Synthesis and application of a novel bis-1,2,3-triazole ligand containing a 2,2'-bipyrrolidine core

Article abstract of DOI:10.24820/ark.5550190.p010.320

Herein, we describe the synthesis of a novel bis-1,2,3-triazole ligand which contains an internal N-alkylated 2,2'-bipyrrolidine linker. By using simple starting materials, the ligand could be generated in good yield through several synthetic steps. To investigate the potential for the application of this ligand in transition metal catalysis, we generated a bis-Au(I) complex in nearly quantitative yield and examined its reactivity in the context of alkyne hydration. Both alkyl and aryl terminal alkynes could be efficiently converted to their corresponding ketones in nearly quantitative yields with only 1% catalyst loading under mild conditions.

Full text of DOI:10.24820/ark.5550190.p010.320

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Arkivoc 2018, part ii, 280-287
Organic Chemistry
Synthesis and application of a novel bis-1,2,3-triazole ligand
containing a 2,2’-bipyrrolidine core
Stephen E. Motika and Xiaodong Shi*
Department of Chemistry, University of South Florida, Tampa, FL 33620, USA
Email: xmshi@usf.edu
Dedicated to Dr. Kenneth Laali for his outstanding contributions in the field of synthetic organic chemistry
Received 08-28-2017
Accepted 12-15-2017
Published on line 01-28-2018
Abstract
Herein, we describe the synthesis of a novel bis-1,2,3-triazole ligand which contains an internal N-alkylated
,2’-bipyrrolidine linker. By using simple starting materials, the ligand could be generated in good yield
2
through several synthetic steps. To investigate the potential for the application of this ligand in transition
metal catalysis, we generated a bis-Au(I) complex in nearly quantitative yield and examined its reactivity in the
context of alkyne hydration. Both alkyl and aryl terminal alkynes could be efficiently converted to their
corresponding ketones in nearly quantitative yields with only 1% catalyst loading under mild conditions.
Keywords: 1,2,3-Triazole, gold catalysis, alkyne hydration
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Introduction
Over the past century, ligand design has been integral to the realization of new catalytic approaches relying on
transition metals. In many cases, subtle changes in ligand structure and electronic character have dramatic
influences on the stability and reactivity of the metal to which it is bound. This intimate relationship between
structure and reactivity has therefore been an impetus to pursue new ligand systems. Despite the structural
complexity inherent to many effective classes of ligand, much of this work relies on the inherent properties of
privileged small molecules, which when derivatized in unique ways, form structurally unique ligand scaffolds.
In the past decade, our group has found success in implementing functionalized 1,2,3-triazoles (TAs) as
ligands for late transition metals. Thus far, we have demonstrated that these electron-poor heterocycles have
1
2
3
4
5-9
a high affinity to bind to mid to late transition metals such as Rh, Pd, Fe, Ir, and Au. In the case of Au(I),
10,11
neutral TA ligands can dramatically enhance the thermal stability and chemoselectivity of the Au-cation.
In
the absence of neutral secondary ligands or strong sigma-donating spectator ligands, Au-cation often
1
2
decomposes to a metallic form through external reduction or disproportionation pathways. By harnessing
the productive partnership between Au(I) and TA, we have broadened the scope of Au-catalysis by generating
new catalyst libraries that offer broad electronic and structural range.
Our insight and background in TA synthesis and its metal coordination has naturally led us to consider new
and abstract ligand systems containing this heterocycle. Furthermore, we were particularly interested in the
prospect of a bis-TA ligand that could simultaneously accommodate two metal atoms, as described in Scheme
1
. In the context of Au-catalysis, generating a new class of bis-Au(I) complexes may provide new avenues to
access and productively utilize Au-Au intermediates. Additionally, the 2-coordinate nature of Au(I) would
allow us to avoid the formation of chelation complexes. To establish this structural paradigm, we realized it
would necessary to identify an adequate TA scaffold and linker. After considering several viable linkers, we
chose to investigate the 2,2’-bipyrrolidine structure, as this would provide a mild synthetic platform hinging on
N-alkylation, a step easily conceived through an S 2 reaction. Moreover, a TA subunit containing a leaving
N
group would be paramount to execute this design.
