Gold(III)-catalyzed chemoselective annulations of anthranils with N-allylynamides for the synthesis of 3-azabicyclo[3.1.0]hexan-2-imines

Article abstract of DOI:10.1039/c9cc04027g

We herein report the gold(iii)-catalyzed selective annulation of anthranils with N-allylynamides under mild conditions. By trapping the in situ-generated α-imino gold carbenes, 3-azabicyclo[3.1.0]hexan-2-imines were obtained in high synthetic efficiency. The reaction, which can be conducted in the gram scale, tolerates electron-rich and electron-deficient anthranils as well as a diverse set of functionalized ynamides (aryl- and alkyl-substituted terminal).

Full text of DOI:10.1039/c9cc04027g

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DOI: 10.1039/C9CC04027G
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Gold(III)-Catalyzed Chemoselective Annulations of Anthranils with
N-Allylynamides for the Synthesis of 3-Azabicyclo[3.1.0]hexan-2-
imines
Received 00th January 20xx,
Accepted 00th January 20xx
Lina Song,a Xianhai Tian,a Matthias Rudolph,a Frank Rominger a and A. Stephen K. Hashmi *ab
DOI: 10.1039/x0xx00000x
www.rsc.org/
We herein report the gold(III)-catalyzed selective annulation of Especially, because of the adjacent nitrogen atom, the C–C
anthranils with N-allylynamides under mild conditions. By trapping triple bond is highly activated which facilitates a transition
the
in
situ-generated
-imino
gold
carbenes,
3- metal-catalyzed oxygen transfer under mild conditions to
azabicyclo[3.1.0]hexan-2-imines were obtained in high synthetic generate a -keto metal carbene, which subsequently
efficiency. The reaction, which can be conducted in gram scale, undergoes an intramolecular cyclopropanation to deliver an 3-
tolerates electron-rich and electron-deficient anthranils as well as azabicyclo[3.1.0]hexan-2-one.6f-g
Whereas
oxidative
a diverse set of functionalized ynamides (aryl-, alkyl-substituted, cyclopropanations of N-allylynamides by oxygen donors are
terminal).
well explored, the corresponding cyclopropanations by -imino
gold carbenes, derived from nitrene transfer reagents, remain
comparatively underdeveloped.7 Only our group recently
reported an intermolecular gold nitrene transfer from N-
arylsulfilimines7b to ynamides for the synthesis of 3-
azabicyclo[3.1.0]hexan-2-imines enabled by -imino gold
carbene intermediates. However, this reaction is limited to
sulfilimines bearing strong electron-withdrawing groups (Ms,
NO2, CF3) on the arene rings, and a general cyclopropanation
reaction with excellent functional group tolerance is highly
challenging and of great significance.
The cyclopropane core has attracted tremendous attention as it
widely exists in natural products and synthetic bioactive agents,
and it also can serve as a versatile intermediate in organic
synthesis.1 Among the methods established for preparing
cyclopropanes,2 transition metal-catalyzed reactions of 1,5-
enynes3 are straightforward and efficient. These versatile
unsaturated systems can undergo diverse cyclizations to form
novel carbocycles and heterocycles. Based on their  acidity,
among the applied transition metals, gold catalysts4 have
become a very powerful tool for catalytic cyclizations of 1,5-
enynes, by enabling the activation of C–C triple bonds, followed
by the intramolecular nucleophilic attack of olefins. This is
exemplified by the cycloisomerisation of 1,5-enynes for the
synthesis of bicyclo[3.1.0]hexenes.4b Recently, the gold-
catalyzed synthesis of cyclopropyl indanone derivatives from
fused 1,5-enynes through -oxo gold carbene intermediates
were reported.5 Typically, the gold-activated C–C triple bond of
an 1,5-enyne was treated with a carbene precursor (commonly
a N-oxide) to form a highly reactive gold carbene intermediate,
which was rapidly trapped by an alkenyl group to produce a
cyclopropane-containing bicycle. This strategy was applied for
the enantioselective synthesis of (−)-Nardoaristolone B.5f N-
Allylynamides,6 as aza-1,5-enynes, were also suitable substrates.
