Efficient Synthesis of Phthalimides via Cobalt-Catalyzed C(sp2)?H Carbonylation of Benzoyl Hydrazides with Carbon Monoxide

Article abstract of DOI:10.1002/adsc.201800388

A cobalt-catalyzed C?H carbonylation of benzoyl hydrazides has been developed by using 2-(1-methylhydrazinyl)pyridine as the bidentate directing group. This transformation is mild, efficient, operationally simple, and highly functional-group-tolerant. The protocol has generated a broad range of phthalimide derivatives in good to excellent yields. The ligand moiety can be readily removed through hydrogenolysis. (Figure presented.).

Full text of DOI:10.1002/adsc.201800388

Title: Efficient Synthesis of Phthalimides via Cobalt-Catalyzed C(sp2)
̶
H Carbonylation of Benzoyl Hydrazides with Carbon Monoxide
Authors: Shuxian Qiu, Shengxian Zhai, Huifei Wang, Cheng Tao, Hua
Zhao, and Hongbin Zhai
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Advanced Synthesis & Catalysis
10.1002/adsc.201800388
COMMUNICATION
2
Efficient Synthesis of Phthalimides via Cobalt-Catalyzed C(sp )
̶
H Carbonylation of Benzoyl Hydrazides with Carbon Monoxide
a
a,b
a
a,b
a
Shuxian Qiu, Shengxian Zhai, Huifei Wang, Cheng Tao, Hua Zhao, and Hongbin
*a,b,c
Zhai
a
The State Key Laboratory of Chemical Oncogenomics and the Key Laboratory of Chemical Genomics, Shenzhen
Graduate School of Peking University, Shenzhen 518055, China, E-mail: zhaihb@pkusz.edu.cn
The State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou
University, Lanzhou 730000, China
b
c
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), China
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: A cobalt-catalyzed C–H carbonylation of C–H carbonylation assisted by oxalyl amide for 3,4-
benzoyl hydrazides has been developed by using 2-(1- dihydroisoquinolinone was described by Zhao et al.
[7f]
methylhydrazinyl)pyridine as the bidentate directing group. (Scheme 1c).
This transformation is mild, efficient, operationally simple,
and highly functional-group-tolerant. The protocol has
generated a broad range of phthalimide derivatives in good
to excellent yields. The ligand moiety can be readily
removed through hydrogenolysis.
Keywords: Phthalimides; Cobalt catalyst; C ̶ H
carbonylation; Benzoyl hydrazides; Hydrogenolysis
Introduction
Over the past few decades, transition-metal-catalyzed
direct C–H functionalization has become a powerful
methodology for efficient construction of organic
building blocks, providing an attractive alternative to
the traditional cross-coupling reactions without
[1]
prefunctionalization of the starting materials.
Meanwhile, significant progress has been made in the
carbonylation of C–H bonds using CO as the C1
feedstock.[ The first carbonylation via directed,
transition-metal-catalyzed functionalization of a C–H
2
Scheme 1. Bidentate Directing-based C(sp )–H
Carbonylation with CO.
2]
bond was disclosed by Murahashi in 1955, in which
was employed as the catalyst.[ Since this
3]
The phthalimide unit is a key synthetic constituent
of many bioactive molecules and pharmaceuticals
Co
2
(CO)
8
[9]
pioneering work, numerous metals have been found
[10]
2
such
as
thalidomide,
to be effective in carbonylation of C(sp )–H or
[11]
[12]
[13]
3
[4]
[5]
amphotalide, taltrimide, and talmetoprim
C(sp )–H bonds, such as palladium, ruthenium,
[6]
and rhodium, and various methodologies have been
developed for direct carbonylation of C–H bonds by
(Figure 1), and they display outstanding biological
and pharmacological activities, such as sedative,
antifungal, antiepileptic or antibacterial activity.
Consequently, development of a direct and efficient
method to rapidly construct phthalimide derivatives is
still highly desirable. Recently, our group developed
novel bidentate directing group 2-(1-
methylhydrazinyl)pyridine applied in cobalt-
Compared with
other bidentate directing groups, the ligand can be
reductively cleaved under mild conditions. Herein we
[4-6]
employing monodentate
directing groups. As for
directing-based
the
bidentate[
7]
C(sp )–H
2
carbonylation, Chatani and co-workers developed a
Ru-catalyzed carbonylation of aromatic amides with
CO by utilizing the bidendate pyridine-2-
[7a]
a
ylmethyamine moiety in 2009 (Scheme 1a).
Subsequently, Daugulis’s group reported a Co-
catalyzed C–H carbonylation directed by 8-
aminoquinoline[ in the presence of an atmospheric
[14]
catalyzed C−H functionalization.
