, 3 H), 7.03–7.16 (m,
6 H), 7.20 (dt, J = 8.1, 1.6 Hz, 1 H), 7.26 (t, J = 7.6 Hz, 2 H), 7.41
(d, J = 7.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.3
(CH3), 106.3 (CH), 116.4 (CH), 120.6 (C), 120.8 (CH), 120.9 (CH),
124.9 (CH), 125.5 (C), 125.8 (CH), 126.5 (CH), 126.6 (CH), 127.3
(CH), 128.2 (CH), 128.6 (CH), 129.5 (CH), 130.1 (CH), 131.1 (C),
(E)-1-(4-Methoxyphenyl)-2-methyl-5-phenyl-3-styryl-1H-pyrrole
1
132.0 (C), 134.9 (C), 138.4 (C), 152.3 (C) ppm. IR: ν = 3421 (m),
˜
(6g): H NMR (600 MHz, CDCl3): δ = 2.11 (s, 3 H), 3.72 (s, 3 H),
3026 (m), 2991 (m), 2918 (m), 1720 (m), 1636 (m), 1597 (s), 1497
(s), 1447 (s), 1374 (s), 1236 (s), 1203 (s), 1072 (m), 1029 (m), 953
(m), 908 (m), 757 (s), 694 (s) cm–1. HRMS: calcd. for C25H21NO
351.1623 [M]+; found 351.1623.
6.59 (s, 1 H), 6.77–6.80 (m, 3 H), 6.99 (d, J = 8.8 Hz, 2 H), 7.02–
7.14 (m, 7 H, 7-H or 8-H), 7.24 (t, J = 7.6 Hz, 2 H), 7.40 (d, J =
7.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 11.0 (CH3),
55.4 (CH3), 105.3 (CH), 114.2 (CH), 119.4 (C), 121.3 (CH), 124.2
(CH), 125.7 (CH), 126.0 (CH), 126.3 (CH), 127.9 (CH), 128.0
(CH), 128.5 (CH), 129.4 (CH), 131.0 (C), 131.7 (C), 132.9 (C),
(E)-2-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)aniline (6c): 1H
NMR (600 MHz, CDCl3): δ = 2.06 (s, 3 H), 3.50 (br. s, 2 H, NH),
6.65–6.69 (m, 3 H), 6.79 (d, J = 16.1 Hz, 1 H), 6.93 (dd, J = 7.7,
1.2 Hz, 1 H), 7.02–7.06 (m, 2 H), 7.09–7.17 (m, 6 H), 7.25 (t, J =
7.76 Hz, 2 H), 7.40 (d, J = 7.5 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 10.2 (CH3), 105.5 (CH), 115.8 (CH), 118.5 (CH), 119.9
(C), 121.2 (CH), 124.2 (CH), 124.6 (C), 125.7 (CH), 126.2 (CH),
126.3 (CH), 127.1 (CH), 128.0 (CH), 128.5 (CH), 129.5 (CH), 129.7
(CH), 130.9 (C), 132.5 (C), 134.3 (C), 138.5 (C), 143.7 (C) ppm.
134.9 (C); 138.7 (C), 158.7 (C) ppm. IR: ν = 3024 (m), 2911 (w),
˜
1633 (m), 1599 (m), 1512 (s), 1448 (m), 1293 (m), 1247 (s), 1182
(m), 1167 (m), 1029 (m), 951 (m), 838 (m), 758 (m), 695 (m) cm–1.
MS (EI): m/z (%) = 365 (100) [M]+, 350 (8), 288 (6), 215 (6).
HRMS: calcd. for C26H23NO 365.1779 [M]+; found 365.1778.
(E)-2-Methyl-1-(4-nitrophenyl)-5-phenyl-3-styryl-1H-pyrrole (6h):
1H NMR (600 MHz, CDCl3): δ = 2.18 (s, 3 H), 6.62 (s, 1 H), 6.80
(d, J = 16.1 Hz, 1 H), 6.97 (d, J = 6.7 Hz, 2 H), 7.01 (d, J =
16.1 Hz, 1 H), 7.07–7.16 (m, 4 H), 7.19 (d, J = 8.9 Hz, 2 H), 7.26
(t, J = 7.5 Hz, 2 H), 7.41 (d, J = 7.5 Hz, 2 H), 8.14 (d, J = 8.9 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 11.3 (CH3), 107.3
(CH), 120.5 (CH), 121.0 (C), 124.4 (CH), 125.6 (CH), 125.8 (CH),
126.7 (CH), 126.8 (CH), 128.1 (CH), 128.3 (CH), 128.6 (CH), 128.9
(CH), 129.8 (C), 132.2 (C), 134.9 (C), 138.2 (C), 144.5 (C), 146.3
IR: ν = 3461 (m), 3380 (m), 3057 (m), 3026 (m), 2922 (m), 2853
˜
(m), 1633 (s), 1616 (s), 1597 (s), 1501 (s), 1462 (s), 1448 (s), 1419
(s), 1372 (s), 1311 (m), 1264 (m), 1184 (m), 1156 (m), 1073 (m),
1028 (m), 952 (s), 908 (m), 751 (s), 694 (s) cm–1. MS (EI): m/z (%)
= 350 (100) [M]+, 335 (10), 273 (9), 269 (12), 246 (9), 187 (9).
HRMS: calcd. for C25H22N2 350.1783 [M]+; found 350.1783.
(E)-1-(2-Bromophenyl)-2-methyl-5-phenyl-3-styryl-1H-pyrrole (6d):
1H NMR (600 MHz, CDCl3): δ = 2.05 (s, 3 H), 6.63 (s, 1 H), 6.80
(d, J = 16.1 Hz, 1 H), 7.02–7.09 (m, 6 H), 7.10 (t, J = 7.3 Hz, 1
H), 7.13–7.17 (m, 2 H), 7.22 (td, J = 7.6, 1.4 Hz, 1 H), 7.24 (t, J =
7.6 Hz, 2 H), 7.40 (d, J = 7.3 Hz, 2 H), 7.56 (dd, J = 7.9, 1.1 Hz,
1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.6 (CH3), 105.5
(C) ppm. IR: ν = 3070 (w), 3055 (w), 3030 (w), 2924 (w), 1592 (s),
˜
1514 (s), 1498 (s), 1369 (m), 1335 (s), 965 (m), 856 (m), 765 (m),
757 (m), 753 (m), 706 (m), 697 (m) cm–1. MS (EI): m/z (%) = 380
(100) [M]+, 334 (8). HRMS: calcd. for C25H20N2O2 380.1524
[M]+; found 380.1524.
(CH), 119.8 (C), 121.2 (CH), 124.3 (C), 124.5 (CH), 125.7 (CH), Methyl (E)-3,5-Dibromo-2-(2-methyl-5-phenyl-3-styryl-1H-pyrrol-1-
126.3 (CH), 126.4 (CH), 127.7 (CH), 128.0 (CH), 128.2 (CH), 128.5 yl)benzoate (6i): 1H NMR (600 MHz, CDCl3): δ = 2.01 (s, 3 H),
(CH), 129.8 (CH), 130.7 (C), 131.1 (CH), 132.7 (C), 133.3 (CH), 3.54 (s, 3 H), 6.59 (s, 1 H), 6.75 (d, J = 16.1 Hz, 1 H), 6.98–7.25
134.9 (C), 138.5 (C), 138.6 (C) ppm. IR: ν = 3056 (m), 3026 (m),
(m, 9 H), 7.37 (d, J = 7.4 Hz, 2 H), 7.78 (d, J = 2.2 Hz, 1 H), 7.87
˜
2920 (m), 1635 (m), 1596 (m), 1481 (s), 1447 (m), 1419 (m), 1373 (d, J = 2.2 Hz, 1 H) ppm. 13C NMR (150 MHz, CDCl3): δ = 10.4
(m), 1073 (m), 1028 (m), 953 (m), 757 (s), 731 (m), 695 (s) cm–1. (CH3), 52.9 (CH3), 106.0 (CH), 120.2 (C), 121.1 (CH), 122.6 (C),
MS (EI): m/z (%) = 415 (98) [C25H2081BrN], 413 (100) [M]+, 293
124.5 (CH), 125.7 (CH), 126.3 (CH), 126.7 (CH), 127.3 (C), 127.6
7360
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Eur. J. Org. Chem. 2013, 7354–7365

Substituted Pyrroles from 1-Vinylpropargyl Alcohols and Amines
(CH), 128.1 (CH), 128.5 (CH), 130.5 (C), 132.3 (C), 132.7 (CH), (t, J = 7.4 Hz, 1 H), 7.12 (t, J = 7.3 Hz, 1 H), 7.22 (d, J = 8.1 Hz,
134.2 (C), 134.8 (C), 136.8 (C), 138.5 (C), 138.7 (CH), 163.8 1 H), 7.26 (t, J = 7.7 Hz, 2 H), 7.39 (d, J = 7.6 Hz, 2 H), 7.82 (br.
