Angewandte

Communications Chemie

International Edition: DOI: 10.1002/anie.201607742

Dehydrogenative Coupling Hot Paper German Edition: DOI: 10.1002/ange.201607742

Direct Synthesis of Pyrroles by Dehydrogenative Coupling of Diols and

Amines Catalyzed by Cobalt Pincer Complexes
Prosenjit Daw+, Subrata Chakraborty+, Jai Anand Garg, Yehoshoa Ben-David, and
David Milstein*
Abstract: Herein, the first example of base-metal-catalyzed amines, and base was demonstrated by Beller et al.[16] An
dehydrogenative coupling of diols and amines to selectively interesting dehydrogenative coupling of 2,5-hexanediol and
form functionalized 1,2,5-substituted pyrroles liberating water amines to form pyrroles, albeit in modest yields (45–48 %),
and hydrogen gas as the sole by-products is presented. The catalyzed by a ruthenium complex in the presence of sodium
reaction is catalyzed by pincer complexes of earth-abundant formate, was developed by Crabtree et al.[17]
cobalt. However, despite the importance of such elegant methods
for the synthesis of pyrroles employing noble metals, the
Pyrroles and their derivatives are valuable intermediates in development of nonprecious base-metal catalysts would be
the synthesis of numerous natural products, agrochemicals, a significant advance from the perspective of abundance, cost,
flavors, dyes, and functional materials.[1] They also have and sustainability.[18] Moreover, precious metals are often
antibacterial, antitumor, anti-inflammatory, and antifungal toxic, and potential contamination by particles of these metals
properties.[2] Polypyrroles are conducting polymers and used is a significant issue in the pharmaceutical industry. Remark-
in solar cells[3] and batteries;[4] they can also be used as able progress has been made in recent years regarding
antioxidants and gas sensors.[5] The classical methods for catalysis by complexes of first-row base metals (Fe, Mn, Ni,
pyrrole synthesis involve the Knorr,[6] Paal–Knorr[7] and Co).[19–21] For example, several homogeneous cobalt catalysts
Hantzsch[8] reactions. Lately, metal-catalyzed cyclization[9] were discovered to be effective in the hydrogenation of
and multicomponent coupling reactions[10] have been devel- olefins,[21a,f] imines,[21a] ketones,[21b] and CO2.[21h,i] Recently, we
oped for the synthesis of functionalized pyrroles. Although reported the first ester hydrogenation[22a] and nitrile hydro-
these protocols are effective, most of them suffer from several genation[22b] reactions catalyzed by a pyridine-based PNNH–
shortcomings, such as poor availability of starting materials, Co pincer complex. Homogeneous cobalt catalysts have also
multi-step synthetic operations, and copious waste genera- been exploited for dehydrogenation and dehydrogenative
tion. coupling reactions. Hanson and Zhang first reported dehy-
In terms of sustainable synthesis, an environmentally drogenation of secondary alcohols and dehydrogenative
benign route to pyrroles from renewable resources would be coupling of alcohols and amines to form imines, catalyzed
highly desirable. In this respect direct access to substituted by a cationic PNP–Co pincer complex (Figure 1 a).[21b] Jones
pyrroles from readily available feedstocks like alcohols and et al. described the acceptorless dehydrogenation and hydro-
polyols is attractive since alcohols are either industrial genation of N-heterocycles using the same catalyst.[23] Very
products or can be derived from lignocellulosic biomass.[11] recently the groups of Kempe,[24a] Zhang,[24b] and Kirchner[24c]
Indeed, notable progress has been made in recent years in independently reported cobalt-catalyzed amine alkylation
sustainable pyrrole synthesis based on the acceptorless reactions by alcohols (Figure 1 a).
dehydrogenation of alcohols[12] using complexes based on Herein, we report a pyrrole synthesis catalyzed for the
the noble metals Ir and Ru.[13] Kempe and Michlik first first time by a base-metal complex. It involves acceptorless
reported the efficient synthesis of pyrroles by reaction of dehydrogenative coupling of 1,4-substituted 1,4-butanediols
amino alcohols with secondary alcohols catalyzed by triazine– and various amines using a cobalt pincer complex to generate
iridium complexes,[14] and we reported in the same year that 1,2,5-substituted pyrroles with extrusion of water and H2 as
PNN–ruthenium pincer complexes are efficient catalysts for the only by-products.
this reaction.[15] Attractive synthesis of various substituted Initially, we explored the possibility of pyrrole formation
pyrroles catalyzed by [Ru3(CO)12]/Xantphos and [RuCl2(p- from diols and amines using our most promising PNNH–Co
cymene)]2/Xantphos systems using ketones, vicinal diols, precatalyst 1[22a] (Figure 1 b). To generate the active species,
the use of one equiv of NaHBEt3 and tBuOK as hydride
source and base, respectively, was envisioned as observed in
[*] Dr. P. Daw,[+] Dr. S. Chakraborty,[+] Dr. J. A. Garg, Y. Ben-David, our earlier work on PNNH–Co-catalyzed ester and nitrile
Prof. D. Milstein
hydrogenations.[22]
Department of Organic Chemistry, Weizmann Institute
Rehovot, 76100 (Israel) Reaction of 2,5-hexanediol with n-heptylamine using
E-mail: david.milstein@weizmann.ac.il NaHBEt3, tBuOK, and complex 1 in toluene in a closed
[+] These authors contributed equally to this work. system in the presence of 4 c molecular sieves resulted in the
Supporting information and the ORCID identification number(s) for formation of N-heptyl-2,5-dimethylpyrrole in 74 % yield at
the author(s) of this article can be found under http://dx.doi.org/10. 120 8C and in 92 % yield at 150 8C after 24 h (Table 1, entries 1
1002/anie.201607742. and 2). Analysis of the gas phase by gas chromatography