8]
[7d]
pressure of CO (Scheme 1b), and a Pd-catalyzed
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201800388
2
conditions,[7d] phthalimide 2a was obtained in only
17% yield.
describe
a
cobalt-catalyzed
C(sp )–H
carbonylation[ assisted by this bidentate directing
group, a useful method for facile synthesis of
phthalimide derivatives (Scheme 1d).
15]
Table 1. Optimization of the Reaction Conditions.[a]
Ag
(
2
CO
3
T
yield
entry
[Co]
solvent
o
[b]
equiv.)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.0
1.2
1.2
1.2
1.2
1.2
1.2
1.2
/
( C) (%)
1[c]
2[c]
3[c]
4[c]
5[c]
6[c]
7[c]
8
Co(OAc)
·4H
O
O
O
PhCl
PhCl
PhCl
PhCl
PhCl
150
120
100
65
75
90
2
2
2
2
2
2
Co(OAc)
Co(OAc)
·4H
·4H
CoBr
2
100 trace
Co(acac)
2
100
55
91
30
99
90
99
94
91
Co(OAc)
Co(OAc)
Co(OAc)
Co(OAc)
2
2
2
2
·4H
·4H
·4H
·4H
2
2
2
2
O
O
O
O
toluene 100
TFE 100
Figure 1. Phthalimide motifs in pharmaceuticals.
toluene 100
toluene 100
toluene 100
toluene 100
toluene 100
9
Results and Discussion
10
Co(OAc) ·4H O
2
2
2
2
2
2
1
1[d] Co(OAc)
2[e]
·4H
·4H
O
O
Initially, N'-methyl-N'-(2-pyridinyl)benzohydrazide
1
Co(OAc)
16]
13[f] Co(OAc) ·4H O
toluene 100 trace
(
1a)[ was chosen as a substrate. To our delight,
2
2
treatment of 1a with an atmospheric pressure of CO
in the presence of Co(OAc) ·4H O (10 mol %),
Ag CO (2.0 equiv.) and NaOAc (1.0 equiv.) in PhCl
14
15
16
17
Co(OAc) ·4H O
toluene
toluene
90
80
94
89
2
2
2
2
Co(OAc)
/
Co(OAc)
2
·4H
2
O
2
3
toluene 100
toluene 100
ND
ND
at 150 °C for 12 h afforded the desired phthalimide
product 2a in 65% yield (Table 1, entry 1). Lowering
the reaction temperature to 120 or 100 °C improved
the yield to 75% or 90%, respectively (entries 2 and
2
·4H
2
O
[
a]
Reaction conditions: 1a (0.2 mmol), Co(OAc)
mol %), Ag CO , CO (1 atm), solvent (2 mL), 12 h, sealed tube.
Isolated yield.
Co(OAc) ·4H
O (5 mol %). [e] Co(OAc)
Mn(OAc) ·2H O was used instead of Ag
2 2
·4H O (10
2
3
[
b]
[c]
[d]
NaOAc (1.0 equiv.) was added.
·4H
O (2.5 mol %). [f]
CO
2
2
2
2
3
). Encouraged by this result, we then investigated
other cobalt salts and found that trace product was
obtained from the CoBr -catalytic system, while
product 2a was isolated in 55% yield with Co(acac)
entries 4 and 5). Solvent screening showed that the
use of toluene resulted in 91% for the product (entries
and 7). We then chose more environmentally
3
2
2
3
.
2
With the optimized conditions established, we then
explored the scope of the current C–H carbonylation
reaction (Scheme 2). In general, the reaction showed
good functional group tolerance and provided the
desired phthalimide products in good to excellent
yields. First, substrates with a variety of either
electron-donating (2b, 2c, 2d, 2e, 2f, 2g, 2h and 2i)
or electron-withdrawing (2j, 2k, 2l, 2m, 2n, 2o and
2
(
6
friendly toluene as the solvent to carry out the further
investigation. Surprisingly, the reaction still
proceeded smoothly in 99% yield without NaOAc
2
p) para-substituents on the aromatic ring were
(
entry 8). The yield decreased to 90% when the
amount of Ag CO was reduced from 2.0 equiv. to
.0 equiv. in the absence of NaOAc (entry 9).
Nevertheless, the product could be obtained in 99%
yield with 1.2 equiv. of Ag CO added as the oxidant
entry 10). When 5.0 mol % or 2.5 mol % of
Co(OAc) ·4H O was used, the yield was slightly
(entries 11 and 12). When
·2H O was used as oxidant instead of
compatible with the catalytic system. However, the
benzoyl hydrazides bearing a strong electron-
withdrawing group on the benzene ring led to slightly
reduced yields (2q, 2r). Although meta-substituted
benzoyl hydrazides afforded the corresponding
products in excellent yields with high regioselectivity
(2s-2u), the piperamide gave two regioisomers with a
ratio of 1:1 (2ab/2ab’). A possible reason for such a
difference in the selectivity is the free rotation of the
methoxy group in 1t, causing a shielding effect that
prevents the metal from approaching the C−H bond.