(C) ppm. MS (EI): m/z (%) = 553 (55) [C27H2181Br2NO2], 551 (100) s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 11.2 (CH3),
[C27H21Br81BrNO2], 549 (51) [M]+, 479 (20), 477 (35), 475 (19). 27.1 (CH2), 52.7 (CH3), 58.2 (CH), 104.9 (CH), 110.4 (C), 110.9
HRMS: calcd. for C27H21Br2NO2 548.9934 [M]+; found 548.9934.
(CH), 117.9 (CH), 119.4 (CH), 120.3 (C), 121.2 (CH), 121.7 (CH),
123.0 (CH), 124.2 (CH), 125.7 (CH), 126.3 (CH), 127.0 (C), 127.2
(CH), 128.0 (CH), 128.1 (C), 128.5 (CH), 129.4 (CH), 132.7 (C),
(E)-1-Benzyl-2-methyl-5-phenyl-3-styryl-1H-pyrrole (6j): 1H NMR
(600 MHz, CDCl3): δ = 2.12 (d, J = 1.2 Hz, 3 H), 5.03 (s, 2 H),
6.49 (d, J = 1.7 Hz, 1 H), 6.76 (d, J = 16.0 Hz, 1 H), 6.87 (d, J =
7.6 Hz, 2 H), 7.02 (dd, J = 16.0, 1.6 Hz, 1 H), 7.06–7.11 (m, 1 H),
7.14–7.18 (m, 2 H), 7.20–7.25 (m, 8 H), 7.38 (d, J = 7.7 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.3 (CH3), 47.7 (CH2),
105.0 (CH), 119.5 (C), 121.4 (CH), 123.8 (CH), 125.6 (CH), 125.7
(CH), 126.2 (CH), 127.0 (CH), 127.1 (CH), 128.4 (CH), 128.5
(CH), 128.7 (C), 128.8 (CH), 129.5 (C), 133.1 (C), 135.3 (C), 138.5
135.8 (C), 136.5 (C), 138.6 (C), 171.5 (C) ppm. IR: ν = 3414 (m),
˜
3055 (m), 3025 (m), 2949 (m), 2925 (m), 1738 (s), 1632 (m), 1597
(m), 1455 (s), 1429 (s), 1356 (s), 1727 (m), 1220 (s), 1172 (m), 1093
(m), 1071 (s), 1028 (m), 1010 (m), 986 (m), 954 (m), 792 (m), 762
(s), 742 (s), 695 (s) cm–1. MS (EI): m/z (%) = 460 (100) [M]+, 331
(21), 272 (18), 260 (26), 130 (34). HRMS: calcd. for C31H28N2O2
460.2146 [M]+; found 460.2145.
1
(C), 138.7 (C) ppm. IR: ν = 3058 (m), 3025 (m), 2912 (m), 1633
(E)-1-Benzhydryl-2-methyl-5-phenyl-3-styryl-1H-pyrrole (6n): H
˜
(s), 1598 (s), 1495 (s), 1452 (s), 1428 (s), 1350 (s), 1165 (m), 1072 NMR (600 MHz, CDCl3): δ = 1.82 (d, J = 0.8 Hz, 3 H), 6.55 (s, 1
(m), 1028 (m), 952 (s), 756 (s), 728 (s), 693 (s) cm–1. MS (EI): m/z H), 6.78 (s, 1 H), 6.81 (d, J = 16.0 Hz, 1 H), 7.02 (dd, J = 16.0,
(%) = 349 (100) [M]+, 258 (28), 243 (40). HRMS: calcd. for 0.6 Hz, 1 H), 7.11–7.16 (m, 5 H), 7.24–7.33 (m, 13 H), 7.42 (d, J
C26H23N 349.1831 [M]+; found 349.1830.
= 8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 12.7 (CH3),
62.5 (CH), 105.2 (CH), 120.2 (C), 121.3 (CH), 123.9 (CH), 125.7
(CH), 126.2 (CH), 127.3 (CH), 127.4 (CH), 128.2 (CH), 128.3
(CH), 128.4 (CH), 128.5 (CH), 129.4 (CH), 129.9 (C), 133.6 (C),
(E)-2-Methyl-5-phenyl-1-[2-(1H-pyrrol-1-yl)benzyl]-3-styryl-1H-pyr-
1
role (6k): H NMR (600 MHz, CDCl3): δ = 2.04 (s, 3 H), 4.81 (s,
2 H), 6.22 (t, J = 1.9 Hz, 2 H), 6.46 (s, 1 H), 6.56 (t, J = 2.0 Hz, 2
H), 6.62–6.64 (m, 1 H), 6.73 (d, J = 16.1 Hz, 1 H), 6.98 (d, J =
16.1 Hz, 1 H), 7.06–7.09 (m, 2 H), 7.15–7.23 (m, 9 H), 7.36 (d, J
= 8.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.1 (CH3),
43.8 (CH2), 105.3 (CH), 109.4 (CH), 119.6 (C), 121.3 (CH), 121.9
(CH), 123.9 (CH), 125.7 (CH), 126.3 (CH), 126.7 (CH), 126.9
(CH), 127.2 (CH), 127.8 (CH), 128.4 (CH), 128.5 (CH), 128.6
136.6 (C), 138.7 (C), 139.3 (C) ppm. IR: ν = 3057 (m), 3025 (m),
˜
2920 (m), 1632 (m), 1598 (m), 1494 (m), 1446 (s), 1427 (m), 1352
(m), 1178 (m), 1153 (m), 1071 (m), 1028 (m), 952 (m), 761 (s), 749
(s), 721 (s), 697 (s), 603 (m) cm–1. MS (EI): m/z (%) = 425 (35)
[M]+, 167 (100). HRMS: calcd. for C23H27N 425.2143 [M]+; found
425.2146.
(CH), 128.7 (CH), 129.3 (C), 132.9 (C), 134.9 (C), 135.3 (C), 138.5 (E)-2-Methyl-1-phenethyl-5-phenyl-3-styryl-1H-pyrrole (6o): 1H
(C), 138.6 (C) ppm. IR: ν = 3057 (m), 3025 (m), 2922 (m), 2853 NMR (600 MHz, CDCl3): δ = 2.21 (d, J = 0.7 Hz, 3 H), 2.65 (t, J
˜
(m), 1633 (m), 1599 (m), 1500 (s), 1479 (m), 1457 (m), 1428 (m), = 7.9 Hz, 2 H), 3.98 (t, J = 7.3 Hz, 2 H), 6.35 (s, 1 H), 6.68 (d, J
1349 (m), 1326 (m), 1167 (m), 1092 (m), 1070 (m), 1015 (m), 952 = 16.0 Hz, 1 H), 6.82 (d, J = 7.4 Hz, 2 H), 6.99 (dd, J = 16.0,
(m), 925 (m), 758 (s), 728 (s), 693 (s) cm–1. MS (EI): m/z (%) = 414
0.7 Hz, 1 H), 7.06–7.14 (m, 4 H), 7.20–7.33 (m, 7 H), 7.37 (d, J =
(100) [M]+, 258 (24), 243 (23),156 (48). HRMS: calcd. for C30H26N2 7.7 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.2 (CH3),
414.2095 [M]+; found 414.2095.