Angew. Chem. Int. Ed. 2016, 55, 14373 –14377 T 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 14373
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Figure 1. a) Known Co-catalyzed dehydrogenation and dehydrogenative coupling reactions. b) Co pincer complexes explored in this study for
pyrrole synthesis.

Table 1: Optimization of the reaction conditions for the dehydrogenative formation of pyrrole at 150 8C (Table 1, entry 5), probably due
coupling of 2,5-hexanediol and heptylamine. to steric effects, whereas isopropyl-substituted catalyst 2 b
produced 21 % of N-heptyl-2,5-dimethylpyrrole (entry 6) and
complex 3 yielded 77 % of the pyrrole (entry 7). However, the
yield of pyrrole was only 4 % when the bipyridine-based
complex 4 was used (entry 8). Therefore the best-performing
Entry[a] Cat. x Base (y) T [88C] Conv[b] Yield[b] complex 1 was chosen for further optimization studies.
[%] [%] Exploring the effect of various bases, KHMDS, NaOEt,
1 1 5 tBuOK (5) 120 99 74 and KH were employed under similar reaction conditions
2 1 5 tBuOK (5) 150 99 92[c] giving decent yields of pyrroles (entries 9–11). Further testing
3[d] 1 5 tBuOK (5) reflux 99 71 revealed that in the absence of NaHBEt3, using 5 mol % of
4[e] 1 5 tBuOK (5) 150 99 40 pre-catalyst 1 and 5 mol % tBuOK at 120 8C, no conversion
5 2a 5 tBuOK (5) 150 0 0
was observed (entry 12), in the absence of base, using 5 mol %
6 2b 5 tBuOK (5) 150 82 21
7 3 5 tBuOK (5) 150 99 77[c] NaHBEt3 and 5 mol % of 1, only 16 % of N-heptyl-2,5-
8 4 5 tBuOK (5) 150 66 4 dimethylpyrrole were obtained (entry 13), and in the absence
9 1 5 KHMDS (5) 150 99 85[c] of both tBuOK and NaHBEt3, no reaction took place
10 1 5 NaOEt (5) 150 99 79[c] (entry 14). The aforementioned experiments indicate that
11 1 5 KH (5) 150 99 90[c] both NaHBEt3 and tBuOK play crucial roles in generating the
12 1 – tBuOK (5) 120 0 0 catalytically active species. However, higher loading of either
13 1 5 – 120 99 16
of them (tBuOK or NaHBEt3) (to 10 mol %) under otherwise
14 1 – – 120 0 0
15 1 10 tBuOK (5) 120 99 72 identical conditions did not significantly improve the yield of
16 1 5 tBuOK (10) 120 99 70 pyrrole (entries 15 and 16). Changing the solvent to 1,4-
17[f ] 1 5 tBuOK(5) 120 99 71 dioxane instead of toluene at 120 8C did not have a significant
[a] Conditions: 2,5-hexanediol (0.5 mmol), heptylamine (0.5 mmol), and effect (entry 17). It is worth mentioning at this point that the
dry toluene (2 mL) heated in a closed Teflon Schlenk tube at 120 or difference in 2,5-hexanediol conversion and yield of pyrrole
150 8C bath temperature in the presence of 4 b molecular sieves. as observed in Table 1 indicates formation of a mixture of
[b] Yields and conversions determined by GC and conversion based on unindentified products resulting from 2,5-hexanediol. Also
2,5-hexanediol consumption. [c] Yield of isolated product. [d] The formation of small amounts of N-heptylidene-1-heptylamine
reaction was carried out in an open system under N2 atmosphere while
and N-heptyl-1-heptylamine was detected by GC-MS, most
refluxing. [e] The reaction was carried out in the absence of molecular
sieves. [f ] The reaction was carried out using 1,4-dioxane as the solvent.
likely as a result of dehydrogenative coupling of unreacted
heptylamine catalyzed by Co.[27] The formation of N-heptyl-
idene-1-heptylamine was further confirmed by performing
a separate reaction of heptylamine in the absence of 2,5-
(GC) revealed the formation of H2. A reaction carried out in hexanediol using 5 mol % of complex 1, 5 mol % NaHBEt3,
an open system in refluxing toluene in the presence of and 5 mol % tBuOK giving 45 % of N-heptylidene-1-heptyl-
molecular sieves generated 71 % of the pyrrole product amine after 24 h at 150 8C. However, the diamine N-heptyl-1-
(entry 3) indicating that the reaction is not affected signifi- heptylamine was not observed in this case.
cantly by the presence of hydrogen in the closed system. Using the optimized reaction conditions, the scope of this
However, in the absence of molecular sieves in the closed base-metal-catalyzed dehydrogenative coupling reaction was
system, a lower yield of pyrrole (40 %) was obtained under probed with 2,5-dihydroxyhexane and different amines. As
otherwise similar condition (entry 4). shown in Table 2, various linear primary alkyl amines coupled
Our previously reported PNP– and PNN–Co dihalo with dehydrogenated 2,5-hexanediol to yield the correspond-
complexes 2,[25] 3,[22a] and 4[26] (Figure 1 b) were then screened. ing 1,2,5-substituted pyrroles in excellent yields (Table 2,
Surprisingly, tBu-substituted complex 2 a did not show any entries 1–4).

