Gold-Catalyzed Synthesis of Dibenzo[1,5]diazocines from β-(2-Aminophenyl)-α,β-ynones

Article abstract of DOI:10.1002/adsc.201700694

β-(2-Aminophenyl)-α,β-ynones afforded exclusively challenging dibenzo[1,5]diazocines by means of (JonPhosAuNCMe)SbF₆ catalysis. In contrast with the known gold-catalyzed reaction path of 2-alkynylanilines that leads to indoles, ynones underwent an auto intermolecular hydroamination. This process resulted finally in the formation of an eight-membered ring, likely through a selective 8-exo-dig intramolecular hydroamination that prevailed over the possible cyclocondensation reaction (that would result in the formation of 4-aminoquinoline derivatives). The easy availability of β-(2-aminophenyl)-α,β-ynones and the simple cyclization procedure make this approach suitable for the preparation of a wide range of useful dibenzodiazocines. The methodology can be extended to the use of β-(2-aminophenyl)-α,β-ynoates as substrates. (Figure presented.).

Full text of DOI:10.1002/adsc.201700694

Title: Gold Catalyzed Synthesis of Dibenzo[1,5] diazocines from β-(2-
aminophenyl)-α-βααynones
Authors: Navnath Dnyaneshwar Rode, Antonio Arcadi, Marco Chiarini,
Fabio Marinelli, and Gustavo Portalone
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700694
Link to VoR: http://dx.doi.org/10.1002/adsc.201700694

10.1002/adsc.201700694
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Gold Catalyzed Synthesis of Dibenzo[1,5] diazocines from -(2-
aminophenyl)---ynones
Navnath D. Rode,a Antonio Arcadi,a Marco Chiarini,b Fabio Marinelli a* and Gustavo
Portalone c.
a
Dipartimento di Scienze Fisiche e Chimiche, Università di L’Aquila, Via Vetoio- 67010 Coppito (AQ), Italy. E-mail:
fabio.marinelli@univaq.it.
b
Facoltà di Bioscienze e Tecnologie Agro-alimentari e Ambientali, Università di Teramo, Via Lerici 1, 64023-
Mosciano Sant'Angelo (Te), Italy.
Dipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, 00185 Roma, Italy.
c
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract.
-(2-aminophenyl)--ynones
afforded
exclusively challenging dibenzo [1,5]diazocines by means of
(JonPhosAuNCMe)SbF6 catalysis. In contrast with the
known Au-catalyzed reaction path of 2-alkynylanilines that
leads to indoles, ynones underwent an auto intermolecular
hydroamination. This process resulted finally in the
formation of an eight-membered ring, likely through a
selective 8-exo-dig intramolecular hydroamination that
prevailed over the possible cyclocondensation reaction (that
would result in the formation of 4-aminoquinoline
derivatives). The easy availability of -(2-aminophenyl)-
-ynones and the simple cyclization procedure make this
approach suitable for the preparation of a wide range of
useful dibenzodiazocines. The methodology can be extended
to the use of -(2-aminophenyl)--ynoates as substrates.
Keywords: Dibenzodiazocines; Alkynones; Gold catalysis;
Medium-ring compounds; Hydroamination; Alkynoates.
the formation of quinolines 2 (Scheme 1). Conversely,
when primary amines were used as nucleophiles in
the conjugate addition to 1, intramolecular hydrogen
bond between the N-H and carbonyl oxygen moieties
determined the formation of the (Z) -enaminone 3 (in
which –NH2 is trans respect to the carbonyl), and
isomerization of the C-C double bond was needed to
Introduction
β-(2-Aminophenyl) α,β-ynones
1
represent
powerful building blocks for the synthesis of
[1]
quinoline derivatives.
Over the years, we have
developed different strategies for the preparation of
quinoline derivatives from 1, including Pd-catalyzed
transfer hydrogenation, Rh and Pd-catalyzed
[3]
achieve the formation of the quinoline ring
(Scheme 2).
hydroarylation with organoboron derivatives,
conjugate additions
[2]
and cycloadditions. The
common feature of these methodologies is
represented by the conversion of the C-C triple bond
of the ynone into an alkene moiety in
Scheme 2. Conjugate addition of primary amines to 1-
cyclization reaction
Scheme 1. General strategy for the synthesis of quinolines
from 1
which –NH2 and carbonyl groups are in a cis
relationship; sequential cyclocondensation resulted in
Very surprisingly, during an attempt to extend the
[4]
use of 1 as versatile precursor of indoloquinolines
[5]
to the significant 4-(1-indolyl) quinolines 6,
we
1
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10.1002/adsc.201700694
Advanced Synthesis & Catalysis
discovered an unpredictable Au(I)-catalyzed process
that resulted in the coupling of two units of ynones 1
to afford a challenging eight membered ring (scheme
3).