37.4 (CH2), 45.7 (CH2), 105.2 (CH), 119.1 (C), 121.5 (CH), 123.6
(CH), 125.6 (CH), 126.1 (CH), 126.5 (CH), 127.2 (CH), 128.4
(CH), 128.5 (CH), 128.5 (CH), 128.6 (CH), 128.8 (C), 129.2 (CH),
(E)-3-[2-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)ethyl]-1H-
1
indole (6l): H NMR (600 MHz, CDCl3): δ = 2.28 (s, 3 H), 2.82 (t,
133.6 (C), 134.5 (C), 138.0 (C), 138.8 (C) ppm. IR: ν = 3058 (m),
˜
J = 7.9 Hz, 2 H), 4.06 (t, J = 7.9 Hz, 2 H), 6.39 (s, 1 H), 6.69 (d,
J = 1.8 Hz, 1 H), 6.71 (d, J = 16.0 Hz, 1 H), 6.93 (t, J = 7.1 Hz, 1
H), 7.01–7.04 (m, 2 H, 7-H or 8-H), 7.06–7.10 (m, 2 H), 7.21–7.34
(m, 8 H), 7.39 (d, J = 7.5 Hz, 2 H), 7.82 (br. s, 1 H, NH) ppm. 13C
NMR (100 MHz, CDCl3): δ = 10.3 (CH3), 26.9 (CH2), 44.9 (CH2),
105.1 (CH), 111.1 (CH), 112.1 (C), 118.3 (CH), 119.0 (C), 119.3
3025 (m), 2928 (m), 1633 (m), 1598 (m), 1448 (m), 1429 (m), 1352
(s), 1165 (m), 1072 (m), 1029 (m), 952 (m), 909 (m), 750 (s), 697
(s) cm–1. MS (EI): m/z (%) = 363 (100) [M]+, 272 (64). HRMS:
calcd. for C27H25N 363.1981 [M]+; found 363.1982.
1
(E)-1-Allyl-2-methyl-5-phenyl-3-styryl-1H-pyrrole (6p): H NMR
(CH), 121.5 (CH), 121.8 (CH), 121.9 (CH), 123.5 (CH), 125.6 (600 MHz, CDCl3): δ = 2.25 (s, 3 H), 4.37–4.38 (m, 2 H), 4.83 (dd,
(CH), 126.1 (CH), 127.0 (C), 127.2 (CH), 128.4 (CH), 128.5 (CH), J = 17.1, 0.8 Hz, 1 H), 5.13 (dd, J = 10.4, 0.9 Hz, 1 H), 5.82–5.87
128.9 (C), 129.3 (CH), 133.6 (C), 134.5 (C), 136.0 (C), 138.8 (m, 1 H), 6.41 (s), 6.71 (d, J = 16.0 Hz, 1 H), 7.01 (d, J = 16.0 Hz,
(C) ppm. IR: ν = 3420 (s), 3056 (m), 3027 (m), 2923 (m), 2854 (m),
1 H), 7.09 (t, J = 7.4 Hz, 1 H), 7.22–7–25 (m, 3 H), 7.30 (t, J =
7.6 Hz, 2 H), 7.34 (d, J = 7.2 Hz, 2 H), 7.38 (d, J = 7.3 Hz, 2
˜
1719 (m), 1632 (s), 1597 (s), 1456 (s), 1429 (s), 1353 (s), 1165 (m),
1092 (m), 1073 (m), 1029 (m), 1011 (m), 954 (s), 761 (s), 742 (s), H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.0 (CH3), 46.5 (CH2),
695 (s) cm–1. MS (EI): m/z (%) = 402 (100) [M]+, 272 (72), 260
(22), 130 (21). HRMS: calcd. for C29H26N2 402.2095 [M]+; found
402.2095.
104.7 (CH), 116.1 (CH2), 119.1 (C), 121.4 (CH), 123.6 (CH), 125.6
(CH), 126.1 (CH), 127.1 (CH), 128.3 (CH), 128.5 (CH), 128.7
(CH), 129.5 (C), 133.2 (C), 134.5 (CH), 134.9 (C), 138.8 (C) ppm.
IR: ν = 3057 (m), 3024 (m), 2923 (m), 2853 (m), 1633 (s), 1599 (s),
˜
Methyl (E)-3-(1H-Indol-3-yl)-2-(2-methyl-5-phenyl-3-styryl-1H-pyr-
rol-1-yl)propanoate (6m): The amine was generated in situ from l-
tryptophan methyl ester and Et3N (1 equiv.). Polarimetric analysis
1447 (m), 1428 (s), 1364 (m), 1350 (s), 1166 (s), 1072 (s), 953 (s),
916 (m), 787 (m), 767 (s), 755 (s), 693 (s) cm–1. MS (EI): m/z (%)
= 299 (100) [M]+, 243 (41), 215 (16). HRMS: calcd. for C22H21N
299.1674 [M]+; found 299.1673.
1
and H NMR experiments in the presence of a chiral shift reagent
(Eu[tfc]3, 1.1 equiv.) revealed that the product was racemic. 1H
NMR (600 MHz, CDCl3): δ = 2.34 (s, 3 H), 3.13 (dd, J = 15.0,
(E)-1-(But-3-en-1-yl)-2-methyl-5-phenyl-3-styryl-1H-pyrrole (6q):
9.2 Hz, 1 H), 3.58 (dd, J = 15.0, 5.9 Hz, 1 H), 3.74 (s, 3 H), 5.05 1H NMR (600 MHz, CDCl3): δ = 2.17 (q, J = 7.5 Hz, 2 H), 2.30
(dd, J = 9.2, 5.9 Hz, 1 H), 6.23 (s, 1 H), 6.51 (d, J = 2.3 Hz, 1 H),
6.69 (d, J = 16.0 Hz, 1 H), 6.80 (d, J = 7.1 Hz, 2 H), 6.81 (t, J =
7.3 Hz, 1 H), 6.91 (d, J = 7.9 Hz, 1 H), 7.01–7.05 (m, 4 H), 7.09
(d, J = 1.0 Hz, 3 H), 3.83 (t, J = 7.5 Hz, 2 H), 4.87–4.90 (m, 2 H),
5.45–5.55 (m, 1 H), 6.34 (d, J = 1.7 Hz, 1 H), 6.68 (d, J = 16.1 Hz,
1 H), 7.00 (dd, J = 16.1, 1.5 Hz, 1 H), 7.07 (t, J = 7.3 Hz, 1 H),
Eur. J. Org. Chem. 2013, 7354–7365
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7361

N. Thies, M. Gerlach, E. Haak
FULL PAPER
7.20–7.25 (m, 3 H), 7.30–7.32 (m, 4 H), 7.35 (d, J = 7.9 Hz, 2
7.3 Hz, 1 H), 7.23–7.27 (m, 4 H), 7.30–7.37 (m, 4 H), 7.40 (d, J =
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.4 (CH3), 35.2 (CH2), 7.5 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.2 (CH3),
43.6 (CH2), 105.1 (CH), 117.1 (CH2), 119.1 (C), 121.4 (CH), 123.6
41.8 (CH2), 105.1 (C), 107.2 (CH), 110.3 (CH), 119.4 (C), 121.3
(CH), 125.6 (CH), 126.1 (CH), 127.1 (CH), 128.4 (CH), 128.5 (CH), 123.4 (CH), 125.7 (CH), 126.2 (CH), 127.2 (CH), 128.5
(CH), 128.8 (C), 129.1 (CH), 133.6 (C), 134.1 (CH), 134.5 (C), (CH), 128.4 (CH), 129.1 (CH), 129.6 (C), 133.1 (C), 135.1 (C),
138.8 (C) ppm. IR: ν = 3058 (m), 3027 (m), 2976 (m), 2905 (m),
138.7 (C), 142.1 (CH), 151.3 (C) ppm. IR: ν = 3057 (m), 3025 (m),
˜
˜
1631 (s), 1594 (m), 1443 (m), 1428 (m), 1353 (s), 1169 (m), 1073 2915 (m), 1633 (s), 1598 (s), 1447 (s), 1428 (s), 1338 (s), 1166 (m),
(m), 1021 (m), 994 (m), 950 (s), 923 (m), 799 (m), 749 (s), 696 1146 (m), 1072 (m), 1010 (s), 751 (s), 693 (s) cm–1. MS (EI): m/z (%)
(s) cm–1. MS (EI): m/z (%) = 313 (100) [M]+, 272 (80). HRMS: = 339 (46) [M]+, 258 (54), 243 (100). HRMS: calcd. for C24H21NO
calcd. for C23H23N 313.1826 [M]+; found 313.1825.
