Unprecedented Oxycyanation of Methylenecyclopropanes for the Facile Synthesis of Benzoxazine Compounds Containing a Cyano Group

Article abstract of DOI:10.1002/chem.201505224

A novel intramolecular oxycyanation of methylenecyclopropanes is reported that proceeds through oxidative cleavage of the N-CN bond and subsequent palladium transfer from N to O of the amide group. A range of substituted benzo[d][1,3]oxazines with a cyano group are readily furnished by this newly developed oxycyanation reaction. Tris(4-trifluoromethylphenyl)phosphine as a ligand has been found to be crucial to effectively promote the transformation with high chemo- and regioselectivity. Moreover, the reaction outcome can be significantly affected by the electronic effect of the acyl group attached to the nitrogen atom of methylenecyclopropanes. When R³ is a chloromethyl group, the pyrrolo[2,3-b]quinoline derivative is obtained by thermal-induced [3+2] cycloaddition of methylenecyclopropane to the methanediimine intermediate. An intramolecular oxycyanation of methylenecyclopropanes, which proceeds through oxidative cleavage of the N-CN bond and subsequent palladium transfer from N to O of the amide group, has been developed (see scheme). A range of substituted benzo[d][1,3]oxazines with the cyano functionality are readily furnished along with the pyrrolo[2,3-b]quinoline derivative by thermal-induced [3+2] cycloaddition of methylenecyclopropane with the methanediimine intermediate.

Full text of DOI:10.1002/chem.201505224

DOI: 10.1002/chem.201505224
Communication
&
Cyclization
Unprecedented Oxycyanation of Methylenecyclopropanes for the
Facile Synthesis of Benzoxazine Compounds Containing a Cyano
Group
Yu-Chao Yuan, Hai-Bin Yang, Xiang-Ying Tang,* Yin Wei,* and Min Shi*[a]
ly aminocyanation[4,12] of alkynes and/or alkenes have been re-
Abstract: A novel intramolecular oxycyanation of methyle-
necyclopropanes is reported that proceeds through oxida-
tive cleavage of the NÀCN bond and subsequent palladi-
um transfer from N to O of the amide group. A range of
substituted benzo[d][1,3]oxazines with a cyano group are
readily furnished by this newly developed oxycyanation
alized by using a transition metal as catalyst to give nitriles
containing a functional group at the b-position to the cyano
group. Most cyano-functionalization reactions rely on the
cleavage of the functional group (FG)–CN bonds by electron-
rich late-transition-metal complexes, such as nickel(0), palladi-
um(0), and platinum(0), through oxidative addition as a key
step in their proposed catalytic cycles. For example, in 2012
and 2014, Nakao and co-workers reported the intramolecular
oxycyanation and aminocyanation of alkenes by cooperative
Pd/BPh3 catalysis (Scheme 1a).[3,4] Although the oxycyanation
reaction.
Tris(4-trifluoromethylphenyl)phosphine
as
a ligand has been found to be crucial to effectively pro-
mote the transformation with high chemo- and regiose-
lectivity. Moreover, the reaction outcome can be signifi-
cantly affected by the electronic effect of the acyl group
attached to the nitrogen atom of methylenecyclopro-
panes. When R3 is a chloromethyl group, the pyrrolo[2,3-
b]quinoline derivative is obtained by thermal-induced
[3+2] cycloaddition of methylenecyclopropane to the
methanediimine intermediate.
Benzoxazines are an important class of organic compounds
that are found in a number of thermoset materials,[1] optoelec-
tronic materials, and pharmaceuticals.[2] Some of benzoxazine-
containing compounds also show antibacterial or analgesic ac-
tivity. Meanwhile, nitriles, which can serve as versatile synthetic
intermediates for esters, amides, amines, aldehydes, and car-
boxylic acids, also play a pivotal role in organic synthesis. Ac-
cordingly, the development of novel and efficient synthetic
methods for heterocyclic compounds containing a cyano
group has been largely concerned in synthetic organic chemis-
try.[3,4] Metal-catalyzed cyanation reactions of unsaturated com-
pounds, such as alkenes and alkynes, to access a variety of ni-
triles in highly chemo- and stereoselective manners have thus
gained much interest. The silylcyanation,[5] germylcyanation,[6]
stannylcyanation,[7] borylcyanation,[8] carbocyanation,[9] thiocya-
nation,[10] bromocyanation,[11] oxycyanation,[3] and most recent-
Scheme 1. Metal-catalyzed cyanation reactions of unsaturated compounds.
