Highly Active Manganese to C?O Cross-Coupling Reaction for the Synthesis of N-Hydroxyphthalimide Esters

Full text of DOI:10.1002/bkcs.11461

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DOI: 10.1002/bkcs.11461
BULLETIN OF THE
S.-R. Joo et al.
KOREAN CHEMICAL SOCIETY
Highly Active Manganese to C O Cross-Coupling Reaction for the
Synthesis of N-Hydroxyphthalimide Esters
Seong-Ryu Joo,† Jong-Sung Kim,† Soo-Youl Park,‡ and Seung-Hoi Kim†,
*
†Department of Chemistry, Dankook University, Cheonan 31116, South Korea.
*E-mail: kimsemail@dankook.ac.kr
‡Interface Chemistry & Engineering Research Team, Korea Research Institute of Chemical Technology,
34114, South Korea
Received February 25, 2018, Accepted March 29, 2018, Published online April 25, 2018
Keywords: Active manganese, C O coupling, N-hydroxyphthalimide ester, Manganese-alkoxide
Since the first report of the direct preparation of highly
active manganese (Mn*) and its application in organic
chemistry has been reported,1 this protocol along with
transmetallation methodology has been widely utilized for
the preparation of organomanganese reagents.2 To date,
most of the successful experiments using Mn* focused on
the construction of C C bond via cross-coupling reactions.
Very recently, we reported a somewhat different type of
Mn* application to cross-coupling reactions, resulting in
C O bond formation.3 In the study, highly active manga-
nese played a role as a reaction promoter to provide the
corresponding esters from the reactions of normal alcohols
with acid chlorides. Albeit the mechanistic details of this
transformation were not investigated in that study, the reac-
tion could be presumably completed via a manganese
alkoxide-like intermediate.
Prompted by this observation, we decided to perform a
further study on the diversification of highly active manga-
nese in C O cross-coupling reactions. To address this issue,
N-hydroxyphthalimide (NHPI) was among the best candi-
date to execute our strategy, since NHPI is a slightly differ-
ent type of hydroxyl-group-containing compound from the
alcohols used in our previous research.3 More interestingly,
NHPI has proved to be an efficient and broadly applicable
radical precursor in cross-dehydrogenative coupling (CDC)
reactions.4 Therefore, we assumed that the utilization of
NHPI in our reaction system could be very useful to deter-
mine the role of highly active manganese (i.e., radical versus
metal alkoxide source). Secondly, the application of NHPI
in the CDC strategy with aldehydes and alcohols has been
intensively developed to provide facile protocols for the
preparation of N-hydroxyimide esters,5,6 which could be the
resulting products from our C O coupling reaction strategy.
In addition, these active esters have often been used in ami-
dation and peptide synthesis as valuable coupling intermedi-
ates.5,7 Therefore, we anticipated that our strategy would
provide an alternative synthetic tool for the synthesis of N-
hydroxyimide esters.
then the obtained complex was subjected to coupling with
carbonyl compounds.
Since our first goal was to find out the best coupling
partner, we decided to carry out the screening test with var-
ious carbonyls. As described in Table 1, NHPI was initially
treated with Mn* in THF at room temperature, resulting in
the formation of a dark solution (1a). Next, an appropriate
carbonyl compound (1.0 equiv) was added to the solution
(1a). To our delight, the expected N-hydroxyphthalimide
ester, 1,3-dioxoisoindolin-2-yl benzoate (3a), was obtained
from the reaction of benzoyl chloride in 75% isolated yield.
With the expectation of forming 3a by using an aldehyde
or a carboxylic acid as a coupling partner, both benzalde-
hyde and benzoic acid were also examined in the system.
Unfortunately, no coupling reaction took place. Compared
with the positive outcome delivered by benzoyl chloride,
benzoic anhydride turned out to be less effective in our sys-
tem, but it still gave rise to the corresponding product 3a
with a diminished yield (25%). For fine tuning of the ratio
of Mn* to NHPI, additional tests using 1.0 equiv of
Mn*/1.0 equiv of NHPI/1.0 equiv. of benzoyl chloride, and
1.0 equiv. of Mn*/1.5 equiv of NHPI/1.0 equiv of benzoyl
chloride were carried out. However, no improvement in
terms of isolated yield was observed. A mixture of uniden-
tified products was obtained instead.
In addition to the preliminary tests with the carbonyls
above, various coupling partners such as acid anhydrides
and sulfonyl chlorides, were employed to elucidate the
applicability of our system and the results are described in
Scheme 1.