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Table 2: Dehydrogenative coupling of diols and various amines cata- The reaction between 2,5-hexanediol and cyclohexyl-
lyzed by complex 1. amine gave 70 % yield of 1-cyclohexyl-2,5-dimethylpyrrole
(entry 5). Similarly, 62 % yield of N-phenethyl-2,5-dimethyl-
pyrrole was obtained from 2,5-hexanediol and 2-phenethyl-
amine (entry 6). Exploring the scope further, reactions of 2,5-
hexanediol with various benzylamines were studied, resulting
in moderate to good yields (entries 7–9). On the other hand
Entry[a] Diol Amine (RNH2) t [h] Yield of pyrrole [%] dehydrogenative coupling of less basic 4-trifluoromethylben-
zylamine with 2,5-hexanediol resulted in an only moderate
1 24 88[b] 60 % yield of the pyrrole (entry 10). Reaction of the less
nucleophilic anilines with 2,5-hexanediol resulted in low
yields (entries 11 and 12).
2 24 93[b] However, 2,5-hexanediol dehydrogenatively coupled with
(1-naphthylmethyl)amine to yield the corresponding 1,2,5-
substituted pyrrole in 78 % yield (entry 13). The catalytic
performance of 1 in the dehydrogenative coupling of 1,4-
3 24 86[b]
diphenyl-1,4-butanediol and heptylamine was also checked,
producing a moderate 56 % yield of 1-heptyl-2,5-diphenyl-
pyrrole (entry 14). Dehydrogenative coupling of primary 1,4-
4 24 90[b] butanediol with heptylamine resulted in 1-heptylpyrrole in
58 % yield as observed by GC-MS (entry 15) along with other
as yet unidentified products.[17]
5 24 70[b] Regarding the nature of the active cobalt catalyst, we
previously reported that treatment of complex 1 with one
equiv of NaHBEt3 at room temperature gave the para-
6 24 62[b] magnetic complex (PNNH)CoICl, characterized by X-ray
crystallography.[22a] This CoI complex was prepared and
isolated separately and tested in the dehydrogenative cou-
7 24 89[b] pling of 2,5-hexanediol and heptylamine. Using 5 mol % of
(PNNH)CoICl and 5 mol % tBuOK at 150 8C yielded 86 % of
N-heptyl-2,5-dimethylpyrrole after 24 h, which is comparable
8 36 68[b]
to the results obtained when using CoII complex 1 in the
presence of NaHBEt3 and tBuOK (Table 1, entry 2). This
suggests that the actual catalyst is a CoI complex. However,
attempts to isolate the active CoI catalyst by treating
9 24 87[b]
(PNNH)CoICl with one equiv of tBuOK failed. We also
could not isolate an in situ generated intermediate in the
reactions. Nevertheless, we believe that under the reaction
10 24 60[b] conditions, a mono-deprotonated CoI complex is formed by
dehydrohalogention via either the N@H or the methylene
proton of the N-arm of the pincer ligand. The unique feature
11 36 25[c] of the metal complexes developed with the PNNH ligand is
that they have the potential for metal–ligand cooperation by
both amine–amide and aromatization–dearomatization
12 36 22[c] ligand transformations.[28] The possibly generated highly
unsaturated CoI complex is anticipated to be stabilized by
potential binding with alcohol giving an alkoxy– CoI complex,
13 36 78[b] which could undergo dehydrogenation under the catalytic
conditions to give the ketone, liberating H2. The ketone
subsequently could couple with the present amine and form
the N-substituted pyrrole and water in a Paal–Knorr con-
14 36 56[c]
densation (Scheme 1). This step was confirmed by a separate
experiment starting from 2,5-hexanedione with heptylamine
at 150 8C in the absence of catalyst, quantitatively yielding the
15 24 58[c] corresponding N-heptyl-2,5-dimethylpyrrole. However, dehy-
drogenation of 2,5-hexanediol in the absence of an amine
[a] Conditions: diol (0.5 mmol), amine (0.5 mmol), toluene (2 mL), and resulted in a mixture of unidentified products, not including
4 b molecular sieves heated in an closed Schlenk tube for the specified 2,5-hexanedione. Nevertheless, the ability of catalyst 1 in the
time. [b] Yield of isolated product. [c] Yield determined by GC. dehydrogenation of a secondary alcohol was demonstrated

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