Palladium-Catalyzed Carbonylative Synthesis of 3-Methyleneisoindolin-1-ones from Ketimines with Hexacarbonylmolybdenum(0) as the Carbon Monoxide Source

Article abstract of DOI:10.1002/cctc.201601306

An interesting procedure for the palladium-catalyzed carbonylative synthesis of 3-methyleneisoindolin-1-ones from ketimines was established. By using Mo(CO)₆ (0.3 equiv.) as the solid CO source and through C(sp²)?H bond activation, t

Full text of DOI:10.1002/cctc.201601306

Accepted Article
Title: Palladium-Catalyzed Carbonylative Synthesis of 3-
Methyleneisoindolin-1-ones from Ketimines with Mo(CO)6 as the
CO Source
Authors: Xiao-Feng Wu, Zechao Wang, Fengxiang Zhu, and Yahui Li
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10.1002/cctc.201601306
ChemCatChem
COMMUNICATION
Palladium-Catalyzed Carbonylative Synthesis of 3-Methyleneisoindolin-1-
ones from Ketimines with Mo(CO)6 as the CO Source
Zechao Wang,[a] Fengxiang Zhu,[a] Yahui Li,[a] and Xiao-Feng Wu*[a]
Abstract: An interesting procedure on palladium-catalyzed
carbonylative synthesis of 3-methyleneisoindolin-1-ones from
ketimines has been established. With 0.3 equivalent of Mo(CO)6 as
the solid CO source via C(sp2)-H bond activation, moderate to good
yields of the desired 3-methyleneisoindolin-1-ones were isolated.
activation was applied in 3-methyleneisoindolin-1-ones synthesis
as well. By the cyclization of benzimidates or aromatic nitriles
with alkenes via C-H bond activation, moderate to good yields of
the desired products can be formed.[7,8] More recently, a
palladium-catalyzed
cyclization
of
readily
available
carboxamides with carboxylic acids or anhydrides to produce
isoindolinones was reported.[9] A broad range of substrates can
be applied to give the desired products in good yields with good
functional group tolerates.
Heterocyclic compounds are presenting dominantly in biological
active molecules.[1] Among them, 3-methyleneisoindolin-1-ones
are one of the most important structures which are presenting in
nature products and also in various pharmaceutical molecules
(Scheme 1).[2] For example AKS 186 (I) has been known as
vasoconstriction inhibitor,[2b] compound II have been reported
with anesthetic activity,[2c] and compound-III is exhibiting
On the other hand, transition-metal-catalyzed carbonylation
reactions have already become one of the most powerful toolbox
in modern organic chemistry.[10] With carbon monoxide (CO) as
the C1 source, valuable carbonyl-containing organic molecules
can be easily prepared. Hence the developing of new
carbonylative transformations is meaningful. Additionally, as the
above mentioned importance of heterocycles, the application of
carbonylation in heterocycles synthesis is even more
attractive.[11] Indeed, carbonylation procedures for 3-
methyleneisoindolin-1-ones synthesis have been developed. A
procedure through palladium-catalyzed Sonogashira coupling-
carbonylation-hydroamination sequence in phosphonium salt-
based ionic liquids was reported in 2008 by Alper and co-
workers.[5f] Good yields of desired products were produced from
2-halogen-iodobenzenes. Recently, Gabriele, Mancuso and co-
workers developed an interesting PdI2-catalyzed cyclization of 2-
alkynylbenzamides with secondary amines under oxidative
sedative
activity
(Scheme
1).[2d]
Additionally,
3-
methyleneisoindolin-1-ones are serving as key intermediates in
organic synthesis as well.[3]
carbonylation
conditions.
Good
yields
of
3-
[(dialkylcarbamoyl)methylene]isoindolin-1-ones were formed.[12]
Jiang’s group reported an attractive palladium-catalyzed
carbonylation of aromatic oximes for the preparation of 3-
methyleneisoindolin-1-ones via C-H bond activation.[13] With
oximes as the substrates under atmosphere of carbon monoxide,
good yields of the desired heterocycles were isolated. More
recently, Huang and co-workers developed a novel rhodium-
catalyzed oxidative carbonylation of ketimines.[14] Good yields of
3-methyleneisoindolin-1-ones were obtained under 30 bar of CO
via C-H activation. Although carbon monoxide as one of the
cheapest C1 sources, hold advantages in industrial scale
applications, its special characters (high toxicity, smell-less,
flammable and etc.) limited its usage in laboratories. Hence, the
developing of synthetic procedures based on CO surrogates will
be interesting for our synthetic community.[15] Among all the
candidates, Mo(CO)6 as a non-toxic solid is an attractive CO
source.[16] Under these backgrounds, we wish to report here a
new palladium-catalyzed carbonylative intramolecular cyclization
of ketimines via C-H bond activation with [Mo(CO)6] as the solid
and safe CO source. In the presence of palladium catalyst and
0.3 equivalent of Mo(CO)6, moderate to good yields of the
desired substituted 3-methyleneisoindolin-1-ones were isolated.