339.1618 [M]+; found 339.1618.
(E)-2-Methyl-5-phenyl-3-styryl-1-[(tetrahydrofuran-2-yl)methyl]-
1H-pyrrole (6r): H NMR (600 MHz, CDCl3): δ = 1.15–1.21 (m, 1 isoindole (7a): H NMR (400 MHz, CDCl3): δ = 1.73 (quint., J =
H), 1.52–1.62 (m, 3 H), 2.34 (d, J = 1.2 Hz, 3 H), 3.50–3.59 (m, 2 6.0 Hz, 2 H), 2.27 (s, 3 H), 2.68 (t, J = 6.2 Hz, 2 H), 2.73 (t, J =
(E)-4-Benzylidene-3-methyl-1,2-diphenyl-4,5,6,7-tetrahydro-2H-
1
1
H), 3.81 (quint., J = 6.1 Hz, 1 H), 3.92 (d, J = 6.4 Hz, 2 H), 6.36
(d, J = 1.4 Hz, 1 H), 6.68 (d, J = 16.0 Hz, 1 H), 7.02 (d, J =
6.0 Hz, 2 H), 6.62 (s, 1 H), 6.92 (d, J = 7.2 Hz, 2 H), 7.03–7.26 (m,
13 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.3 (CH3), 23.4
16.0 Hz, 1 H), 7.07 (t, J = 7.3 Hz, 1 H), 7.17 (t, J = 7.5 Hz, 1 H), (CH2), 25.5 (CH2), 29.1 (CH2), 118.8 (C), 119.6 (C), 121.0 (CH),
7.22 (t, J = 7.4 Hz, 2 H), 7.29–7.34 (m, 4 H), 7.38 (d, J = 125.6 (CH), 125.7 (CH), 126.2 (C), 127.3 (CH), 127.7 (CH), 127.9
7.6 Hz) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.6 (CH3), 25.1 (C), 128.0 (CH), 128.8 (CH), 128.9 (CH), 129.3 (CH), 129.4 (CH),
(CH2), 28.9 (CH2), 47.8 (CH2), 67.8 (CH2), 78.3 (CH), 105.5 (CH), 132.8 (C), 135.8 (C), 138.8 (C), 138.9 (C) ppm. IR: ν = 3057 (m),
˜
119.1 (C), 121.5 (CH), 123.5 (CH), 125.6 (CH), 126.0 (CH), 126.9
3028 (m), 2924 (m), 1663 (m), 1597 (s), 1495 (s), 1448 (s), 1374 (s),
(CH), 128.3 (CH), 128.4 (CH), 129.3 (CH), 129.6 (C), 133.8 (C), 1316 (m), 1266 (m), 1177 (m), 1073 (m), 1028 (m), 910 (m), 761
134.7 (C), 138.8 (C) ppm. IR: ν = 3058 (m), 3025 (m), 2927 (m), (m), 731 (s), 698 (s) cm–1. MS (EI): m/z (%) = 375 (20) [M]+, 314
˜
1632 (m), 1598 (m), 1448 (m), 1429 (m), 1352 (s), 1165 (m), 1027 (38), 300 (21), 180 (45), 105 (100). HRMS: calcd. for C28H25
N
(m), 1029 (m), 952 (m), 750 (s), 697 (s) cm–1. MS (EI): m/z (%) =
343 (100) [M]+, 272 (36), 259 (38), 169 (41). HRMS: calcd. for
C24H25NO 343.1931 [M]+; found 343.1931.
375.1987 [M]+; found 375.1989.
(E)-2-Benzyl-4-benzylidene-3-methyl-1-phenyl-4,5,6,7-tetra-
1
hydro-2H-isoindole (7b): H NMR (600 MHz, CDCl3): δ = 1.73
(E)-2-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)ethanol (6s): H (quint., J = 6.0 Hz, 2 H), 2.29 (s, 3 H), 2.59 (t, J = 6.0 Hz, 2 H),
1
NMR (600 MHz, CDCl3): δ = 2.24 (s, 3 H), 3.43 (t, J = 6.1 Hz, 2
2.72 (t, J = 6.0 Hz, 2 H), 5.03 (s, 2 H), 6.56 (s, 1 H), 6.91 (d, J =
H), 3.90 (t, J = 6.1 Hz, 2 H), 6.29 (s, 1 H), 6.62 (d, J = 16.0 Hz, 1 7.2 Hz, 2 H), 7.17–7.27 (m, 13 H) ppm. 13C NMR (150 MHz,
H), 6.93 (d, J = 16.0 Hz, 1 H), 7.01–7.27 (m, 8 H), 7.32 (d, J = CDCl3): δ = 13.1 (CH3), 22.8 (CH2), 25.4 (CH2), 29.2 (CH2), 47.5
7.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.5 (CH3), (CH2), 118.3 (C), 118.7 (C), 120.4 (CH), 124.9 (C), 125.4 (CH),
45.9 (CH2), 62.0 (CH2), 105.5 (CH), 119.2 (C), 121.2 (CH), 123.8
125.7 (CH), 126.9 (CH), 127.0 (CH), 128.0 (CH), 128.2 (C), 128.3
(CH), 125.6 (CH), 126.2 (CH), 127.2 (CH), 128.4 (CH), 128.5 (CH), 128.7 (CH), 129.2 (CH), 129.9 (CH), 132.8 (C), 136.0 (C),
(CH), 129.2 (CH), 129.5 (C), 133.4 (C), 134.7 (C), 138.7 (C) ppm.
138.3 (C), 139.0 (C) ppm. HRMS: calcd. for C29H27N 389.2143
[M]+; found 389.2143.
IR: ν = 3402 (m), 3057 (m), 3026 (m), 2935 (m), 1632 (s), 1598 (s),
˜
1494 (m), 1448 (s), 1429 (m), 1357 (m), 1203 (m), 1167 (m), 1053
(m), 954 (m), 752 (s), 697 (s) cm–1. MS (EI): m/z (%) = 303 (100)
[M]+, 272 (31), 260 (45), 127 (60), 118 (43), 105 (23). HRMS: calcd.
for C21H21NO 303.1618 [M]+; found 303.1618.