Previous work:
Ts
N
Ph
Ts
N
[Au]
O
N
Au(I)
DCE
O
N
N
Ph
-[Au]
C-H insertion
N
Ts
1
H
(a)
Ph
4
O
2
-imino gold carbene
This work:
Ts
N
Ts
N
Ph
Ph
O
N
Au(III)
toluene
O
N
[Au]
cyclopropanation
-imino gold carbene
-[Au]
N
N
Ts
1
Ph
2
3
CHO
(b)
Scheme 1 Gold-catalyzed divergent annualtion of anthranils with ynamides.
Gold-catalyzed oxygen,8 nitrene7b,9 and carbene transfer10
provides access to functionalized gold carbenes, which are
subsequently trapped by different functional groups to produce
structural diversity, have experienced a rapid development in
the last two decades. Since the first gold-catalyzed annulation
between isoxazoles and ynamides was reported by Ye et al.,9k
a.Institute of Organic Chemistry, Heidelberg University, Im Neuenheimer Feld 270,
69120 Heidelberg, Germany. E-mail: hashmi@hashmi.de
b.Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah
21589, Saudi Arabia
† Electronic Supplementary Information (ESI) available: Experimental procedures,
characterization data and copies of NMR spectra, See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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these versatile reagents have been vastly used as gold carbene azabicyclo[3.1.0]hexan-2-imines 3c-e. An electron-sufficient
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precursors, allowing the facile syntheses of various aza- substrate, 5-methylanthranil 1f, gave tDhOeI:d1e0s.1i0re39d/Cp9rCoCd0u4c0t27iGn
heterocycles. Our group described a [3 + 2] C–H annulation of good yield. As a sensitive electron-donating group, a hydroxyl
anthranils with ynamides for the synthesis of 7-acylindoles9l group remained untouched and the desired hydroxyl-
(Scheme 1a). Inspired by previous research,8-11 with N- containing bicycle 3g was prepared in 43% yield. 6-Chloro- and
allylynamides, we presumed that a bicyclic product 3 might be 6-bromoanthranils reacted smoothly with N-allylynamide 2a,
formed through cyclopropanation of the generated -imino furnishing 3h and 3i in excellent yield. 3-Substituted anthranils
gold carbene intermediates (Scheme 1b).
1j and 1k afforded the targets in lower yields.
With this in mind, our investigation began by employing
anthranil 1a and N-allylynamide 2a as model substrates (Table
1). First, IPrAuCl/AgNTf2 as catalyst delivered indole 4a and 3-
azabicyclo[3.1.0]hexan-2-imine 3a in 30% and 65% yields at
room temperature (Table 1, entry 1). We then sought to
selectively synthesize the bicycle 3a by optimizing the reaction
conditions. Phosphine ligands such as PPh3 and JohnPhos didn’t
improve the selectivity (Table 1, entries 2-3). AuCN led to indole
4a as a major product (Table 1, entry 4). A gold(III) catalyst,
PicAuCl2, significantly improved the reaction with a high ratio of
3a/4a (Table 1, entry 5). The solvent (DCE, THF, CH3CN)
screening showed that using this procedure with toluene as the
solvent provided the highest yield of 3a (Table 1, entries 6-8).
Simple NaAuCl4∙2H2O, was highly beneficial for the formation of
product 3a and thus was chosen as the best performer (Table 1,
entry 9). Furthermore, in the absence of a gold catalyst, no
reaction was observed (Table 1, entry 10).