possible implications. Dibenzodiazocine scaffold has
[12]
been object of attention in medicinal chemistry
[13]
and in organometallic chemistry;
science, copolymers
in material
containing
diaryldibenzodiazocines find potential application as
molecular actuators. [14] Moreover a class of bridged
analogues of 7, i.e. Tröger’s base and its derivatives,
[15]
possess a chiral cleft structure that makes them
interesting scaffolds in supramolecular chemistry. [16]
Scheme 3. Gold Catalyzed Synthesis of Dibenzo[1,5]
diazocines 7
Results and Discussion
We began our work by investigating the reaction of
2-phenylethynylaniline 4a with the ynone 1a. Under
the conditions previously described by Cacchi & coll.
for the conjugate addition type reaction of 4 to 3-
arylpropiolates, [6] we failed to obtain the desired 5a
(deriving from conjugate addition of 4a to 1a) in
satisfactory yields; the target product was obtained in
24% yield, together with a small amount of 4-(1-
indolyl) quinoline 6a, likely formed by in situ
cyclization of 5a (Scheme 4, a). We then envisaged
Scheme 4. Reaction of 1a with 4a under different reaction
conditions.
that a transition metal catalyst could be beneficial for
[7]
this process.
Recent developments highlight
relevant progresses in the applications of gold-
catalysis to the synthesis of the heterocylic
Therefore the synthesis of diazocines and the
derivatives through selective hydroamination
study of their properties represents a topic of
[8]
reactions.
We therefore investigated the use of
[17]
current interest,
and the development of new
cationic gold catalysts. Previously, Liu & coll.
reported an efficient (PPh3)AuCl/AgOTf catalysed
addition of 2-acylanilines to propiolates followed by
selective routes towards this class of compounds
can be of great importance in different research
fields.
sequential
cyclization,
that
afforded
We therefore attempted the optimization of the
reaction conditions to address the selective
preparation of 7a from 1a (Table 1). The efficiency
of this (JohnPhosAuMeCN)SbF6 catalysed cascade
autoassembly of 1a to 7a resulted highly dependent
on the reaction medium: in DMF 7a was obtained in
only 24% yield together with various unidentified
byproducts (entry 1); by switching to toluene we
isolated 7a as the sole product in 75 % yield (entry 2).
We briefly investigated the influence of the
temperature: at 80 °C the reaction afforded 7a in a
slight better yield than at 100 °C (entry 3), while at
40 °C a poorer result was observed (entry 4). The
unique ability of (JohnPhosAuMeCN)SbF6 to
promote the efficient formation of 7a is revealed by
the comparison of the results of entry 3 with those of
entries 5-10: other cationic Au(I) or Au(III) catalysts
were less effective (entries 5-7). The use of AgOTf or
ZnBr2 gave poor results (entries 8, 9); it is worth
noting
polyfunctionanised quinolines in good to excellent
[9]
yields.
same
When we reacted 1a with 4a under the
reaction conditions, intramolecular
hydroamination of 4a leading to 2-phenylindole
prevailed over the intermolecular addition of 4a to
the activated triple bond of the ynone 1a (Scheme 4,
b). In this experiment 5a was not isolated; probably it
was formed in low amount and cyclized to 6a in the
[10]
reaction mixture.
Very surprisingly, when the
reaction was carried out in the presence of
(JohnPhosAuMeCN)SbF6 as catalyst, [11] the in-depth
analysis of the reaction mixture revealed the
formation of a product whose molecular weight was
found to be exactly twice the molecular weight of 1a.
The HRMS spectrum, combined with the observation
13
of only 13 peaks in the C spectrum (see Supporting
Information Section) led us to assign to this new
compound the symmetrical dibenzo[1,5]diazocine
structure 7a (Scheme 4, c). Intrigued by this
unexpected result, we decided to investigate its
2
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10.1002/adsc.201700694
Advanced Synthesis & Catalysis
however that the silver catalyst afforded also a small
amount of the 2-acylindole through a 5-endo-dig
unimolecular process. PdCl2 was completely unactive
(entry 10), and a quantitative recovery of starting
1a was observed by omitting the catalyst (entry
11). Attempts to obtain 7a through a base
[18]
promoted process
in the presence of Cs2CO3
meet with failure, and no formation of diazocine
was observed; using DMF as solvent resulted in a
complex reaction mixture (entry 12), while in
toluene 1a was recovered in 71% yield (entry 13).