of alkenes by cooperative Pd/BPh3 catalysis has been disclosed,
the oxycyanation of alkenes caused by the oxidative cleavage
of the NÀCN bond and the subsequent palladium transfer
from N to O of the amide group has never been reported. In
this paper, we wish to report the intramolecular oxycyanation
reaction of cyanamido group substituted methylenecyclopro-
panes[13,14] catalyzed cooperatively by a palladium catalyst and
BEt3, providing useful benzoxazine derivatives incorporating
a cyano group (Scheme 1b).
[a] Y.-C. Yuan, Dr. H.-B. Yang, Prof. Dr. X.-Y. Tang, Prof. Dr. Y. Wei,
Prof. Dr. M. Shi
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
345 Lingling Road, Shanghai, 200032 (China)
E-mail: siocxiangying@mail.sioc.ac.cn
weiyin@mail.sioc.ac.cn
The aniline-tethered alkylidenecyclopropanes were prepared
according to the previous literature.[15] With these substrates in
hand, we first examined the intramolecular oxycyanation reac-
mshi@mail.sioc.ac.cn
Supporting information for this article can be found under http://
dx.doi.org/10.1002/chem.201505224.
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Table 1. Optimization of the reaction conditions.[a]
Entry
Cat.
Ligand
Lewis acid
Solvent
T [oC]
Conv. [%]
Yield [%][b]
2a
34
68
63
44
49
92 (89)
35
<10
<10
26
31
51
37
65
40
13
26
33
3a
1
2
3
4
5
6
7
8
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
–
Xantphos
PPh3
P(p-CH3OC6H4)3
dppf
PPhMe2
P(p-CF3C6H4)3
–
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BPh3
Zn(OTf)2
–
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
BEt3
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DMF
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
130
150
110
110
110
93
80
82
99
52
99
83
70
62
88
82
82
79
91
98
89
99
69
99
99
93
92
96
trace
trace
trace
24
trace
7 (6)
trace
trace
trace
trace
trace
trace
trace
trace
10
trace
trace
trace
trace
5
–
–
9
–
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Pd(OAc)2
[Pd2(dba)3]
PdCl2
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
–
[Pd(OAc)2(Py)2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[{PdCl(allyl)}2]
[Ni(cod)2]
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
P(p-CF3C6H4)3
–
dioxane
toluene
toluene
toluene
toluene
toluene
64
57
79
82 (77)
78
trace
trace
trace
[{RhCl(cod)}2]
[Ru(C5H5)2]
[a] Reaction conditions: 1 (0.1 mmol), catalyst (10 mol%), ligand (20–40 mol%) and Lewis acid (40 mol%) in solvent (1.0 mL) stirred for 24 h under Ar.
1
[b] Determined by H NMR spectroscopy using 1,3,5-trimethoxybenzene as an internal standard. The isolated yield is shown in parentheses.
tion in the presence of various transition-metal catalysts. We
found that when the reaction was carried out in toluene at
110 8C, two new compounds could be formed in the presence
of the palladium catalyst and BEt3. This result encouraged us
to more carefully examine the reaction outcomes.
vealed that triethylborane was the Lewis acid of choice (en-
tries 14–15). More importantly, the reaction only gave 2a in
13% yield in the absence of triethylborane (entry 16), indicat-
ing that triethylborane plays a crucial role in activating the NÀ
CN bond.[3,4] After screening of solvents, we found that toluene
was the best one for this reaction (entries 17–18). Further stud-
ies were focused on the reaction temperature effect, and we
found that the intramolecular oxycyanation was sensitive to
the reaction temperature and the best results were obtained
at 110 8C (entries 19–20). Other transition-metal catalysts, such
as [Ni(cod)2], [{RhCl(cod)}2], and [bis(cyclopentadienyl)rutheni-
um], were also tested, but inferior results were obtained (en-
tries 21–23). Finally, we identified [{PdCl(allyl)}2] as the best cat-
alyst for this reaction (for more details on the optimization of
reaction conditions, see the Supporting Information).