Scheme 1. Basic design for the synthesis of bis-1,2,3-triazole-Au(I) complex.
Results and Discussion
As described in the introduction, our first task was to generate a TA subunit that would be poised for
amination in the presence of 2,2’-pyrrolidine backbone. This would ultimately involve discerning a TA-
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synthesis that would easily allow the incorporation of a leaving group. With this in mind, we could easily
adopt an adequate alkyne precursor for the formation of the heterocyclic core. As described in Scheme 2,
alkyne 2 could be easily generated under typical alkyne-acylation procedures. From alkyne 2, we could
efficiently access TA 3 through cycloaddition with NaN with good overall yield. The ester on TA 3 was then
3
reduced to the corresponding alcohol using excess LiAlH , which will be important for the generation of a good
4
leaving group later. Following reduction, N2-alkylation was performed to give TA 5 in high yields and N2
selectivity. The N2 selectivity was confirmed by performing a series of 1D NOE experiments on the product
obtained. This step was performed for two reasons, the first being to inhibit unwanted dimerization when
the subsequent alkyl bromide is formed, and the second being to specifically investigate N1 or N3 binding with
the Au-cation. Compound 5 was then treated with PBr at lower temperatures to give the key and final
3
product, TA 6.
Scheme 2. Synthesis of TA subunit.
Following the successful synthesis of TA 6, we proceeded with the di-N-alkylation of (2R,2'R)-2,2'-
bipyrrolidine as illustrated in Scheme 3. After a brief reaction screening, it was determined that treating the
two components with potassium carbonate at room temperature in DCM efficiently provided target 7 in good
yield. With the desired compound in hand, we then generated the bis-Au complex 8 by treating the ligand
with two equivalents of Ph PAuCl and two equivalents of AgOTf. Upon the addition of AgOTf, a white
3
precipitate (AgCl) could be seen almost immediately. The complex prepared through this step was
1
13
31
characterized using H, C, and P NMR analysis. However, we have not been able to grow an adequate
crystal for X-ray analysis. It is important to note that the broad nature of the NMR spectra for the complex
suggests some dynamic bonding behavior in solution. This is likely due to the coalescence of a number of
1
13
different regioisomer signals at room temperature. Nevertheless, the dramatic change in H and C NMR
spectra are strongly indicative of some significant level of bonding interaction. Additionally, the difference in
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3
1
chemical shift (δ 25.8 ppm) observed in the P NMR signal relative to pure Ph PAuCl (δ 34.3 ppm) and
3
1
0
Ph PAuOTf (δ 28.8 ppm) is a compelling result that strongly supports complex formation. At this point
3
though, it is difficult to determine any specific binding motif in solution. It is also important to note here that
the complex generated when using only one equivalent of Ph PAuCl was quite unstable and clearly started to
3
decompose upon work up and solvent removal.
Scheme 3. Synthesis of bis-TA-ligand and complexation to Au(I).
Following the synthesis of complex 8, we next wanted to establish some catalytic activity. To accomplish
this, we investigated terminal alkyne hydration under relatively mild conditions. At room temperature, very
little alkyne hydration could be seen after 24 hours. However, as shown in Scheme 4, when the reaction
o
temperature was raised to 50 C both alkyl and aryl terminal alkynes could undergo hydration in almost
quantitative yield. Interestingly, only the free ligand could be observed at the end of the reaction, which
suggests that the Au-catalyst is decomposing upon reaction completion. This is perhaps due to a
decomposition pathway resulting from competitive coordination from water or the resulting ketone product.
Despite the decomposition of the catalyst observed upon complete conversion of the starting material, we
were surprised to see such high efficiency given the presence of a tertiary amine within the ligand. In some
1
3
cases, amines and thiols lead to Au(I)-catalyst deactivation due to their high nucleophilicity. However , the
bulkier tertiary amine and competitive coordination of other functional groups in the ligand is likely to inhibit
deactivation to any great extent.
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Scheme 4. Assessing catalytic activity in alkyne hydration.