Table 1. Optimization of the preparation of
dibenzo[1,5]diazocine 7a from 1a.a
Entr Catalyst
y
Solvent t (h)
T
7a
(°C) yieldb
1
2
3
4
5
6
JPAuc
JPAuc
JPAuc
JPAuc
DMF
toluene
toluene
5
3
3
100 24e
100 75
80
40
78f
toluene 16
67(17)d
AuPPh3NTf2 toluene 16
100 26(29)d
100 12(38)d
AuClPPh3/
AgOTf
AuCl3/
AgOTf
AgOTf
ZnBr2
PdCl2
toluene 16
7
toluene 16
100 11(31)d
8
9
10
11
12
13
toluene 16
toluene 24
100 25(10)d,i
100 13(38)d
80
MeCN
toluene
DMF
24
4
1.5
3
- (35)d
none
none
none
80
- (93)d
g,h
100
-
toluene
100 - (71)c,g
Scheme 5. Scope of the preparation of dibenzo[1,5]
diazocines 7 from 1a-u.
a)Reactions were carried on a 0.1 mmol scale using 5 mol%
of catalyst in 1 mL of solvent. b) HPLC yields. c)JPAu =
(JohnPhosAuMeCN)SbF6. d) Figures in parentheses refer
to the recovered 1a e)Unidentified byproducts were formed.
f)Isolated yield. g)In the presence of 1 equiv. of Cs2CO3.
coupling of aryl iodides or vinyl triflates with 2-
ethynylaniline or b) reaction of aldehydes with
ethynylmagnesium bromide followed by Sonogashira
coupling of the resulting terminal propargylic alcohol
with 2-iodoaniline and oxidation. The alkynoate 1v
was prepared by Sonogashira coupling of 4-chloro-2-
iodoaniline with propiolic acid, followed by reaction
with MeI in the presence of K2CO3.
i)
h)Decomposition of the starting material was observed. 2-
benzoylindole was formed in 12% yield.
As reported in Scheme 5, the present cyclization
proved to be a wide scope process, and a variety of
dibenzodiazocines 7a-u were obtained from 1a-u as
sole products in moderate to high yields. Aryl,
heteroaryl, vinyl, dienyl and alkyl substituents -R,
originating ultimately from aldehydes (RCHO) or
from organic electrophiles such as halides (R = aryl,
heteroaryl) or triflates (R = vinyl) were introduced in
With the optimized conditions in hand, we explored
the scope of this unprecedented gold catalysed
synthesis of dibenzo[1,5]diazocines from -(2-
aminophenyl)-ynones 1. Starting compounds
1a-u (see Supporting Information section for the
corresponding structures) were readily prepared as
previously reported by us, [2] through a) carbonylative
3
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10.1002/adsc.201700694
Advanced Synthesis & Catalysis
the acyl frameworks of the target products, and alkyl
endo-dig or 4-exo-dig unimolecular paths); b) the 8-
group gave particularly good results (7p-r). Moreover, exo-dig cyclization should be faster than E/Z
substitution in the aniline ring of target diazocines
was achieved (products 7r-u); the corresponding
ynones 1r-u were easily prepared using substituted 2-
isomerization of the enaminone III, that should
afford the corresponding quinoline. It is worth noting
that when 4a reacted with 1a, this latter reaction took
place: likely, nor 8-exo-dig nor alternative 9-endo-dig
path were competitive with isomerization/cyclization
of the intermediate (Z) enaminone [3] (formed through
addition of 4a to 1a) that afforded 6a (Scheme 3, b).
The low amount of 6a produced in this case is likely
due to the depletion of 4a, that preferentially cyclized
to 2-phenylindole before adding to 1a. A further
evidence of the possibility of isomerization/
cyclization path to occur with o-substituted anilines
was obtained through the control experiment showed
in Scheme 7: the reaction of the 2-iodoaniline with 1a
(in the absence of possibility of intramolecular
hydroamination of the enaminone) gave the quinoline
8 as main product.[23]
iodoanilines
in
the
Sonogashira
coupling.
Interestingly, the methodology can be extended to
alkynoates, and diazocine 7v (R = -OMe) was
obtained in moderate yield.
A reasonable mechanistic picture that accounts for
the present reaction outcome is depicted in Scheme 6.
After initial coordination of 1 to Au(I) and formation
of complex I, a regio- and stereoselective
intermolecular hydroamination generates the
intermediate II which undergoes protodeauration to
give the intermediate III. Subsequently, a quite
unusual gold-catalyzed 8-exo-dig annulation delivers
the dibenzodiazocine 7.
Scheme 7. Isomerization-cyclization of enaminone moiety.