The coupling of 1a with acetic anhydride led to the forma-
tion of the corresponding product, 1,3-dioxoisoindolin-2-yl
acetate (2a), in a relatively lower yield (24%). The result
obtained from utilizing trifluoroacetic anhydride (2b, 29%
isolated yield) was not very different. Furthermore, to
explore O S bond formation, both benzene sulfonyl chloride
and p-toluenesulfonyl chloride were reacted with 1a under
the same conditions. To our great delight, the corresponding
products, 1,3-dioxoisoindolin-2-yl benzenesulfonate (2c)
and 1,3-dioxoisoindolin-2-yl 4-methylbenzenesulfonate (2d)
Based on this assumption, our initial set of experiment
involved reacting highly active manganese with NHPI, and
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Table 1. Screening for coupling partners.
a
Isolated yield (based on NHPI).
were successfully produced, but in severely reduced isolated
yields (16% and 8%, respectively). Additionally, ethyl chlor-
oformate was also reacted with 1a, resulting in a partially sat-
isfied outcome (2e, 18%).
On the basis of all of the outcomes above, it could be
inferred that acid chlorides would be the most suitable sub-
strates to couple with 1a, giving rise to the corresponding
coupling products in terms of isolated yield.
Next, two control experiments were also performed to
explore the role of Mn*. As shown in Scheme 2, NHPI
was reacted with benzoyl chloride in the absence of any
catalyst in THF at room temperature, resulting in no reac-
tion. To address an oxide-type coupling procedure, a typi-
cal Et3N-catalyzed coupling reaction of 1a with benzoyl
chloride was carried out providing 3a in 34% isolated yield.
The use of other organic bases such as DBU and (n-
Bu)2NH also provided 3a in the range of 40–45% isolated
yields. Based upon these results, it could be perceived that
the presence of the phthalimide N-oxide-like intermediate
(1a) was critical for the effective completion of C O bond
forming even though there is no obvious evidence, and
highly active manganese was a suitable reagent for produc-
ing the intermediate 1a.
Scheme 2. Controlled reactions searching for the role of Mn*.
To gain further insight into the presence of potential radi-
cal species, phthalimide N-oxy (PINO), a brief control
experiment was set up in the following manner (Scheme 3).
Since this radical species has been reported and considered
to be a reaction intermediate in previous similar studies,4
the test would enable us to determine whether radical spe-
cies existed in our system. When the coupling reaction of
1a with benzoyl chloride was carried out in the presence of
a radical scavenger 2,2,6,6-tetramethylpiperidine N-oxide
(TEMPO, 1.0 equiv) under the same conditions used
before, smooth progress was indicated, furnishing the
desired product (3a) with a slightly reduced isolated yield
(71%). Considering the results obtained thus far, even
though detailed mechanistic studies have not performed, we
inferred that our reaction system worked via a manganese
alkoxide-like intermediate rather than a radical pathway.
With the above observations in hand, we began to exam-
ine the scope of this strategy to develop a novel synthetic
pathway for the preparation of N-hydroxyphthalimide esters
using a variety of acid chlorides. The results are summa-
rized in Table 2.
The coupling reactions with halobenzoyl chlorides were
examined first, generating the desired esters (3b-d, Table 2)
with moderate isolated yields. Next attempts were con-
ducted with electron-rich and electron-deficient aryl acid
chlorides. As depicted below, coupling with aryl acid chlo-
rides bearing electron-donating groups such as methyl,
methoxy, and t-butyl moieties produced the corresponding
products (3g-i, Table 2) in higher yields (78–85%) than that
(3e and 3f, 57 and 40%, respectively) of electron-
withdrawing groups. The following two reactions (entries
9 and 10, Table 2) clearly showed a steric effect on the
coupling reaction. A mixture of indistinguishable products
was obtained from the reaction with 1-naphthanoyl chloride
Scheme 1. Coupling of 1a with anhydrides and sulfonyl
chlorides.
Scheme 3. Control reaction with TEMPO.
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Table 2. Scope of the reaction of 1a with acid chlorides.
Scheme 4. Reaction with N-hydroxysuccimide.
under the conditions used whereas 2-naphthanoyl chloride
reacted well with 1a affording 3j in 44% isolated yield.