Our initial investigation was started with the reaction of 1-
phenyl-2-(1-phenylethylidene)hydrazine (1a), in the presence of
10 mol% of Pd(OAc)2, [Mo(CO)6] (1 equiv.) and Cu(OAc)2 (2
equiv.) in 1,2-dichloroethane (DCE) at 80 oC, to our delight, 33%
of the desired N-(1-methylene-3-oxoisoindolin-2-yl)benzamide
(2a) was formed after 20 hours (Table 1, entry 1). Based on this
initial finding, various oxidants were tested subsequently. The
Scheme 1. Representative pharmaceutical molecules.
Due to the proven importance of 3-methyleneisoindolin-1-
ones, considerable attentions have been attracted to develop
new procedures for their preparation. Traditionally, 3-
methyleneisoindolin-1-ones were prepared from phthalimides
either by Wittig reactions or via the addition of organometallic
reagents and followed by dehydration sequence.[4] Alternative
procedures have been established as well. Most of the reported
methodologies are using o-(1-alkynyl)benzamides as the
substrates or through it as the intermediates via
heteroannulation to give the final target products.[5] Recently,
procedures based on C-H activation have been developed as
well. In 2013, Li, Zhou and co-workers reported a novel rhodium-
catalyzed annulation of aryl ketone O-methyl oximes with
isocyanates for the synthesis of 3-methyleneisoindolin-1-ones.[6]
Good yields of the desired products can be obtained by C-H
bond activation. In 2014, ruthenium-catalyzed C-H bond
[a]
Z. Wang, F. Zhu, Y. Li, Prof. Dr. X. -F. Wu
Leibniz-Institut für Katalyse e.V. an der Universität Rostock
Albert-Einstein-Straße 29a, 18059 Rostock (Germany)
E-mail: xiao-feng.wu@catalysis.de
Supporting information for this article is given via a link at the end of
the document.
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yield of product 2a was decreased to 18% when AgOAc was
used as the oxidant (Table 1, entry 2). No product could be
detected with PhI(OAc)2 or K2S2O8 as the oxidant (Table 1,
entries 3 and 4). Improved results could be obtained when BQ
(p-benzoquinone) was applied as the oxidant (Table 1, entry 5).
In order to further improve the outcome, the effects of bases
were investigated (Table 1, entries 6-11). Positive effects were
observed with NaOAc, CsF and Li2CO3, 56% yield can be
achieved with Li2CO3 (Table 1, entry 10). However, only trace of
desired product can be detected with DBU (Table 1, entry 11). In
the loading variation of BQ, 3 equivalents of BQ gave the best
results (Table 1, entry 12). The screening of the solvents
revealed that toluene, DMSO (dimethyl sulfoxide), 1,4-dioxane,
and DMF (N,N-dimethylmethanamide) were all inferior to DCE
(Table 1, entries 14-17). Interestingly, when 0.3 equivalent of
Mo(CO)6 was added, the yield of the targeted 3-
methyleneisoindolin-1-one can be improved to 86% isolated
yield (Table 1, entry 18).
explored and afforded the corresponding products in moderate
to good yields (Table 2, 2b, 2d, 2h, 2i, 2j). When methoxy group
substituted at meta-position of the substrate, only trace of the
desired product 2r can be detected by GC-MS. Interestingly, (E)-
N'-(1-(cyclohex-1-en-1-yl)ethylidene)benzohydrazide can be
applied as starting material as well and gave the corresponding
product 2c in 51% yield without further optimization. In addition
to benzohydrazide, other related derivatives can be applied as
well. 4-Chlorobenzohydrazide, 4-(trifluoromethyl)benzohydrazide
and 4-methoxybenzohydrazide are all shown proper substrates
here and gave the desired products in 43-81% yields (Table 2,
2e-2m).