Conclusions
As reported here, we have been able to synthesize a new bis-TA ligand which appeared to bind effectively to
Au(I). Based on NMR data, the ligand is interacting with Au(I) in a very dynamic fashion. This catalyst exhibits
good thermal stability and high efficiency in the hydration reaction of terminal aryl and alkyl alkynes, which
proves that the tertiary amines within the ligand do not lead to Au(I) deactivation. In summary, we believe
these results may give way to new ligand-metal paradigms that will offer insight to new methodological
advances.
Experimental Section
General. All reactions were carried out under an atmosphere of nitrogen using oven or flame dried glassware
and standard syringe/septa techniques. Unless noted, all commercial reagents and solvents were used without
further purification. Flash column chromatography was performed on 230-430 mesh silica gel. Analytical thin
layer chromatography was performed with pre-coated, glass-baked plates (250μ) and visualized by
1
fluorescence or charring with potassium permanganate stain. Melting point were recorded on Mel-Temp. H
1
3
31
NMR, C NMR and P NMR spectra were recorded on an Agilent 400 MHz spectrometer. Chemical shifts for
starting materials and products were reported relative to tetramethylsilane (0.00 ppm) or CD OD (3.31 ppm)
3
1
13
31
for H NMR data, CDCl (77.0 ppm) or CD OD (49.9) for C NMR and H PO /D O for P NMR data. Data are
3
3
3
4
2
presented as follows: chemical shift (ppm), multiplicity (s = singlet, d = doublet, t = triplet, dd = doublet of
doublets, m = multiplet, br = broad), coupling constant J (Hz) and integration. ESI-MS spectra were collected
using a Thermo Scientific Orbitrap Q Extractive Plus (Bremen, Germany) in the positive ion mode. The samples
were infused with a flow rate of 10 μL/min and sprayed at a high voltage of 5 kV.
Synthesis of ethyl 3-phenylpropiolate (2). To a nitrogen flushed round bottom flask with a solution of
o
phenylacetylene (2.04 g, 20 mmol) in distilled THF (20 mL) at –78 C was added n-BuLi (8.4 mL, 21 mmol, 2.5 M
in hexane) dropwise. The solution was stirred at this temperature for approximately 1 hour. After this time,
o
ethyl chloroformate (2.3 mL, 24 mmol, neat) was added at -78 C. The solution stirred at this temperature and
was monitored by TLC. Complete conversion could be observed after approximately 2.5 hours. Upon
completion, the reaction was quenched through the addition of a saturated solution of NH Cl at room
4
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temperature. The organic layer was extracted with ethyl acetate (3 × 20 mL) and dried using sodium sulfate.
This solution was filtered through a plug of cotton and concentrated by rotary evaporation. The crude
reaction product was then purified using column chromatography (gradient from 20:1 to 5:1 hexanes: ethyl
1
13
acetate) to give 2.8 g (80% yield) of the alkyne as a clear oil. The H and C NMR spectra for this internal
1
4, 15, 16
alkyne matched identically to the many previous reported syntheses.
Synthesis of ethyl 5-phenyl-1H-1,2,3-triazole-4-carboxylate (3). To a gently stirred solution of alkyne 2 (1.75 g, 10
mmol) in DMSO (20 mL, 0.5 M) was added NaN (1.9 g, 30 mmol) in four portions over 20 minutes. Once the
3
o
NaN was completely dissolved, the unsealed reaction was heated to 80 C for 8 hours. Upon completion,
3
distilled water was slowly added to the reaction followed by slow and incremental addition of 1.0 M HCl until a
pH of 1 was reached. The solution was then extracted using DCM (3 x 30 mL). The organic layer was washed
with brine and dried over sodium sulfate. Following filtration and concentration of the organics by rotary
evaporation, the crude product was purified via recrystallization (5:1 Hexanes: DCM) to give triazole 3 (1.7 g,
o
1
8
6
0%) as an off-white powder. mp 92-93 C. H-NMR (400 MHz; CDCl ): δ 7.79 (m, 2H), 7.40 (m, 3H), 4.36 (q, J
3
1
3
.9 Hz, 2H), 1.28 (t, J 7.2 Hz, 3H); C-NMR (101 MHz; CDCl ): δ 161.2, 129.7, 129.2, 128.2, 61.6, 13.9. HRMS
3
+
Calculated for C H N O [M+H] : 218.0924, Found: 218.0930.