Table 2 Scope with respect to anthranilsa, b
Ts
R1
N
Ph
N
·
R2
NaAuCl4 2H2O (5 mol%)
R2
N
O
toluene, rt
N
Ts
3
R1
Cl
O
Ph
1
2a
F
Ph
N
Ph
Ph
Ph
N
N
N
N
Br
N
N
N
Ts
Ts
Ts
CHO
3d
Ts
CHO
CHO
, 99%
CHO
, 99%
3a
3c
, 95%
3b
, 98%
Cl
HO
Cl
Br
Ph
N
Ph
Ph
N
Ph
N
N
N
N
Ts
N
N
Ts
CHO
, 80%
Ts
CHO
3g
Ts
CHO
3e
CHO
3h
3f
, 43%
, 99%
, 99%
Br
Ph
Ph
N
Ph
N
N
N
N
N
Ts
Ts
Ts
CHO
Ph
O
, 83%
O
3k
3i
, 96%
3j
, 87%
Table 1 Optimization of the reaction conditionsa,b
a
Optimized reaction conditions: 1 (0.2 mmol, 1.0 equiv.), 2a (0.24 mmol, 1.2
Ph
equiv.), NaAuCl4∙2H2O (5 mol%, 4.0 mg), toluene (2.0 mL, 0.1 M). b Isolated yield of
products 3 are shown.
Ts
N
Ph
N
gold catalyst
solvent, rt
N
O
N
N
Ts
N
2a
H
1a
Ts
4a
undesired
CHO
3a
CHO
Ph
Encouraged by the excellent performance of anthranils, we
further investigated the scope by using a variety of N-
allylynamides (Table 3). Gratifyingly, a broad range of
substituted N-allylynamides is tolerated. Ynamide 2b with a
bromo substituent gave product 3l in 99% yield, which is an
excellent substrate for further classic cross coupling reactions.
Bicycle 3m was prepared from 3-chlorophenyl ynamide 2c, the
structure of which was further confirmed by X-ray crystal
structure analysis.12 Ynamides 2d-f, bearing electron-donating
groups (methyl, ethyl, tert-butyl) at 3- or 4-positions of the
arene rings, afforded the desired targets 3n-p12 all in 99% yields.
A CF3-containing ynamide 2g was also found to be suitable,
albeit in 87% yield (3q). Other protecting groups including n-
PrSO2, BnSO2 and the easily removable 4-nitrophenylsulfonyl
did not retard the annulation reaction (3r-t). 2-Methylallyl
ynamide 2k (R2 = Me) reacted efficiently with 5-bromoanthranil,
yielding product 3u with two vicinal quaternary carbon centers.
An internal alkene-derived ynamide 2l delivered 6-methyl-3-
desired
yield of
3a
65%
54%
entry
catalyst
solvent
yield of 4a
1
2
IPrAuClc/AgNTf2
PPh3AuCl/AgNTf2
JohnPhosAuCld/
AgNTf2
AuCN
PicAuCl2
PicAuCl2
PicAuCl2
PicAuCl2
NaAuCl4∙2H2O
-
toluene
toluene
30%
40%
3
toluene
39%
53%
4
5
6
7
8
toluene
toluene
DCE
24%
91%
20%
82%
57%
97%
n. d.e
65%
6%
55%
13%
18%
trace
n. d.e
THF
CH3CN
toluene
toluene
9
10
a
General reaction conditions: 1a (0.1 mmol, 1.0 equiv.), 2a (0.12 mmol, 1.2
b
equiv.), catalyst (5 mol%), solvent (1.0 mL, 0.1 M). Yields of 3a and 4a
measured by 1H NMR with 1,3,5-trimethoxybenzene as the internal standard. c
d
IPr
=
1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene.
JohnPhos = 2-(di-tert-butylphosphino)biphenyl. e n. d.: not detected.
azabicyclo[3.1.0]hexan-2-imine 3v in 95% yield in
a
diastereomeric ratio of 6.3:1. Moreover, a terminal ynamide
also readily underwent the cyclopropanation pathway (3w).
While our previous work has demonstrated that the -imino
gold carbene generated from an alkyl ynamide and anthranil
will undergo a 1,2-hydride shift to form an unsaturated amidine,
this reaction was compatible with a butyl-derived ynamide,
delivering the desired product 3x in 70% yield. This indicates,
Having established the optimal reaction conditions, we
examined the reaction scope with respect to anthranils. As
shown in Table 2, the unsubstituted anthranil 1a gave product
3a in 95% yield. 3-Bromoanthranil 1b is also a successful
participant in this cyclopropanation reaction. Benzoisoxazoles
1c-e bearing halogens such as F, Cl, Br were particularly well
tolerated to quantitatively produce the desired 3-
2 | J. Name., 2012, 00, 1-3
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Ts
that the intramolecular cyclopropanation of the gold carbene is
much faster than a competing 1,2-C–H-insertion (Scheme 2).