(E)-3-[2-(4-Benzylidene-3-methyl-1-phenyl-4,5,6,7-tetrahydro-2H-
isoindol-2-yl)ethyl]-1H-indole (7c): H NMR (600 MHz, CDCl3): δ
= 1.69–1.71 (m, 2 H), 2.50 (s, 3 H), 2.51–2.53 (m, 2 H), 2.70 (t, J
= 5.8 Hz, 2 H), 2.86 (t, J = 8.3 Hz, 2 H), 4.04 (t, J = 8.3 Hz, 2 H),
1
Methyl (E)-2-(2-Methyl-5-phenyl-3-styryl-1H-pyrrol-1-yl)propano- 6.59 (s, 1 H), 6.72 (d, J = 2.0 Hz, 1 H), 6.91 (d, J = 4.0 Hz, 2 H),
ate (6t): The amine was generated in situ from l-alanine methyl
ester and Et3N (1 equiv.). Polarimetric analysis and H NMR ex-
periments in the presence of a chiral shift reagent (Eu[tfc]3,
1.1 equiv.) revealed that the product was racemic. 1H NMR
(600 MHz, CDCl3): δ = 1.62 (d, J = 7.3 Hz, 3 H), 2.32 (s, 3 H),
7.05–7.08 (m, 1 H), 7.11–7.13 (m, 1 H), 7.15–7.20 (m, 2 H), 7.24–
7.30 (m, 6 H), 7.34–7.37 (m, 2 H), 7.83 (br. s, 1 H, NH) ppm. 13C
NMR (100 MHz, CDCl3): δ = 12.9 (CH3), 22.5 (CH2), 25.4 (CH2),
27.3 (CH2), 29.1 (CH2), 44.7 (CH2), 111.0 (CH), 112.4 (C), 117.8
(C), 118.4 (CH), 118.6 (C), 119.3 (CH), 120.2 (CH), 121.7 (CH),
1
3.78 (s, 3 H), 5.03 (q, J = 7.3 Hz, 1 H), 6.47 (s, 1 H), 6.81 (d, J = 121.9 (CH), 124.1 (C), 125.3 (CH), 126.9 (CH), 127.0 (C), 127.5
16.0 Hz, 1 H), 7.08 (d, J = 16.0 Hz, 1 H), 7.20 (t, J = 7.9 Hz, 1 H),
7.34 (t, J = 7.6 Hz, 2 H), 7.38–7.44 (m, 5 H), 7.48 (d, J = 8.1 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10.9 (CH3), 17.7
(C), 128.0 (CH), 128.4 (CH), 129.2 (CH), 130.4 (CH), 133.2 (C),
136.1 (C), 139.0 (C), 140.7 (C) ppm. IR: ν = 3418 (s), 3054 (m),
˜
2923 (s), 2854 (m), 1600 (s), 1566 (m), 1488 (m), 1456 (s), 1443 (m),
(CH3), 52.7 (CH3), 53.2 (CH), 105.4 (CH), 120.2 (C), 121.0 (CH), 1420 (m), 1351 (m), 1164 (w), 1095 (m), 1074 (m), 1029 (m), 1011
124.4 (CH), 125.7 (CH), 126.3 (CH), 127.5 (CH), 128.3 (C), 128.5
(m), 909 (m), 740 (s), 700 (s) cm–1. MS (EI): m/z (%) = 442 (100)
(CH), 128.4 (CH), 129.4 (CH), 133.1 (C), 135.3 (C), 138.6 (C), [M]+, 312 (65), 300 (22), 273 (20), 105 (21). HRMS: calcd. for
171.9 (C) ppm. IR: ν = 3056 (m), 3025 (m), 2996 (m), 2949 (m),
C32H30N2 442.2409 [M]+; found 442.2408.
˜
1742 (s), 1622 (m), 1597 (m), 1489 (m), 1431 (m), 1357 (m), 1297
(m), 1224 (s), 1172 (m), 1123 (m), 1089 (m), 1072 (m), 1028 (m),
953 (s), 910 (m), 761 (s), 695 (s) cm–1. MS (EI): m/z (%) = 345 (100)
[M]+, 286 (38), 258 (48), 243 (30), 215 (61), 143 (23), 106 (26).
HRMS: calcd. for C23H23NO2 345.1729 [M]+; found 345.1729.
2-[(2Z,4E)-3-Ethynyl-1,5-diphenylpenta-2,4-dien-1-yl]aniline (8a):
1H NMR (600 MHz, CDCl3): δ = 3.35 (s, 1 H), 3.60 (br. s, 2 H,
NH), 5.39 (d, J = 10.4 Hz, 1 H), 6.44 (d, J = 10.4 Hz, 1 H), 6.62
(d, J = 7.8 Hz, 1 H), 6.70 (t, J = 7.5 Hz, 1 H), 6.73 (d, J = 15.7 Hz,
1 H), 6.94 (d, J = 15.9 Hz, 1 H), 6.98 (d, J = 7.7 Hz, 1 H), 7.02 (t,
(E)-1-(Furan-2-ylmethyl)-2-methyl-5-phenyl-3-styryl-1H-pyrrole J = 7.6 Hz, 1 H), 7.16–7.21 (m, 4 H), 7.23–7.28 (m, 4 H), 7.34 (d,
1
(6u): H NMR (600 MHz, CDCl3): δ = 2.30 (s, 3 H), 4.93 (s, 2 H),
5.89 (d, J = 1.3 Hz, 1 H), 6.22 (d, J = 1.4 Hz, 1 H), 6.43 (s, 1 H),
6.74 (d, J = 16.1 Hz, 1 H), 7.02 (d, J = 16.0 Hz, 1 H), 7.11 (t, J =
J = 8.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 47.6
(CH), 78.5 (C), 84.7 (CH), 116.5 (CH), 118.8 (CH), 122.6 (C), 126.6
(CH), 126.8 (CH), 127.2 (C), 127.7 (CH), 127.8 (CH), 128.0 (CH),
7362
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Eur. J. Org. Chem. 2013, 7354–7365

Substituted Pyrroles from 1-Vinylpropargyl Alcohols and Amines
128.1 (CH), 128.6 (CH), 128.8 (CH), 129.0 (CH), 131.7 (CH), 136.8 29.3 (CH2), 32.9 (CH2), 47.4 (CH2), 115.1 (CH2), 118.1 (C), 119.2
(C), 141.9 (C), 142.2 (CH), 144.6 (C) ppm.
(C), 119.6 (CH), 125.4 (CH), 125.7 (CH), 126.8 (CH), 127.0 (CH),
128.0 (CH), 128.2 (CH), 128.3 (C), 128.6 (CH), 128.8 (C), 129.3
(CH), 130.0 (CH), 132.8 (C), 135.6 (C), 137.7 (CH), 139.0 (C),
4-[(2Z,4E)-3-Ethynyl-1,5-diphenylpenta-2,4-dien-1-yl]aniline (8b):
1H NMR (600 MHz, CDCl3): δ = 3.37 (s, 1 H), 3.61 (br. s, 2 H,
NH), 5.38 (d, J = 10.4 Hz, 1 H), 6.49 (d, J = 10.4 Hz, 1 H), 6.64
(d, J = 8.5 Hz, 2 H), 6.78 (d, J = 15.7 Hz, 1 H), 7.00 (d, J =
15.7 Hz, 1 H), 7.02 (d, J = 8.1 Hz, 2 H), 7.21–7.25 (m, 4 H), 7.29–
7.34 (m, 4 H), 7.41 (d, J = 7.2 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 50.8 (CH), 78.7 (C), 83.9 (CH), 115.3 (CH), 121.9 (C),
126.4 (CH), 126.6 (CH), 127.6 (CH), 128.3 (CH), 128.4 (CH), 128.5
(CH), 128.6 (CH), 129.2 (CH), 131.3 (CH), 133.1 (C), 136.9 (C),
143.6 (C), 144.3 (CH), 144.9 (C) ppm.
139.2 (C) ppm. IR: ν = 3060 (m), 3027 (m), 2927 (s), 1664 (m),
˜
1640 (m), 1601 (s), 1495 (s), 1452 (s), 1354 (s), 1329 (m), 1265 (m),
1177 (m), 1074 (m), 1029 (m), 1001 (m), 916 (m), 754 (s), 733 (s),
700 (s) cm–1. MS (EI): m/z (%) = 429 (36) [M]+, 389 (38), 388 (100),
338 (23), 296 (18). HRMS: calcd. for C32H31N 429.2457 [M]+;
found 429.2456.