Initial examinations using 1a as the substrate were aimed at
determining the reaction outcome and subsequently optimiz-
ing the reaction conditions. The results are summarized in
Table 1. Product 2a was obtained in 34% yield as the major
product with concomitant formation of thermal-induced [3+2]
cycloaddition adduct 3a in 3% yield (see Table 4), when the re-
action was carried out in toluene under the catalysis of
[{PdCl(allyl)}2] (10 mol%) with Xantphos ligand and triethylbor-
ane Lewis acid at 110 8C for 24 h (Table 1, entry 1). We next
screened different phosphine ligands, such as PPh3, P(p-
CH3OC6H4)3, dppf, PPhMe2, P(p-CF3C6H4)3 (entries 2–7). It was
found that P(p-CF3C6H4)3 combined with [{PdCl(allyl)}2] gave the
desired product 2a in 89% isolated yield along with only trace
of 3a. Without the palladium catalyst and phosphine ligand or
in the absence of palladium catalyst, phosphine ligand, and
Lewis acid, yields of 2a were less than 10% (entries 8–9). Sub-
sequent examination of palladium catalysts using P(p-CF3C6H4)3
as the ligand did not give better results (entries 10–12). The
combination of Pd(OAc)2/Py also did not facilitate the forma-
tion of 2a (entry 13). The examination of Lewis acid effects re-
With the optimized reaction conditions in hand, we next in-
vestigated the generality of this intramolecular oxycyanation
reaction, and the results are shown in Table 2. As for substrate
1, in which R1 =H, R3 =Me, both electron-withdrawing (1b,
1 f–1g) and -donating (1c–1d) substituents at the para-posi-
tion of aromatic rings were tolerated, providing the corre-
sponding products (2b–2d and 2 f–2g) in good to excellent
yields. In addition, an electron-donating (1e) substituent at the
meta-position of the aromatic ring also afforded the desired
product (2e) in excellent yield. Importantly, we also found that
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Table 2. Substrate scope for palladium-catalyzed intramolecular oxycya-
nation of methylenecyclopropanes with different aryl groups.[a,b]
Table 3. Substrate scope for palladium-catalyzed intramolecular oxycya-
nation methylenecyclopropanes with different acyl substituents.[a,b]
[a] Reaction conditions:
1 (0.2 mmol), [{PdCl(allyl)}2] (10 mol%), P(p-
CF3C6H4)3 (20 mol%) and BEt3 (40 mol%) are stirred in toluene (1 mL) for
24 h under Ar. [b] Isolated yield. [c] 15% of 1f was recovered.
two electron-withdrawing group substituted 1h was also suit-
able for this reaction, affording the desired product 2h in ex-
cellent yield. The structures of 2b and 2h were unambiguously
confirmed by X-ray diffraction. Their ORTEP drawings are
shown in Figure 1 and the corresponding CIF data are present-
ed in the Supporting Information.[16]
[a] Reaction conditions:
CF3C6H4)3 (20 mol%) and BEt3 (40 mol%) are stirred in toluene (1 mL) for
24 h under Ar. [b] Isolated yield.
1 (0.1 mmol), [{PdCl(allyl)}2] (10 mol%), P(p-
To further extend the substrate scope of this reaction, a varie-
ty of alkyl-, alkenyl- and aryl-substituted acyl groups incorpo-
rated substrates were examined (Table 3). As expected, for
both alkyl- and alkenyl-substituted acyl groups (1i–1m), such
as propionyl, acrylyl, butyryl, (E)-2-butenoyl, or isovaleryl in-
stead of acetyl, the reaction occurred effectively, affording the
corresponding products (2i–2m) in moderate to good yields.
Furthermore, we found that when a phenyl- or cyclopentyl-
substituted acyl group (1n–1p) was introduced in substrate 1,
the reaction proceeded smoothly to furnish the desired prod-
ucts 2n–2p in 62–80% yields. It should be noted that in the
cases of substrates 1n and 1o, the thermal-induced reaction
Table 4. The thermal-induced reaction.[a,b]
[a] Reaction conditions: 1 (0.1 mmol) is stirred in toluene (1 mL) for 24 h.
[b] Isolated yield.
Figure 1. ORTEP drawings of 2b and 2h (the thermal ellipsoids are set at
a 30% probability level).