Thus, C−H activation would take place selectively at
the other side. In contrast, the 1,3-dioxo group in
2
3
1
2
3
(
2
2
decreased
Mn(OAc)
3
2
2 3
Ag CO , only a trace amount of product was obtained
(
entry 13). The yield dropped when the temperature
o
was lowered to 80-90 C (entries 14 and 15). Control
experiments showed that both the catalyst and the
oxidant were essential for the carbonylation reaction
(
entries 16 and 17). Note that when the reaction of
substrate 1a was carried out under Daugulis's
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201800388
Scheme 3. Mechanistic Studies of the C−H Activation.
A plausible mechanism for the carbonylation
reaction is proposed in Scheme 4. Hydrazide 1a first
II
coordinates with the Co complex to give
intermediate A, which leads to the 5-membered
II
cobaltacycle B upon oxidation of Co with Ag
2
CO
3
Scheme 2. Substrate Scope of the Benzoyl Hydrazides.
and the subsequent carboxylate or carbonate-
mediated ortho-proton abstraction (path
Alternatively, the reaction may proceed
[15l,15m,15u,17]
a).
with oxidation of Co to Co by Ag
chelation with 1a and the subsequent C–H activation,
hydrazide 1ab is locked so that the metal can
approach the C−H bond without any unfavorable
interactions and C–H activation could take place at
both ortho positions of the carbonyl group. ortho-
Substituted aromatic hydrazides provided the
corresponding phthalimides in 95-98% yields (2v,
II
III
2
CO prior to the
3
[15h,15j,15n,15p,15r]
generating intermediate B (path b).
Insertion of carbon monoxide into the C–Co bond in
B affords the 6-membered cobaltacycle C, which
undergoes reductive elimination to give phthalimide
2
w). Multisubstituted benzoyl hydrazides behaved
I
similarly (2x, 2y, 2aa and 2ac). 1-Naphthamide
derivative gave an excellent yield of 96% (2z). As a
heteroaromatic substrate, isonicotinamide seemed to
be less efficient under the standard reaction
conditions, generating 2ad in only 39% yield. The
hydrazide with a cyclopentene moiety failed to give
the desired product (2ae).
2a with simultaneous release of the Co species. The
I
II
Co species is reoxidized to the Co species by
Ag CO to complete the catalytic cycle.
2
3
Relevant experiments were carried out to probe the
mechanism of the carbonylation reaction (Scheme 3).
The intermolecular competition experiment between
1
a and [D
and [D ]-2a with a ratio of 1.5:1 (Scheme 3a),
suggesting that the C–H bond activation step is not
the rate determining step. When 1a and [D ]-1a were
subjected to the standard conditions with the addition
of 10 equiv. of CD OD and CH OH, respectively
Scheme 3b), no H/D exchange was observed, which
5
]-1a gave the carbonylation products 2a
4
5
3
3
(
indicated that the C–H bond cleavage should be an
irreversible process. Furthermore, addition of radical
scavengers such as TEMPO (2.0 equiv.) or BHT (2.0
equiv.) led only to slight decrease in the yield of 2a
(
82% and 59%, respectively), and increasing the
amount of TEMPO to 4.0 equiv. still gave a yield of
9% for 2a (Scheme 3c), which implied that a single
Scheme 4. Proposed Mechanism.
7
electron transfer (SET) process might not be involved
in the reaction.
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201800388
To demonstrate the synthetic utility of this method,
several notable transformations were conducted
Scheme 5). First, carbonylation of hydrazide 1a was
hexanes/EtOAc (5:1 ~ 3:1, v/v)] to afford corresponding
product 2.
(
scaled up to gram scale with comparable yield and
efficiency under the standard reaction conditions
Acknowledgements
(
Scheme 5a). Treatment of compound 2a with Raney
We thank the NSFC (21732001, 21672017, 21472072, 21290183),
Shenzhen Science and Technology Innovation Committee
(JCYJ20150529153646078,
Program for Changjiang Scholars and Innovative Research Team
in University (PCSIRT: IRT_15R28), and “111” Program of
MOE for financial support.
Ni successfully cleaved the N−N bond to give
[18]
phthalimide 3a in 78% yield. In addition, treatment
of 2a under acidic conditions afforded the ring
opening product 3b in 89% isolated yield.
Sonogashira coupling of bromide 2l with propargyl
alcohol 4a afforded internal alkyne 3c in good yields.
JSGG20160229150510483),
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