7-Ethynyl-1,2,5-triphenyl-2,3,3a,4,5,7a-hexahydro-1H-isoindole
1
(10a): Major diastereomer: H NMR (600 MHz, CDCl3): δ = 1.72
1-Benzyl-2-(but-3-enyl)-3-methyl-1H-pyrrole (9a): 1H NMR
(400 MHz, CDCl3): δ = 2.05 (td, J = 8.0, 6.8 Hz, 2 H), 2.07 (s, 3
H), 2.56 (t, J = 8.0 Hz, 2 H), 4.91–4.97 (m, 2 H), 5.02 (s, 2 H), 5.77
(ddt, J = 16.8, 10.4, 6.8 Hz, 1 H), 6.00 (d, J = 1.4 Hz, 1 H), 6.53
(d, J = 1.8 Hz, 1 H), 7.01 (d, J = 7.2 Hz, 2 H), 7.24 (t, J = 7.2 Hz,
1 H), 7.31 (t, J = 7.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 11.7 (CH3), 24.2 (CH2), 34.4 (CH2), 50.7 (CH2), 108.9 (CH),
115.0 (CH2), 115.7 (C), 119.8 (CH), 126.5 (CH), 127.4 (CH), 128.8
(dt, J = 13.2, 10.6 Hz, 1 H), 2.08 (dt, J = 13.3, 5.0 Hz, 1 H), 2.67–
2.71 (m, 1 H), 2.73 (s, 1 H), 2.96 (t, J = 7.4 Hz, 1 H), 3.47 (dd, J
= 9.8, 2.1 Hz), 3.61 (m, 1 H), 3.99 (dd, J = 9.7, 7.4 Hz, 1 H), 4.80
(d, J = 7.3 Hz, 1 H), 6.46 (br. s, 1 H), 6.50 (d, J = 7.6 Hz, 2 H),
6.62 (t, J = 7.5 Hz, 1 H), 7.11 (t, J = 7.6 Hz, 2 H), 7.25–7.37 (m,
8 H), 7.46 (d, J = 7.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 33.6 (CH2), 36.2 (CH), 42.1 (CH), 51.4 (CH), 55.0 (CH2), 68.3
(CH), 77.6 (CH), 83.9 (C), 112.8 (CH), 115.8 (CH), 121.2 (C), 126.6
(CH), 127.0 (CH), 127.3 (CH), 127.4 (CH), 128.2 (CH), 128.6
(CH), 128.7 (CH), 140.6 (CH), 143.8 (C), 144.4 (C), 146.8 (C) ppm.
(CH), 128.9 (C), 138.2 (CH), 139.0 (C) ppm. IR: ν = 3065 (m),
˜
3030 (m), 2924 (s), 2860 (s), 1709 (s), 1693 (s), 1640 (s), 1606 (m),
1496 (s), 1489 (s), 1454 (s), 1414 (s), 1384 (s), 1354 (s), 1337 (s),
1259 (m), 1244 (w), 1207 (m), 1189 (w), 1162 (w), 1076 (w), 1050
(w), 1029 (m), 994 (m), 966 (w), 945 (w), 912 (s), 845 (w), 822 (w),
800 (w), 727 (s), 696 (s), 667 (m), 641 (m) cm–1. MS (EI): m/z (%)
= 225 (20) [M]+, 185 (20), 184 (100), 91 (90). HRMS: calcd. for
C16H19N 225.1517 [M]+; found 225.1517.
2-(But-3-enyl)-3-methyl-1-phenethyl-1H-pyrrole (9b): 1H NMR
(400 MHz, CDCl3): δ = 2.08 (s, 3 H), 2.22 (tdt, J = 8.1, 6.7, 1.2 Hz,
2 H), 2.61 (t, J = 8.1 Hz, 2 H), 3.03 (t, J = 7.8 Hz, 2 H), 4.02 (t, J
= 7.8 Hz, 2 H), 5.03 (ddt, J = 10.2, 1.9, 1.1 Hz, 1 H), 5.08 (dq, J
= 17.1, 1.7 Hz, 1 H), 5.88 (ddt, J = 17.1, 10.2, 6.7 Hz, 1 H), 5.99
(d, J = 2.7 Hz, 1 H), 6.54 (d, J = 2.7 Hz, 1 H), 7.18 (d, J = 6.9 Hz,
2 H), 7.28 (t, J = 7.3 Hz, 1 H), 7.35 (t, J = 7.2 Hz, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 11.4 (CH3), 23.7 (CH2), 34.3 (CH2),
38.4 (CH2), 48.1 (CH2), 108.5 (CH), 114.6 (C), 114.8 (CH2), 118.1
(CH), 126.4 (CH), 128.0 (C), 128.5 (CH), 128.6 (CH), 137.9 (CH),
138.4 (C) ppm. HRMS: calcd. for C17H21N 239.1674 [M]+; found
239.1674.
IR: ν = 3059 (m), 3026 (m), 2924 (m), 1598 (s), 1503 (s), 1452 (m),
˜
1343 (m), 1076 (m), 1029 (m), 994 (m), 909 (m), 750 (s), 699
(s) cm–1. MS (EI): m/z (%) = 375 (88) [M]+, 335 (19), 297 (20), 233
(26), 194 (100), 192 (25), 169 (23), 104 (21). HRMS: calcd. for
C28H25N 375.1981 [M]+; found 375.1982.
2-Benzyl-7-ethynyl-1,5-diphenyl-2,3,3a,4,5,7a-hexahydro-1H-iso-
1
indole (10b): Major diastereomer: H NMR (600 MHz, CDCl3): δ
= 1.51 (q, J = 12.8 Hz, 1 H), 2.00 (d, J = 12.8 Hz, 1 H), 2.10 (dd,
J = 10.0, 4.5 Hz, 1 H), 2.32 (s, 1 H), 2.57–2.61 (m, 1 H), 2.85 (t, J
= 10.0 Hz, 1 H), 3.07 (d, J = 13.0 Hz, 1 H), 3.42 (br. d, J = 12.8 Hz,
1 H), 3.48 (dd, J = 9.9, 7.9 Hz, 1 H), 3.53 (d, J = 9.9 Hz, 1 H),
3.82 (d, J = 13.0 Hz, 1 H), 6.36 (br. s, 1 H), 7.21–7.29 (m, 9 H),
7.35–7.37 (m, 4 H), 7.59 (d, J = 7.8 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 35.1 (CH), 37.6 (CH2), 42.8 (CH), 49.7
(CH), 57.6 (CH2), 59.0 (CH2), 73.5 (CH), 76.9 (CH), 83.3 (C),
120.7 (C), 126.5 (CH), 126.7 (CH), 127.3 (CH), 127.5 (CH), 127.9
(CH), 128.1 (CH), 128.5 (C), 128.6 (CH), 129.2 (CH), 139.5 (C),
141.8 (C), 142.0 (CH), 144.9 (C) ppm. IR: ν = 3060 (m), 3026 (m),
˜
(E)-1-Benzyl-2-(but-3-en-1-yl)-5-phenyl-3-styryl-1H-pyrrole (9c): 1H
NMR (600 MHz, CDCl3): δ = 2.10 (q, J = 7.1 Hz, 2 H), 2.63 (t, J
= 7.8 Hz, 2 H), 4.89 (d, J = 10.8 Hz, 1 H), 4.90 (d, J = 16.3 Hz, 1
H), 5.07 (s, 2 H), 5.67–5.77 (m, 1 H), 6.49 (s, 1 H), 6.76 (d, J =
16.0 Hz, 1 H), 6.85 (d, J = 7.2 Hz, 2 H), 7.00 (d, J = 16.0 Hz, 1
H), 7.10–7.31 (m, 11 H), 7.38 (d, J = 7.5 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 24.5 (CH2), 34.9 (CH2), 47.7 (CH2), 105.3
(CH), 115.4 (CH2), 119.7 (C), 121.3 (CH), 123.9 (CH), 125.6 (CH),
125.7 (CH), 126.3 (CH), 127.1 (CH), 127.2 (CH), 128.4 (CH), 128.5
(CH), 128.7 (CH), 128.9 (CH), 133.1 (C), 133.2 (C), 135.3 (C),
2921 (m), 2853 (m), 2789 (m), 1600 (m), 1492 (m), 1451 (m), 1077
(m), 1027 (m), 909 (m), 887 (m), 759 (s), 699 (s) cm–1. MS (EI): m/z
(%) = 389 (80) [M]+, 311 (100), 298 (22), 209 (40), 178 (17). HRMS:
calcd. for C29H27N 389.2143 [M]+; found 389.2141. Minor dia-
stereomer: 1H NMR (600 MHz, CDCl3): δ = 1.89 (br. d, J =
12.6 Hz, 1 H), 2.03 (td, J = 12.6, 7.6 Hz, 1 H), 2.11–2.21 (m, 1 H),
2.56 (s, 1 H), 2.56 (t, J = 10.5 Hz, 1 H), 2.64 (t, J = 9.1 Hz, 1 H),
2.89 (t, J = 8.9 Hz, 1 H), 3.42 (d, J = 13.5 Hz, 1 H), 3.76–3.78 (m,
2 H, 3-Hb), 3.82 (d, J = 13.5 Hz, 1 H), 6.19 (br. s, 1 H), 7.19–7.39
(m, 13 H), 7.59 (d, J = 7.5 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 33.9 (CH2), 36.9 (CH), 41.8 (CH), 51.2 (CH), 54.6
(CH2), 57.4 (CH2), 72.0 (CH), 78.7 (CH), 81.6 (C), 122.2 (C), 126.3
(CH), 126.5 (CH), 127.3 (CH), 127.6 (CH), 128.0 (CH), 128.1
(CH), 128.3 (CH), 128.4 (CH), 129.5 (CH), 139.5 (CH), 140.4 (C),
142.3 (C), 145.4 (C) ppm.
