Palladium-Catalyzed Cascade Reductive and Carbonylative Cyclization of Ortho-Iodo-Tethered Methylenecyclopropanes (MCPs) Using N-Formylsaccharin as CO Source

Article abstract of DOI:10.1002/adsc.201901005

A palladium-catalyzed reductive and carbonylative cyclization of ortho-iodo-tethered methylenecyclopropanes (MCPs) using N-formylsaccharin as CO source has been developed, affording the desired indanone derivatives in moderate to good yields with high regio- and stereoselectivity and good functional group compatibility.

Full text of DOI:10.1002/adsc.201901005

Title: Palladium catalyzed cascade reductive and carbonylative
cyclization of ortho-iodo-tethered methylenecyclopropanes
(MCPs) using N-formylsaccharin as CO source
Authors: Xing Fan, Min Shi, and Yin Wei
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201901005
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10.1002/adsc.201901005
Advanced Synthesis & Catalysis
.
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-Catalyzed Cascade Reductive and Carbonylative Cyclization
of ortho-Iodo-Tethered Methylenecyclopropanes (MCPs) Using N-
Formylsaccharin as CO Source†
Xing Fan,a Min Shi,a,b and Yin Weia*
a
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, University of Chinese
Academy of Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road,
Shanghai 200032, P. R. of China.
b
Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen, Guangdong 518000, P. R. of
China.
Fax: (+86)-21-6416-6128; e-mail: weiyin@sioc.ac.cn
Received: ((will be filled in by the editorial staff))
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 palladium-catalyzed reductive and carbonylative
cyclization of ortho-iodo-tethered methylenecyclopropanes
(MCPs) using N-formylsaccharin as CO source has been
developed, affording the desired indanone derivatives in
moderate to good yields with high regio- and stereoselectivity
and good functional group compatibility.
Carbonylation reactions have been the focus of extensive
research in organic syntheses and industrial processes
employing CO as the C1 source.[3] However, shortcomings such
as high pressure, toxicity, and inflammability limit the overall
utility of CO. Hence, carbonylation methodology conducted
without the use of CO would be a reliable and accessible choice
for the further advancement of sustainable chemistry.
Considerable efforts have been focused on the development of
CO surrogates for carbonylation reactions.[4] The typical known
CO surrogate compounds include methanol,[5] 1,3-dioxolane,[6]
formaldehyde,[7] paraformaldehyde,[8] silacarboxylic acids,[9]
formic acid and its derivatives,[10] acyl chloride derivatives,[11]
carbon dioxide,[12] metal carbonyls,[13] and N-formylsaccharin
(NFS).[14] These reagents offer CO in situ upon heating or metal
catalysis or treatment with acid or base to avoid handling the gas;
some of them even can be recycled after release of CO. For
instance, NFS, working as an easily accessible and highly
reactive crystalline CO surrogate, can be easily synthesized from
saccharin and also can be reused.[14g,h]
In 2013, Manabe’s group reported a novel and practical
method for palladium-catalyzed reductive carbonylation of aryl
halides with N-formylsaccharin to produce aromatic aldehyde
derivatives in good yields. The carbonyl group in product was
derived from NFS, while the hydrogen atom was derived from
Et3SiH (Scheme 1a).[14b]
Due to the highly strained small ring and excellent
reactivity, methylenecyclopropanes (MCPs) can undergo
various ring-opening reactions in the presence of transition
metal catalyst such as palladium catalyst.[15] In 2004,
Yamamoto and co-workers reported a novel Pd(PPh3)4
catalyzed intramolecular cycloadditions of MCPs including
an amine moiety, in which the ring-opening of substrates
occurred at the distal C-C bond, affording the
corresponding hydroamination products (Scheme 1b).[16] In
Keywords:
cyclization; ortho-iodo-tethered methylenecyclopropanes
(MCPs); N-formylsaccharin; indanone derivatives;
stereoselectivity.