(E)-N-(1-Oxo-3-(2-phenylethylidene)isoindolin-2-
yl)benzamide derivatives can be produced in moderate yields as
well (Table 2, 2k-2m). The using of aniline as directing group
was tested as well, 66% of 3-methylene-2-phenylisoindolin-1-
one 2n was produced under the standard conditions. O-
Methylhydroxylamine 2o and acetohydrazide 2p-2q have been
proven as applicable directing groups here and gave the
corresponding products in moderate yields. However, no product
can be detected with phenylhydrazine 2s as the directing group
under our condition. To our delight, 31% of 2,4-
diphenylphthalazin-1(2H)-one (4a) can be produced from 1-
(diphenylmethylene)-2-phenylhydrazine (3a) with high selectivity
using phenylhydrazine as the reaction partner (Scheme 2).
Table 1. Optimization of the reaction conditions.[a]
Entry
Oxidant
Base
Solvent
Yield[%][b]
1
2
Cu(OAc)2
AgOAc
PhI(OAc)2
K2S2O8
BQ
-
DCE
DCE
33
18
-
3
-
DCE
0
4
-
DCE
0
5
-
DCE
46
Scheme 2. Carbonylative synthesis of 2,4-diphenylphthalazin-1(2H)-one.
6
BQ
NaOAc
K2CO3
Cs2CO3
CsF
DCE
51
7
BQ
DCE
40
To prove the applicability of this procedure, a one-pot
synthesis was carried out (Scheme 3). With acetophenone and
benzohydrazide as the substrates in DCE for 10 hours then our
catalyst system was inlet, 45% yield of N-(1-methylene-3-
oxoisoindolin-2-yl)benzamide was isolated.
8
BQ
DCE
43
9
BQ
DCE
49
10
11
12
13
14
15
16
17
18[c]
19[d]
BQ
Li2CO3
DBU
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Li2CO3
DCE
56
BQ
DCE
trace
74
BQ (3 eq.)
BQ (4 eq.)
BQ (3 eq.)
BQ (3 eq.)
BQ (3 eq.)
BQ (3 eq.)
BQ (3 eq.)
BQ (3 eq.)
DCE
DCE
55
toluene
DMSO
1,4-dioxane
DMF
54
28
15
Scheme 3. One-pot synthesis from acetophenone.
trace
84 (86)
58
DCE
Based on these results, a plausible reaction mechanism is
proposed (Scheme 4). First, palladium acetate reacted with
imine 1 to give the ortho activated palladium complex A. Under
the assistant of base, complex B will be generated via
DCE
[a] Reaction conditions: 1-phenyl-2-(1-phenylethylidene)hydrazine 1a (0.5
mmol, 1 equiv.), [Mo(CO)6] (0.5 mmol, 1 equiv.), Pd(OAc)2 (0.05 mmol, 10
mol%), oxidant (1 mmol, 2 equiv.), base (1 mmol, 2 equiv.), and solvent (2 mL)
for 20 h at 80 oC in sealed tubes. [b] Yields were determined by GC-MS.
Isolated yield is in parenthesis. [c] [Mo(CO)6] (0.5 mmol, 0.3 equiv.). [d]
[Mo(CO)6] (0.5 mmol, 0.2 equiv.).
isomerization of imine and
X ligand exchange by the
coordination of CO to give the intermediate B. Meanwhile, CO is
released from Mo(CO)6 under the assistant of BQ coordination.
Acylpalladium C as the key intermediate will be formed after the
reaction of CO with complex B. The final product will be
eliminated after reductive elimination of intermediate C and the
meanwhile formed Pd(0) will be re-oxidized to Pd(II) to complete
the catalytic cycle. However, a Pd(II)/Pd(IV) cycle cannot be
excluded here.
With the optimized conditions, we focused our attention on the
scope of the substrates. Overall, all the substrates studied were
conveniently converted into the corresponding carbonylated
products in moderate to good yields (Table 2, 2a-2q). Substrates
with methyl or methoxy groups on the benzene ring were
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Table 2. Palladium-catalyzed carbonylative synthesis of substituted 3-methyleneisoindolin-1-ones.[a]
[a] Reaction conditions: substrate 1 (0.5 mmol, 1.0 equiv.), Pd(OAc)2 (0.05 mmol, 10 mol%), [Mo(CO)6] (0.15 mmol, 0.3 equiv.), BQ (1.5 mmol, 3 equiv.), Li2CO3
(1.0 mmol, 2 equiv.), DCE (2.0 mL), 80 oC, 20 h, air, isolated yields.
ketimines has been developed. With 0.3 equivalent of Mo(CO)6
as the solid CO source, moderate to good yields of the desired
products were produced via C-H bond activation.