1
1 12 3 2
1
7
Synthesis of (5-phenyl-1H-1,2,3-triazol-4-yl)methanol (4). A solution of 3 (1.5 g, 7 mmol) in THF (23 mL, 0.3 M)
o
was cooled to 0 C in an ice bath. LiAlH (380 mg, 10 mmol) was then added to the solution in four portions
4
over 20 minutes. The reaction mixture was then warmed to room temperature and stirred for 30 minutes.
o
Upon completion, as confirmed by TLC, the reaction was then cooled back down to 0 C and quenched
through dropwise addition of a saturated ammonium cloride solution. The reaction mixture was then acidified
by addition of 1.0 M HCl. This was then extracted using DCM (3 x 30 mL). The organics were then dried over
sodium sulfate, filtered and concentrated via rotary evaporation. The crude reaction material was then
purified using trituration and recrystallization (approximately 3:1 Hexanes: DCM) to give triazole 4 (1.0 g, 82 %)
o
1
as a white solid. m.p. 133-134 C. H-NMR (400 MHz; CD OD): δ 7.59-7.57 (m, 2H), 7.38-7.34 (t, J 7.5 Hz, 2H),
3
1
3
7
.26-7.24 (m, 1H), 4.65 (s, 2H); C-NMR (101 MHz; CD OD): δ 143.2, 140.7, 132.3, 128.7, 127.1, 126.9, 54.6.
3
+
Calculated for C H N O [M+H] : 176.0818, Found: 176.0821.
9
10 3
Synthesis of methyl 2-[4-(hydroxymethyl)-5-phenyl-2H-1,2,3-triazol-2-yl]-2-methylpropanoate (5). A solution
containing alcohol 4 (875 mg, 5 mmol), methyl α-bromoisobutyrate (1.8 g, 10 mmol) and potassium carbonate
o
(
1.37 g, 10 mmol) in DMF (10 mL, 0.5 M) was heated to 60 C for 6 hours. The reaction was cooled to room
temperature and water (20 mL) was added. This solution was then extracted with diethyl ether (3 x 20 mL) and
dried over sodium sulfate. This mixture was filtered and concentrated using rotary evaporation. The crude
product was then purified using column chromatography (gradient from 10:1 to 3:1 hexanes: ethyl acetate) to
1
give 1.20 g (85 % yield) of triazole 5 as a viscous colorless oil. H-NMR (400 MHz; CDCl ): δ 7.83-7.80 (m, 2H),
3
1
3
7
.45-7.41 (m, 2H), 7.36 (dd, J 8.6, 6.1 Hz, 1H), 4.86 (s, 2H), 3.69 (s, 3H), 1.97 (s, 6H); C-NMR (101 MHz; CDCl ):
3
+
δ 172.4, 145.5, 143.8, 130.4, 128.7, 128.3, 127.5, 67.8, 56.2, 52.9, 25.3. Calculated for C H N NaO [M+Na] :
1
4
17
3
3
2
98.1162, Found: 298.1164.
Synthesis of methyl 2-[4-(bromomethyl)-5-phenyl-2H-1,2,3-triazol-2-yl]-2-methylpropanoate (6). A solution
o
of ester 5 (1.10 g, 4 mmol) in DCM (10 mL, 0.4 M) was cooled to 0 C under a stream of nitrogen gas. PBr (1.7
3
g, 6.4 mmol) was then added to the solution dropwise. The reaction was then stirred at this temperature and
monitored by TLC until completion. Upon completion, a saturated sodium bicarbonate solution was added to
o
the reaction at 0 C. Once gas evolution was no longer apparent, water (10 mL) was added to the crude
reaction mixture. This solution was then extracted using DCM (3 x 20 mL). The organic extracts were then
dried over sodium sulfate, filtered and concentrated. The crude reaction mixture was then purified using
column chromatography (gradient from 12:1 to 6:1 hexanes: ethyl acetate) to give 835 mg (62% yield) of
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1
triazole 6 as a white solid. Mp 90-92 C. H-NMR (400 MHz; CDCl ): δ 7.80 (dd, J 8.2, 1.1 Hz, 2H), 7.48-7.44 (m,
3
1
3
2
1
3
H), 7.40-7.38 (m, 1H), 4.66 (s, 2H), 3.70 (s, 3H), 1.98 (s, 6H); C-NMR (101 MHz; CDCl ): δ 172.1, 145.6, 141.0,
3
+
30.0, 128.8, 128.6, 127.6, 68.2, 53.0, 25.3, 22.6. Calculated for C H BrN O [M+H] : 338.0499, Found:
1
4
17
3 2
38.0499.