Pd-catalyzed;
reductive
carbonylative
Indanone derivatives and their analogues are important
bioactive molecules, which are of great significance in
antibacterial, antispasmodic and cytotoxic activities as well
as antineoplastic activity.[1a] For example, Donepezil
hydrochloride acting as an AChE (acetylcholinesterase)
inhibitor has been used for the treatment of mild to moderate
Alzheimer’s disease.[1b] QF 0313B has been employed as a
muscle relaxant reagent and so on.[1c] In addition, some
indanones are important structural motifs in naturally
occurring
compounds;
including
pterosin
Z,[1d]
indacrinone,[1e] (-)-viridin[1f] and pauciflorol F (Figure 1).[1g]
Moreover, indanone derivatives are often used as drug
intermediates and metal ligands for the preparation of metal
complexes.[2]
Figure 1. Natural products and medicines bearing indanone
2017, our group developed
a
palladium-catalyzed
structures.
cyclization of aniline-tethered MCPs under oxidative
1
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10.1002/adsc.201901005
Advanced Synthesis & Catalysis
conditions, in which the insertion of palladium into the
proximal C-C bond took place, giving 2- and 3-vinylindole
derivatives (Scheme 1c).[17] Very recently, our group also
developed a novel palladium-catalyzed cascade cyclization
of MCPs via a cyclopropene intermediate and a vinyl-
palladium carbene species, furnishing spirocyclic
compounds in an unprecedented ring-opening pattern of
MCPs (Scheme 1d).[18]
product (Table 1, entry 1). Elevating the temperature to 70 °C or
75 °C, the conversion of 1g was improved and the yield of 3g
was raised to 48% (Table 1, entries 2 - 3). Carrying out the
reaction at 80 °C gave 3g in the yield of 45% (Table 1, entry 4).
Next, when the amount of the transfer carbonylation reagent
NFS and Et3SiH were increased from 1.5 to 2.0 eq, both of the
conversion of 1g and the yield of 3g were increased, affording
3g in 53% yield (Table 1, entry 5). Using Ph3SiH instead of
Et3SiH, the yield of 3a slightly decreased to 48% (Table 1, entry
6). The screening of palladium catalysts revealed that the use of
Pd(TFA)2 was the best choice, giving 3a in up to 84% yield
(Table 1, entries 7 - 13). The phosphine ligands such as dppe,
dppb and Xantphos, base and solvents were also examined
respectively, but all affording 3g in lower yields (Table 1,
entries 14 - 18). Notably, when the reaction was carried out
under ambient atmosphere or in the absence of phosphine ligand,
or without Et3SiH or in the absence of base, the yields of 3g
were < 10% (Table 1, entry 19). It should be emphasized here
that when 2a was replaced by 1.0 atm CO atmosphere, 3g was
given in < 10% yield as well (Table 1, entry 19) (for more
details see Tables S1 and S2 in the SI). It should be noted that
this reaction could not take place efficiently when Na2CO3 and
DMF were replaced by other bases and solvents. The
information on the use of other solvents and bases in this
reaction has been summarized in Tables S1 and S2.
Table 1. Optimization of the reaction conditions.a,b
Scheme 1. Palladium-catalyzed reductive carbonylation of
aryl halides with N-formylsaccharin and palladium-catalyzed
cyclization reactions of methylenecyclopropanes (MCPs) go
through different ring-opening patterns.
On the basis of previous research work, herein, we aimed to
develop a tandem reductive and carbonylative cyclization of
MCPs using N-formylsaccharin as CO source under the catalysis
of palladium via a new ring-opening pattern. Initially we
investigated the reaction of 1a-Br or 1a-I in DMF at 80 °C
using Pd(OAc)2 as the catalyst and dppp as the ligand. The
desired product 3a was obtained, and its structure was
confirmed by X-ray crystal diffraction (see Supporting
Information for the detail).[19] Interestingly, we identified that
higher conversion of 1a and higher yield of 3a could be realized
when 1a-I was used as substrate, suggesting that Ar-I is more
favorable for the Pd-catalyzed carbonylation process (Scheme 2).