We also carried out the Au-catalyzed cyclization of
1a at room temperature (under otherwise identical
reaction conditions) with the aim of isolating the
intermediate enaminone III (Scheme 8). Besides the
dibenzodiazocine 7a and the recovered ynone, the
reaction afforded a small amount of quinoline 9.
Likely, fast gold-catalysed 8-exo-dig annulation of III
prevents its isolation; however, at room temperature
competitive E/Z isomerization of III followed by
cyclocondensation takes place to some extent.
Scheme 6. Plausible reaction path.
The formation of eight membered rings is
generally not favored due to enthalpic and entropic
barriers. [19] To the best of our knowledge only one
example of Au(I)-catalyzed 8-exo-dig intramolecular
hydroamination has been reported, [20] and took place
with low efficiency (15% yield); 8-endo-dig Au(I)-
catalyzed intramolecular hydroarylation of alkynyl
indoles has been also described.
[21]
Recently, an
intramolecular Au(I)-catalyzed 8-exo-trig dehydrative
alkoxylation process has been used in a formal
synthesis of (+)-laurencin. [22]
The formation of 7 rely on the dual nature of
ynones 1, that are nucleophilic (-NH2) and
electrophilic (conjugated triple bond). In addition, to
obtain the benzodiazocines with high selectivity two
conditions must be met: a) intramolecular
hydroamination shall not take place in the first step,
but only after the formation of III (acylindoles or
benzazetines would be otherwise obtained via 5-
Scheme 8. Au-catalyzed reaction of 1a at room
temperature.
4
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10.1002/adsc.201700694
Advanced Synthesis & Catalysis
A further evidence that the first step in Scheme 6 is
plausible (i.e. that the EWG nature of alkynone
moiety does not hamper the ability of the amino
group of 1 to act as nucleophile in an Au-catalyzed
intermolecular hydroamination) comes from the
experiment illustrated in Scheme 9: the formation of
the quinoline 10 is in accord with this hypothesis. [6]
Scheme 9. Intermolecular hydroamination of 4-phenylbut-
3-yn-2-one with 1p.
Figure 1. ORTEP of 7c.
Experimental Section
Finally, the structure of the products 7 obtained in
the
present
reaction
was
unambiguously
General procedure of synthesis dibendiazocines 7.
demonstrated by single crystal x-ray diffraction of 7a
and 7c (see Supporting Information section). The
ORTEP view of 7c (Figure 1) shows two
centrosymmetric molecules associated by hydrogen
bonds (double dashed red lines) between amino and
carbonyl groups.[24]
To a solution of β-(2-aminophenyl) α,β-ynone 1
(0.17-0.40 mmol) in toluene (1-2 mL) was added
(JohnPhosAuMeCN)SbF6 (5 mol %). The resulting
reaction mixture was stirred at 80 °C under a N2
atmosphere for 3-24 h to give the product 7 as a
single spot (TLC analysis). The mixture was
extracted with water and ethyl acetate (3x). The
organic phase was dried over Na2SO4 and
concentrated under vacuum. The crude product was
purified by using two procedures.
Conclusion
In conclusion, we have described here a Au(I)
catalyzed highly selective formation of an eight-
membered ring, that allows an innovative approach to
the construction of dibenzo[1,5]diazocine skeleton by
means of a cascade intermolecular/intramolecular
hydroaminations of β-(2-aminophenyl) α,β-ynones 1.
The wide availability of the starting materials, the
mild reaction conditions and the high atomic
efficiency of the cyclization makes this methodology
suitable for the synthesis of a library of products that
could be of interest in different field of research
including medicinal chemistry, supramolecular
chemistry and material science. Moreover, the
formation of 2- benzoylindole in the presence of
Ag(I), although in low amount, opens the possibility
Procedure A: column chromatography on silica gel
(petroleum ether /ethyl acetate mixtures as eluent);
compounds 7a, c, g, k, l, m, n, o, r, s, t,v.
Procedure B: the crude product was washed using
diethyl ether (2x2mL); compounds 7b, d, e, f, h, i, j,
p, q.
Acknowledgements
This work was supported by University of L’Aquila.
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10.1002/adsc.201700694
Advanced Synthesis & Catalysis
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6
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Advanced Synthesis & Catalysis
FULL PAPER
Unexpected Gold Catalyzed Synthesis of
Dibenzo[1,5] diazocines from -(2-
aminophenyl)--ynones
Adv. Synth. Catal. Year, Volume, Page – Page
Navnath D. Rode, Antonio Arcadi, Marco Chiarini,
Fabio Marinelli* and Gustavo Portalone.
7
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