N
Ph
View Article Online
·
NaAuCl4 2H2O (2 mol%)
DOI: 10.1039/C9CC04027G
O
N
N
toluene, rt
N
Ts
CHO
Ph
, 4.2 mmol
1a
, 3.5 mmol
3a
Ph
N
, 1.41 g, 94%
2a
O
O
O
P
Ph
O
(2 eq.)
N2
N
N
N
Cs2CO3 (2.5 eq.)
MeOH/THF, rt
Ts
Ts
CHO
6
, 90%
3a
Scheme 3 Gram-scale synthesis and an important transformation.
In conclusion, we developed a gold(III)-catalyzed selective
annulation of anthranils and N-allylynamides for the synthesis
of 3-azabicyclo[3.1.0]hexan-2-imines. This efficiently scalable
reaction is associated with good functional group tolerance,
great efficiency, easy synthesis of starting materials, mild
conditions and 100% atom-economy. This reaction has
significant potential for total synthesis, further applications of
the obtained products will extend the significance of this
methodology.
Figure 1 Solid state molecular structures of 3m (left) and 3p (right).
Table 3 Scope with respect to ynamidesa, b
R5
PG
R4
N
R5
R
R3
R
L. Song and X. Tian are grateful to the CSC (China Scholarship
Council) for a PhD fellowship.
R4
·
NaAuCl4 2H2O (5 mol%)
O
toluene, rt
N
N
N
R3
1
PG
2
CHO
3
Cl
Br
N
Br
Conflicts of interest
There are no conflicts to declare.
Br
Br
N
N
N
N
N
N
N
Ts
CHO
3l
Ts
CHO
3n
Ts
X-ray
Ts
, 99%
CHO
3m
CHO
3o
, 99%
, 99%
, 73%,
F3C
Notes and references
Br
Ph
N
Ph
N
Br
1
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N
N
SO2Bn
N
N
CHO
3s
N
N
Ns
CHO
3r
Ts
Ts
CHO
3p
CHO
3q
, 95%
, 95%
, 87%
Ph
X-ray
, 99%,
Br
Br
Br
Ph
Br
Ph
N
N
N
N
N
N
N
N
Ts
Ts
SO2nPr
CHO
3u
CHO
3w
Ts
CHO
3v
, 95%; dr = 6.3:1
CHO
3t
, 99%
, 89%
, 58%
2
3
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a Optimized reaction conditions: 1 (0.2 mmol, 1.0 equiv.), 2 (0.24 mmol, 1.2 equiv.),
NaAuCl4∙2H2O (5 mol%, 4.0 mg), toluene (2.0 mL, 0.1 M). Isolated yields of
product 3.
b
Ts
Br
Ts
N
N
Br
Br
N
·
NaAuCl4 2H2O (5 mol%)
O
toluene, rt
N
N
N
CHO
, 13%
1e,
0.2 mmol
Ts
CHO
3x
5
2n
, 0.24 mmol
, 70%
4
Scheme 2 Test of an alkyl ynamide.
An efficient scale-up is possible, which was exemplified by the
excellent-yield of a 3.5-mmol scale annulation of anthranil 1a
with ynamide 2a (Scheme 3). 1.4 g of 3a were obtained, 3a was
further converted to an alkynyl product 6 through Seyferth–
Gilbert homologation.
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4 | J. Name., 2012, 00, 1-3
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ChemComm
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DOI: 10.1039/C9CC04027G
Journal Name
COMMUNICATION
Table of Content:
R5
R1
PG
R4
R3
N
R5
R2
R1
NaAuCl4•2H2O (5 mol%)
toluene, rt
R4
R2
O
N
N
N
R3
PG
O
readily available substrates
mild conditions
24 examples
up to 99% yield
100% atom-economy
broad scope
high selectivity and efficiency
efficient gram-scale synthesis
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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