137.5 (CH), 138.7 (C), 138.9 (C) ppm. IR: ν = 3059 (m), 3026 (m),
˜
2924 (s), 2854 (m), 1633 (m), 1598 (m), 1495 (m), 1452 (m), 1353
(m), 1072 (m), 1028 (m), 954 (m), 911 (m), 752 (m), 730 (m), 696
(s) cm–1. HRMS: calcd. for C29H27N 389.2143 [M]+; found
389.2143.
(E)-2-Benzyl-4-benzylidene-3-(but-3-enyl)-1-phenyl-4,5,6,7-tetra- 4-Ethynyl-2,3,6-triphenyl-2,3,3a,6-tetrahydro-1H-isoindole (10c):
1
hydro-2H-isoindole (9d): H NMR (400 MHz, CDCl3): δ = 1.72
Single diastereomer: 1H NMR (600 MHz, CDCl3): δ = 2.72 (s, 1
(quint., J = 6.0 Hz, 2 H), 2.19–2.24 (m, 2 H), 2.56 (t, J = 6.1 Hz, H), 3.41 (br. t, J = 9.5 Hz, 1 H), 4.07 (br. d, J = 10.0 Hz, 1 H),
2 H), 2.71 (t, J = 6.0 Hz, 2 H), 2.77 (t, J = 8.2 Hz, 2 H), 4.87–4.95 4.10 (d, J = 12.4 Hz, 1 H), 4.60 (d, J = 12.4 Hz, 1 H), 4.65 (d, J =
(m, 2 H), 5.05 (s, 2 H), 5.74 (ddt, J = 17.0, 10.2, 6.6 Hz, 1 H), 6.60 8.5 Hz, 1 H), 5.62 (br. s, 1 H), 6.27 (br. s, 1 H), 6.57 (d, J = 8.6 Hz,
(s, 1 H), 6.85 (d, J = 7.0 Hz, 2 H), 7.17–7.27 (m, 13 H) ppm. 13C 2 H), 6.61 (t, J = 7.4 Hz, 1 H), 7.09 (t, J = 7.7 Hz, 2 H), 7.16–7.34
NMR (100 MHz, CDCl3): δ = 22.9 (CH2), 25.1 (CH2), 26.2 (CH2), (m, 8 H), 7.55 (d, J = 7.9 Hz, 2 H) ppm. 13C NMR (100 MHz,
Eur. J. Org. Chem. 2013, 7354–7365
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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7363

N. Thies, M. Gerlach, E. Haak
FULL PAPER
CDCl3): δ = 44.0 (CH), 49.4 (CH), 54.3 (CH2), 68.3 (CH), 78.9
CDCl3) cross peak: 1.99/5.88, Z isomer. HRMS: calcd. for
(CH), 82.5 (C), 113.4 (CH), 116.5 (CH), 117.5 (C), 119.4 (CH), C24H21N 323.1674 [M]+; found 323.1674.
126.9 (CH), 127.3 (CH), 128.0 (CH), 128.1 (CH), 128.3 (CH), 128.7
(E)-N-(1-Phenylhex-1-en-4-yn-3-yl)aniline (12): 1H NMR
(CH), 128.8 (CH), 134.6 (C), 139.8 (CH), 143.3 (C), 143.5 (C),
(400 MHz, CDCl3): δ = 1.78 (d, J = 2.1 Hz, 3 H), 3.70 (br. s, 1 H,
NH), 4.78 (br. s, 1 H), 6.22 (dd, J = 15.8, 5.4 Hz, 1 H), 6.66 (d, J
= 8.0 Hz, 2 H), 6.69 (t, J = 7.3 Hz, 1 H), 6.78 (d, J = 15.8 Hz, 1
H), 7.11–7.33 (m, 7 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 3.6
(CH3), 47.8 (CH), 77.5 (C), 80.8 (C), 114.1 (CH), 118.4 (CH), 126.6
(CH), 127.7 (CH), 127.8 (CH), 128.5 (CH), 129.1 (CH), 131.6
146.8 (C) ppm. IR: ν = 3059 (m), 3028 (m), 2923 (m), 2851 (m),
˜
1696 (s), 1598 (s), 1502 (s), 1469 (s), 1453 (s), 1362 (s), 1252 (m),
1178 (m), 1155 (m), 1075 (m), 1028 (m), 907 (m), 893 (m), 752
(s), 696 (s) cm–1. HRMS: calcd. for C28H23N 373.1830 [M]+; found
373.1830.
4Ј-Ethynyl-3Ј,6Ј-diphenyl-2Ј,3Ј,3aЈ,6Ј-tetrahydrospiro[cyclohexane-
1,1Ј-isoindole] (10d): Single diastereomer: 1H NMR (600 MHz,
CDCl3): δ = 1.20–1.83 (m, 10 H), 2.38 (s, 1 H), 3.34 (tt, J = 10.8,
2.6 Hz, 1 H), 4.00 (d, J = 10.5 Hz, 1 H), 4.10 (br. d, J = 11.2 Hz,
1 H), 5.50 (dt, J = 2.5, 1.7 Hz, 1 H), 6.15 (td, J = 2.5, 1.7 Hz, 1
H), 7.19 (d, J = 7.9 Hz, 2 H), 7.25–7.36 (m, 6 H), 7.54 (d, J =
7.9 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 22.3 (CH2),
23.1 (CH2), 25.6 (CH2), 36.6 (CH2), 40.5 (CH2), 44.4 (CH), 47.2
(CH), 60.5 (C), 65.3 (CH), 78.3 (CH), 82.1 (C), 117.5 (CH), 118.2
(C), 126.7 (CH), 127.5 (CH), 127.9 (CH), 128.1 (CH), 128.6 (CH),
128.7 (CH), 139.5 (CH), 142.4 (C), 144.3 (C), 148.5 (C) ppm.
HRMS: calcd. for C27H27N 365.2143 [M]+; found 365.2143.
(CH), 136.4 (C), 146.4 (C) ppm. HRMS: calcd. for C18H17
N
247.1361 [M]+; found 247.1362.