Compound 3a was obtained specifically in the E-configuration,
and we did not isolate any other isomer under these reaction
conditions.
a
All reactions were carried out with 1g (0.1 mmol), 2a (0.2
mmol), Pd cat. (10 mol%), ligand (15 mol%), “H” source (0.2
mmol), Na2CO3 (0.25 mmol) in 0.3 mL DMF for 16-48 h under
b
argon atmosphere. NMR yields using 1-fluoronaphthalene as
an internal standard. c Isolated yields. d K2CO3 was used as base.
e
No ligand or no Et3SiH or without base or the reaction was
carried out under air or replaced 2a with 1 atm CO gas.
Scheme 2. An initial investigation on Pd-catalyzed
carbonylation process of MCPs.
With the optimized conditions in hand, we next investigated
the substrate scope, and the results are summarized in Table 2. It
might also be noted that the reaction conditions were slightly
modified for some particular substrates to get better yields. For
substrate 1a, the desired product 3a was obtained in 83%. When
a methyl group was introduced at the benzene ring adjacent to
the iodine atom, the reaction took place smoothly, affording the
target product 3b in the yield of 59%. Introducing substituent R1
To quickly optimize the reaction condition, the substrate 1g
was selected as the template substrate using 19F NMR
spectroscopic data to evaluate the yield of 3g, and the results are
shown in Table 1. The reaction was first tested at room
temperature; and only a small amount of starting material was
converted at room temperature without formation of the desired
2
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10.1002/adsc.201901005
Advanced Synthesis & Catalysis
(F, Cl, Br, Me or OMe) at the 4- or 5-position of the benzene
ring bearing an iodine atom, the reactions also proceeded
efficiently, giving the corresponding products 3c - 3j in
moderate to good yields regardless of whether electron-
withdrawing group or electron-donating group was introduced.
When the substituents were introduced at another benzene ring,
the reactions could take place smoothly as well. For example,
when a fluorine atom was introduced at the ortho-position, the
desired product 3k was obtained in the yield of 91%.
Introducing substituents at the meta-position, the reactions
proceeded very well no matter it was an electron-donating group
such as Me, or electron-withdrawing group such as CF3, OCF3
or OCF2H, furnishing the corresponding products 3l - 3o in
moderate to good yields ranging from 35% to 85%. As for
substrates 1p - 1r, in which the substituent was introduced at the
para-position, the desired products 3p - 3r were delivered in
22% to 71% yields. For substrate 1p, adding 50 mg of 4Å MS
was required for obtaining the product 3p. In the cases of
substrates 1s and 1t, in which two substituents were introduced
at the two meta-positions of the benzene ring, the corresponding
products 3s and 3t were yielded in 77% and 69% yields,
respectively.
insertion took place to give 3x. For methylenecyclobutane 1y,
no reaction could take place presumably because the sterically
larger cyclobutane blocked the oxidative addition between Pd
and iodobenzene moiety in 1y. When using a methyl group in
place of the phenyl group (substrate 1z), no reaction occurred;
this is perhaps because the methyl group could not stabilize the
double-bond-migrated intermediate IV (shown in Scheme 4) to
promote the reaction. It should be also emphasized here that the
final products 3 were formed only E-selectively without
formation of their Z-isomers.
Furthermore, 3a could be converted to its indenone analogue
4a in 88% yield with an intermolecular Heck reaction under the
catalysis of Pd(OAc)2 at 110 °C (Scheme 3). The other
unsuccessful transformations are also presented in the
Supporting Information (Scheme S5, p S57).
Scheme 3. Transformation of the compound 3a.
On the basis of these experiments, a plausible mechanism
for this reductive and carbonylative cyclization has been
outlined in Scheme 4. At first, the oxidative addition of Ar-I in
1a with palladium affords intermediate I. At the same time,
upon treating NFS with Na2CO3, CO can be released in situ,
which inserts into intermediate I to afford intermediate II. The
iodine atom can be exchanged with H of Et3SiH to afford
intermediate III. In the presence of base and upon heating, the
corresponding cyclopropene intermediate IV can be formed,
which undergoes a reductive Heck reaction to give intermediate
V.[20] The β-C elimination next takes place to yield intermediate
VI and intermediate VII, which finally affords the desired
product 3a via a reductive elimination (Scheme 4) (for
alternative reaction mechanism see Schemes S2 and S3 in the
Supporting Information). The deuterium labeling experimental
result has been also shown in Scheme S4 in the Supporting
Information.