Synthesis of dimethyl 2,2'-{[(2,2'-bipyrrolidine)-1,1'-diylbis(methylene)]bis-(5-phenyl-2H-1,2,3-triazole-4,2-
diyl)}bis-(2-methylpropanoate) (ligand 7). A solution of 6 (674 mg, 2 mmol), (2R,2'R)-2,2'-bipyrrolidine (265
mg, 1.9 mmol) and potassium carbonate (410 mg, 3 mmol) in DCM (7 mL, 0.3 M) was stirred at room
temperature. The reaction was monitored for completion using TLC. Upon completion, water (10 mL) was
added and extractions using DCM (3x 15 mL) were performed. The organic layers were dried over sodium
sulfate, filtered and concentrated. The crude reaction mixture was then purified using column
chromatography (gradient from 5:1 to 1:1 hexanes ethyl acetate) to give 1.05 g (85% yield) of ligand 7 as a
o
1
light yellow solid. mp 64-65 C, H-NMR (400 MHz; CDCl ): δ 7.94 (d, J 7.3 Hz, 4H), 7.37 (t, J 7.3 Hz, 4H), 7.31 (d,
3
J 7.0 Hz, 2H), 3.97 (d, J 12.8 Hz, 2H), 3.66 (s, 6H), 3.51 (d, J 12.8 Hz, 2H), 2.83 (t, J 7.6 Hz, 2H), 2.76 (t, J 6.5 Hz,
1
3
2
H), 2.28 (td, J 9.6, 6.8 Hz, 2H), 1.92 (2s, J 3.1 Hz, 12H), 1.77 (m, 4H), 1.63 (m, 4H); C-NMR (101 MHz; CDCl3):
δ 172.5, 146.0, 142.8, 131.2, 128.3, 128.1, 127.9, 67.5, 64.8, 54.7, 52.8, 49.6, 26.1, 25.4, 25.2, 23.9. Calculated
+
for C H N O [M+H] : 655.3715, Found: 655.3726.
3
6 47 8 4
Synthesis of complex 8. Ligand 7 (82 mg, 0.125 mmol) and Ph PAuCl (123 mg, 0.25 mmol) were dissolved in
3
DCM (625 µL, 0.2 M) at room temperature. To this solution was added AgOTf (64 mg, 0.25 mmol). AgCl
immediately precipitated out of solution as a white solid. This solution stirred for 2 hours followed by gravity
filtration through two pipettes filled halfway with celite. The filtrate was then collected and concentrated to
give a light yellow solid. Recrystallization was then performed to give 190 mg (95% yield) of complex 8 as an
1
off-white solid. H-NMR (400 MHz; CDCl ): δ 7.56-7.34 (m, 38H), 4.49 (m, 2H), 3.67 (s, 7H), 3.39 (s, 1H), 2.91 (s,
3
1
3
1
1
H), 1.90 (m, 22H); C-NMR (101 MHz; CDCl ): δ 172.1, 134.1, 133.9, 133.8, 132.4, 129.6, 129.5, 129.4, 129.2,
3
3
1
29.1, 128.1, 127.8, 68.7, 53.1, 25.2; P-NMR (162 MHz; CDCl ): δ 25.8.
3
General procedure for alkyne hydration (Scheme 4). In an NMR tube, alkyne (phenylacetylene: 24 mg, 0.24
mmol; 1-hexyne: 20 mg, 0.24 mmol) complex 8 (5 mg, 0.0024 mmol) and p-xylene (25 mg, 0.24 mmol, internal
o
standard) were dissolved in deuterated methanol ( 0.6 mL, 0.4 M). The reaction was then heated to 50 C and
1
monitored every 10 minutes by H NMR until completion.
Acknowledgements
We would like to acknowledge the financial support of the NSF (CHE-1619590), NIH(1R01GM120240-01) and
NSFC (21629201).
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