Experimental Section
General procedure for the synthesis of ketohydrazone (1a-1s)
Benzonylhydrazine (408 mg, 3 mmol, 1.5 equiv.) was added to a stirred
solution of acetophenone (240 mg, 2 mmol, 1 equiv.) in the solvent of
ethanol (15 mL) at 80 oC. After the reaction mixture was heated for 10 h,
the solvent was then evaporated under vacuum. The crude products
were purified by recrystallization from pentane to afford hydrazine 1a as
a white solid.
General procedure for palladium-catalyzed cyclocarbonylation (2a-
2s)
In a 25 mL sealed tube, a mixture of ketohydrazone 1 (0.5 mmol, 1.0
equiv.), Pd(OAc)2 (11.2 mg, 0.05 mmol, 10 mol%), [Mo(CO)6] (39.6 mg,
0.15 mmol, 0.3 equiv.), BQ (162 mg, 1.5 mmol, 3 equiv.) and Li2CO3 (74
mg, 1.0 mmol, 2 equiv.) in DCE (2.0 mL) was stirred at 80 C under air.
After 20 h, the mixture was cooled to room temperature. The residue was
diluted with H2O solution (10 mL) and extracted with EtOAc (3×10 mL).
Scheme 4. Proposed reaction mechanism.
o
In summary, an interesting palladium-catalyzed carbonylative
synthesis of substituted 3-methyleneisoindolin-1-ones from
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The solvent was then evaporated under vacuum. The crude products
were purified by using column chromatography on silica gel
(pentane/ethyl acetate) to give the pure products 2.
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In a 25 mL sealed tube, benzonylhydrazine (136 mg, 1 mmol, 1 equiv.)
was added to a stirred solution of acetophenone (120 mg, 1 mmol,
o
equiv.) in the solvent of DCE (5 mL) at 80 C. The reaction mixture was
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(79.2 mg, 0.3 mmol, 0.3 equiv.), BQ (324 mg, 3.0 mmol, 3 equiv.) and
Li2CO3 (148 mg, 2.0 mmol, 2 equiv.) were added into the sealed tube.
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General procedure for palladium-catalyzed cyclocarbonylation (4a)
In
a 25 mL sealed tube, a mixture of 1-(diphenylmethylene)-2-
phenylhydrazine 3a (0.5 mmol, 1.0 equiv.), Pd(OAc)2 (11.2 mg, 0.05
mmol, 10 mol%), Xantphos (25.9 mg, 0.05 mmol, 10 mmol%), [Mo(CO)6]
(66 mg, 0.25 mmol, 0.5 equiv.), and BQ (162 mg, 1.0 mmol, 2 equiv.) in
HOAc (2.0 mL) was stirred at 110 oC under air. After 18 h, the mixture
was cooled to room temperature. The residue was diluted with H2O
solution (10 mL) and extracted with EtOAc (3×10 mL). The solvent was
then evaporated under vacuum. The crude products were purified by
using column chromatography on silica gel (pentane/ethyl acetate) to
give the pure products 4a.
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Acknowledgements
We thank the Chinese Scholarship Council for financial Support.
We thank the analytical department of Leibniz-Institute for
Catalysis at the University of Rostock for their excellent
analytical service here. We appreciate the general support from
Professor Matthias Beller in LIKAT.
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Keywords: carbonylation • heterocycle synthesis • molybdenum
hexacarbonyl • palladium catalyst • Domino reaction
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Zechao Wang,[a] Fengxiang Zhu,[a] Yahui
Li,[a] and Xiao-Feng Wu*[a]
Page No. – Page No.
Palladium-Catalyzed Carbonylative
Synthesis of 3-Methyleneisoindolin-1-
ones from Ketimines with Mo(CO)6 as
the CO Source
Text for Table of Contents
An interesting procedure on palladium-catalyzed carbonylative synthesis of 3-
methyleneisoindolin-1-ones from ketimines has been established. With
Mo(CO)6 as the solid CO source via C(sp2)-H bond activation, moderate to
good yields of the desired 3-methyleneisoindolin-1-ones were isolated.
For internal use, please do not delete. Submitted_Manuscript
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