Table 2. Substrate scope for the synthesis of 3a,b
It should be mentioned here that no reaction occurred if
using toxic CO gas itself in the reaction and the precursors of
starting materials 2a (N-formylsaccharin as CO source) can be
recovered as well after release of CO, which can be reconverted
to N-formylsaccharin again. Moreover, when using H2 as the
hydrogen source under ambient atmosphere (H2 balloon) to
replace Et3SiH, no reaction occurred under otherwise identical
conditions.[21]
a
All reactions were carried out with 1 (0.2 mmol), 2a (0.4
mmol), Pd cat. (10 mol%), dppp (15 mol%), Et3SiH (0.4 mmol),
Na2CO3 (0.5 mmol) in 0.5 mL DMF for 16-48 h under argon
b
c
d
atmosphere.
Isolated yields.
White Pd was used.
Pd(CH3CN)2Cl2 was used. e 50 mg 4Å MS was added.
In addition, substrate 1u, in which substituents were
introduced at both of the benzene rings, was also tolerated,
giving the corresponding product 3u in 26%. Substrates 1v and
1w, having heteroaromatic rings, were compatible as well,
yielding the target products 3v and 3w in 70% and 22% yields,
respectively. At the same time, substrate 1x, in which the
cyclopropane was replaced by a methyl group, only produced
the aromatic aldehyde 3x in 41% yield as E and Z-isomeric
mixtures (1.8:1), suggesting that the methylenecyclopropane
moiety is essential for this transformation. This is because the
intramolecular double bond migration in the strained small ring
is important for this transformation. Therefore, in the case of
substrate 1x having no cyclopropane, the only Pd-catalyzed CO
3
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10.1002/adsc.201901005
Advanced Synthesis & Catalysis
then the mixture was heated at 75-85 °C for 16-24 h under argon
atmosphere. After completion of the reaction, the mixture was
cooled to room temperature, and the mixture was concentrated
under reduced pressure and the residue was purified by a flash
column chromatography (SiO2, PE/EA = 30:1-15:1) to afford
the product 3.
Acknowledgements
We are grateful for the financial support from the National
Basic Research Program of China [(973)-2015CB856603], the
Strategic Priority Research Program of the Chinese Academy of
Sciences (Grant No. XDB20000000) and sioczz201808, the
National Natural Science Foundation of China (20472096,
21372241, 21572052, 20672127, 21421091, 21372250,
21121062, 21302203, 21772226, 20732008, 21772037 and
21861132014) and the Shenzhen Nobel Prize Scientists
Laboratory Project.
Scheme 4. A Proposed Mechanism.
In summary, we have disclosed a novel palladium-catalyzed
intramolecular transfer carbonylation and reductive Heck
coupling
cyclization
reaction
of
ortho-iodo-tethered
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General Procedures for the Synthesis of 3
In an oven dried 8.0 mL vial, 1 (0.2 mmol, 1.0 eq), 2a (84.5 mg,
0.4 mmol, 2 eq), Pd cat. (0.02 mmol, 10 mol%), dppp (11.6 mg,
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4
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10.1002/adsc.201901005
Advanced Synthesis & Catalysis
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5
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10.1002/adsc.201901005
Advanced Synthesis & Catalysis
UPDATE
Palladium
carbonylative cyclization of ortho-iodo-tethered
methylenecyclopropanes (MCPs) using N-
formylsaccharin as CO source
catalyzed
cascade
reductive
Adv. Synth. Catal. Year, Volume, Page – Page
Xing Fan,a Ruixing Liu,a Min Shia and Yin Weia,b*
6
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