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products 3n and 3o were obtained in 16 and 27% yield, re-
spectively. Disappointingly, when the benzoyl-, tert-butyl ace-
tate-, and tosyl-substituted substrates (1r–1t) were subjected
to the catalytic system, no reaction occurred. Notably, we
found that the thermal-induced [3+2] cycloaddition of sub-
strate 1a gave product 3a in low yield in toluene at 110 8C
(Table 4). The structure of 3a was determined by X-ray diffrac-
tion.[16] Its ORTEP drawing is shown in Figure 2. Interestingly,
with an electron-withdrawing group (such as Cl) at a-position
of the carbonyl group, the corresponding product 3q was ob-
tained in 76% yield (Table 4, 3q).
Scheme 3. Transformation of product 2a.
Scheme 4. Control experiments of 1a in the presence of TEMPO.
ylpiperidine N-oxide (TEMPO; 2.0 equiv), rendering unlikely the
intervention of a radical pathway.
Further control experiments were conducted as shown in
Scheme 5. Substrates 1u, 1v, and 1w without cyclopropane
moiety, could not be converted into the desired products
under the standard conditions, indicating that the strained
small ring plays an important role in the intramolecular oxycya-
nation reaction.
Figure 2. ORTEP drawing of 3a (the thermal ellipsoids are set at a 30%
probability level).
To examine the practicality of this new synthetic method,
scale-up experiment was carried out as shown in Scheme 2.
The use of 1a (2.0 mmol) afforded the desired products 2a
and 3a in 85 and 4% yield, respectively, without notable ero-
Scheme 5. Control experiments of 1u, 1v, and 1w under the standard con-
ditions.
Scheme 2. Scale-up experiment.
Based on the previous reports[4] and the control experi-
ments,
a plausible reaction mechanism is proposed in
Scheme 6. The reaction is initiated by the oxidative addition of
the NÀCN bond in 1 to Pd0, giving intermediate A. Subse-
quently, a palladium transfer from N to O of the amide group
takes place in intermediate A to give oxypalladium species B.
Then, oxypalladation takes place in an exo-trig manner to give
species C, which undergoes reductive elimination to afford 2
as well as the catalytically active palladium and boron species.
The Lewis acid catalyst is crucial for the oxidative addition of
NÀCN bonds, it has also been shown to promote C(sp3) ÀCN
bond-forming reductive elimination from palladium(II) through
coordination of a cyano group to Lewis acid.[17] As for product
3, it can be obtained by 1,3-acyl migration, consecutive 6p-
electrocyclization and the subsequent rearrangement.[18]
sion of yields, demonstrating that the current method is suit-
able for the preparation of benzoxazine building blocks in
practical organic synthesis. To illustrate the synthetic utility of
the obtained products, we further developed a transformation
of 2a to the corresponding aldehyde upon treating 2a with
DIBAL-H in THF at À788C, giving the desired aldehyde 4a in
51% yield (Scheme 3).
To gain mechanistic insights into the intramolecular oxycya-
nation reaction, a control experiment was performed as shown
in Scheme 4. The control experiment confirmed that the reac-
tion under the optimized conditions was almost unaffected by
the addition of the radical inhibitor, such as 2,2,6,6-tetrameth-
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Scheme 6. Proposed reaction mechanism.
In summary, we have developed a novel intramolecular oxy-
cyanation through the amide isomerization by palladium/
boron cooperative catalysis. The process enabled the forma-
tion of a variety of substituted benzoxazine compounds con-
taining a cyano group in good to excellent yields. Furthermore,
the reaction is substrate dependent and the pyrrolo[2,3-b]quin-
oline derivative is obtained by thermal-induced [3+2] cycload-
dition between the methylenecyclopropane and methanedi-
imine intermediate when R3 is a chloromethyl group. Further
development of the enantioselective oxycyanation and more
detailed mechanistic studies are in process in our laboratory.
Acknowledgement
We are grateful for the financial support from the National
Basic Research Program of China (973)-2015CB856603, the Na-
tional Natural Science Foundation of China (20472096,
21372241, 21361140350, 20672127, 21421091, 21372250,
21121062, 21302203, 20732008, and 21572052).
Keywords: amides
·
benzoxazines
·
intramolecular
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