Heteroaromatic carbonyl chlorides were additionally proven
to be suitable partners for our system. For examples,
2-furoyl chloride, 2-thiophenecarbonyl chloride, and
6-chloronicotinoyl chloride were efficiently coupled with
1a to produce the corresponding N-hydroxyimide esters (3l,
3m, and 3n, Table 2) in 38–50% yields.
The coupling reaction with acid chlorides was then
expanded to alkyl acid chlorides. As expected, all the reactions
of cyclic and non-cyclic acid chlorides took place successfully
at room temperature furnishing the corresponding esters (3o–
q, Table 2) in moderate yields. The applicability of 1a was
further examined by the reaction with carbamoyl chlorides
(entries 18 and 19, Table 2). Unlike the previous cyclic acid
chlorides, it was found that no coupling reaction was observed
with a sterically demanded 4-morpholinecarbonyl chloride.
On the other hand, dimethylcarbamoyl chloride gave rise to
the coupling product 3r in 44% isolated yield.
Encouraged by the results described above, the same
reaction environment was adapted to the coupling of N-
hydroxysuccinimide (NHSI) with acid chlorides. Unfortu-
nately, the expected N-hydroxysuccinimide esters were not
generated even at various reaction conditions such as pro-
longed reaction time, elevated temperature, and various
molar ratios. Instead, a mixture of the 1,4-halohydrines
generated from the ring-opening of tetrahydrofuran was
exclusively obtained (Scheme 4).8
In conclusion, we have demonstrated the first example of
a highly active manganese-mediated C O cross-coupling
reaction of readily available NHPI with a variety of acid
chlorides under mild conditions. The resulting products, N-
hydroxyphthalimide esters, were successfully obtained from
the reaction of acid chlorides and NHPI in the presence of
Mn* under mild conditions, whereas no reaction occurred
when utilizing NHSI. A concise mechanistic study showed
that the formation of a manganese alkoxide-like intermedi-
ate could be responsible for producing coupling products.
Further applications of this strategy are currently underway
in our laboratory.
Experiment
A typical preparation of highly active manganese (Mn*): In
a 25 mL round-bottom flask, lithium (9.68 mmol), naphtha-
lene (1.48 mmol), and anhydrous manganese iodide
(4.71 mmol) were placed under argon pressure. Next,
freshly distilled THF (10 mL) was added into the flask,
a
Isolated yield (based on acid chloride).
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then the mixture was allowed to stir at room temperature
for 3 h. The resulting black solution containing highly
active manganese was ready for use.
Representative procedure: (a) Preparation of bis(1,-
3-dioxoisoindolin-2-yloxy)manganese (1a): In 25 mL of
round-bottomed flask containing 1.5 mmol of active man-
ganese in THF was added 0.49 g (3.0 mmol) of N-
hydroxyphthalimide at room temperature. The resulting
mixture was stirred at room temperature for 1.0 h, then set-
tled down at room temperature. The top layer was cannu-
lated into a 25 mL of flask. (b) Cross-coupling reaction of
1a with 4-methoxybenzoyl chloride; To a 25 mL of flask
containing 3 mL (0.5 M in THF, 1.5 mmol) bis(1,-
3-dioxoisoindolin-2-yloxy)manganese (1a) was added
0.51 g (3.0 mmol) of 4-methoxybenzoyl chloride. The
resulting mixture was stirred at room temperature for 3.0 h.
The reaction mixture was quenched with saturated NH4Cl
solution and extracted with ether (10 mL × 3). The com-
bined organic layers were washed with saturated Na2S2O3
solutions and brine and dried over MgSO4. Column chro-
matography with 5% ethyl acetate/95% Hexanes afforded
1.26 g of 3 h (85%) as a pale yellow solid (m.p.
1
ꢀ
76–78 C). H NMR (CDCl3, 500 MHz): 8.16 (dt, J = 2.8,
2.1 Hz, 2H), 7.42 (t, 8.4 Hz, 2H), 7.20 (d, 6.3 Hz, 2H),
6.98 (dt, J = 2.8, 2.1 Hz, 2H), 3.89 (s, 3H); 13C NMR
(CDCl3, 125 MHz): 180.30, 164.94, 163.90, 133.00,
132.30, 129.44, 125.73, 121.82, 113.85, 59.60 ppm.
HRMS; calcd for C16H11NO5 297.0637, found 297.0721.
Acknowledgments. This work was supported in part by
DANKOOK ChemBio Specialization for Creative Korea
(CK)-II in 2017.
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Bull. Korean Chem. Soc. 2018, Vol. 39, 829–832
© 2018 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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