2-Ethyl-1,5-diphenyl-1H-pyrrole (13):[12b] 1H NMR (400 MHz,
CDCl3): δ = 1.07 (t, J = 7.5 Hz, 3 H), 2.40 (q, J = 7.5 Hz, 2 H),
6.05 (d, J = 3.4 Hz, 1 H), 6.32 (d, J = 3.4 Hz, 1 H), 6.98–7.30 (m,
10 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 13.0 (CH3), 20.5
(CH2), 105.6 (CH), 108.6 (CH), 123.5 (C), 125.6 (CH), 127.4 (CH),
127.9 (CH), 128.6 (CH), 128.9 (CH), 129.2 (CH), 134.5 (C), 138.1
(C), 139.3 (C) ppm. HRMS: calcd. for C18H17N 247.1361 [M]+;
found 247.1362.
Complex 14c: A solution of Et3O·BF4 in CH2Cl2 (0.2 mmol, 1 m)
was added dropwise to a solution of catalyst 1 (0.2 mmol) in
CH2Cl2 (5 mL) at 0 °C. The mixture was stirred at room temp. for
1 h under argon. Evaporation of the solvent and flash chromatog-
raphy on silica gel furnished complex 14c as a pale-yellow foam.
1H NMR (400 MHz, CDCl3): δ = 0.69 (t, J = 7.2 Hz, 3 H), 2.20
(s, 6 H), 2.62 (ddd, J = 16.6, 6.6, 3.8 Hz, 2 H), 3.29 (q, J = 7.2 Hz,
2 H), 3.60 (ddd, J = 16.6, 6.6, 3.4 Hz, 2 H), 7.40–7.42 (m, 6 H),
7.57–7.59 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.7
(CH3), 41.6 (CH3), 49.9 (CH2), 72.0 (CH2), 76.0 (C), 118.6 (C),
127.1 (CH), 129.1 (CH), 129.8 (C), 132.8 (CH), 139.7 (C), 192.6
(Z)-N-(3-Methyl-1-phenylhex-2-en-4-yn-1-yl)-2-(1H-pyrrol-1-yl)-
1
aniline (11a): H NMR (400 MHz, CDCl3): δ = 1.91 (br. s, 3 H),
2.11 (br. s, 3 H), 4.28 (br. s, 1 H, NH), 5.57 (br. d, J = 9.0 Hz, 1
H), 5.64 (br. d, J = 9.0 Hz, 1 H), 6.47 (br. s, 2 H), 6.81–6.85 (m, 2
H), 6.98 (br. s, 2 H), 7.23–7.47 (m, 7 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 4.4 (CH3), 23.3 (CH3), 57.8 (CH), 78.5 (C), 91.4 (C),
109.4 (CH), 112.7 (CH), 116.7 (CH), 120.8 (C), 121.7 (CH), 126.0
(CH), 126.8 (CH), 127.2 (CH), 127.4 (C), 128.6 (CH), 128.7 (CH),
136.4 (CH), 142.2 (C), 142.7 (C) ppm; NOESY (600 MHz, CDCl3)
cross peak: 1.91/5.64, Z isomer. HRMS: calcd. for C23H22N2
326.1783 [M]+; found 326.1783.
(C, CO) ppm. IR: ν = 3060 (w), 2958 (m), 2928 (m), 2873 (m), 2857
˜
(m), 2086 (s), 2017 (s), 1730 (w), 1673 (w), 1598 (s), 1501 (s), 1482
(s), 1444 (s), 1417 (s), 1365 (s), 1344 (s), 1316 (s), 1279 (s), 1205
(m), 1119 (m), 1050 (s), 1001 (s), 951 (s), 913 (s), 858 (s), 823 (m),
797 (w), 779 (m), 752 (s), 724 (s), 701 (s) cm–1. MS (EI): m/z (%) =
506 (12), 505 (33), 504 (18), 503 (65) [M]+, 502 (39), 501 (26), 500
(20), 497 (10), 481 (50), 445 (29), 417 (100), 389 (50). HRMS: calcd.
for C25H25N2O3Ru 503.0909 [M]+; found 503.0902.
(Z)-N-(3-Methyl-1,5-diphenylpent-2-en-4-yn-1-yl)-2-(1H-pyrrol-1-
yl)aniline (11b): 1H NMR (400 MHz, CDCl3): δ = 2.01 (br. s, 3 H),
4.31 (br. s, 1 H, NH), 5.61 (br. d, J = 8.8 Hz, 1 H), 5.76 (br. d, J
= 9.0 Hz, 1 H), 6.42 (br. s, 2 H), 6.80 (t, J = 7.5 Hz, 1 H), 6.87 (d,
J = 8.0 Hz, 1 H), 6.93 (br. s, 2 H), 7.20–7.50 (m, 12 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 23.0 (CH3), 58.2 (CH), 88.0 (C),
94.9 (C), 109.5 (CH), 112.7 (CH), 116.9 (CH), 120.5 (C), 121.9
(CH), 123.0 (C), 126.2 (CH), 127.0 (CH), 127.4 (CH), 127.5 (C),
128.3 (CH), 128.4 (CH), 128.7 (CH), 128.8 (CH), 131.5 (CH), 138.2
(CH), 142.0 (C), 142.8 (C) ppm; NOESY (600 MHz, CDCl3) cross
peak: 2.01/5.76, Z isomer. HRMS: calcd. for C28H24N2 388.1939
[M]+; found 388.1939.
Supporting Information (see footnote on the first page of this arti-
cle): Full characterization data, NMR assignments and 1H and 13
NMR spectra of all key intermediates and final products.
C
Acknowledgments
1
(E)-N-(1-Phenylhex-2-en-4-ynyl)aniline (11c): H NMR (600 MHz,
CDCl3): δ = 1.84 (d, J = 2.0 Hz, 3 H), 3.90 (br. s, 1 H, NH), 4.86
(d, J = 5.9 Hz, 1 H), 5.61 (dq, J = 15.8, 1.9 Hz, 1 H), 6.13 (dd, J
= 15.8, 5.9 Hz, 1 H), 6.49 (d, J = 8.0 Hz, 2 H), 6.62 (t, J = 7.3 Hz,
1 H), 7.05 (t, J = 7.5 Hz, 2 H), 7.22–7.26 (m, 5 H) ppm. 13C NMR
(150 MHz, CDCl3): δ = 4.2 (CH3), 60.2 (CH), 77.6 (C), 87.3 (C),
111.8 (CH), 113.5 (CH), 117.8 (CH), 127.2 (CH), 127.7 (CH), 128.8
(CH), 129.1 (CH), 141.2 (C), 142.0 (CH), 146.9 (C) ppm. HRMS:
calcd. for C18H17N 247.1361 [M]+; found 247.1361.
N. T. thanks the state of Saxony-Anhalt for a graduate fellowship.
[1] For selected reviews, see: a) M. Bartlett, Chem. N. Z. 2012, 76,
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1
(Z)-N-(3-Methyl-1,5-diphenylpent-2-en-4-yn-1-yl)aniline (11d): H
NMR (400 MHz, CDCl3): δ = 1.99 (br. s, 3 H), 4.11 (br. s, 1 H,
NH), 5.54 (br. d, J = 8.9 Hz, 1 H), 5.88 (br. d, J = 8.9 Hz, 1 H),
6.71 (d, J = 8.3 Hz, 2 H), 6.73 (t, J = 7.5 Hz, 1 H), 7.17 (t, J =
8.0 Hz, 1 H), 7.29–7.44 (m, 8 H), 7.51 (d, J = 7.6 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 23.1 (CH3), 58.7 (CH), 88.1 (C),
94.9 (C), 113.6 (CH), 117.7 (CH), 120.1 (C), 123.1 (C), 126.6 (CH),
127.4 (CH), 128.3 (CH), 128.4 (CH), 128.9 (CH), 129.2 (CH), 131.6
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7364
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Received: May 30, 2013
Published Online: September 24, 2013
Eur. J. Org. Chem. 2013, 7354–7365
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7365