Rh(III)-Catalyzed Distal C-H Alkenylation of Weakly Coordinating Acetamides Via Desilylation Pathway

Article abstract of DOI:10.1002/adsc.201900307

Rh(III)-Catalyzed distal ortho-C?H alkenylation of arylacetamides have been reported employing acetamide, a weak coordinating group, as a directing group. This challenging C?H alkenylation of arylacetamides has been achieved by using arylalkynyl silanes as a surrogate for terminal alkynes under redox neutral process through desilylation pathway. The control experiments suggest that the in situ generatedRh-species is likely to be Lewis acidic, which is playing a vital role in the desilylation step. (Figure presented.).

Full text of DOI:10.1002/adsc.201900307

Title: Rh(III)-Catalyzed Distal C-H Alkenylation of Weakly Coordinating
Acetamides Via Desilylation Pathway
Authors: Vinay Ramesh, Nachimuthu Muniraj, and Kandikere Prabhu
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900307
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10.1002/adsc.201900307
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Rh(III)-Catalyzed Distal C-H Alkenylation of Weakly
Coordinating Acetamides Via Desilylation Pathway
Vinay Bapu Ramesh,┴a Nachimuthu Muniraj,┴a and Kandikere Ramaiah Prabhu*a
a Department of Organic chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka, India. E-mail:
prabhu@iisc.ac.in
┴ These authors contributed equally
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######
H functionalization of arylacetamides using high-
valent (Cp*M) transition metal catalysts are scarce.
Very recently, Ackermann has reported a distal
ortho-alkenylation of arylacetamides by employing
acrylates (activated olefins) and internal alkynes as
alkene sources.[3]
Abstract.
Rh(III)-Catalyzed
distal
ortho-C-H
alkenylation of arylacetamides have been reported
employing acetamide, a weak coordinating group, as a
directing group. This challenging C-H alkenylation of
arylacetamides has been achieved by using arylalkynyl
silanes as a surrogate for terminal alkynes under redox
neutral process through desilylation pathway. The
control experiments suggest that the in situ generated
Rh-species is likely to be Lewis acidic, which is playing
a vital role in the desilylation step.
Alkenes are important functional groups, which are
susceptible to further synthetic manipulations. Most
of the directed C-H alkenylation reactions using
alkynes were accomplished by utilizing ainternal
alkynes[7-9] as alkene sources under redox-neutral
conditions, whereas compatibility of terminal alkynes
for the similar transformation is limited due to the
presence of relatively acidic proton.[10] Besides,
terminal alkynes are well-known to undergo homo
coupling reaction in the presence of transition metal
catalysts. Generally, Cp*Co(III)-catalytic systems are
quite reactive with terminal alkynes to furnish the
corresponding di-substituted olefin derivatives,[10]
whereas the similar transformation with Cp*Rh(III)-
catalytic systems is rare.[11] This incompatibility of
Keywords: Rhodium; acetamide; alkynyl silane;
alkenylation; desilylation; C-H activation
Directed functionalization is opening up a number of
new avenues for late-stage functionalization of
organic molecules.[1] In the past decade, high-valent
metal-catalyzed (Cp*M, M = Ru, Rh, Co, Ir) C-H
bond activation/functionalization reactions have
received tremendous attention in directing group
strategy as they offer high reactivity, atom- and step-
economical processes under ambient conditions.[1]
Functionalized arylacetamides and arylacetic acids
are essential structural motifs in many biologically
terminal
alkynes
with
Cp*Rh(III)-catalysts
diminishes their synthetic potential in directing group
chemistry. Finding an alternate for terminal alkynes
is highly desirable which remains a challenge. In
continuation of our interest in directing group
chemistry,[12] herein we disclose a distal C-H bond
alkenylation of arylacetamides in the presence of
Cp*Rh(III)-catalyst. This reaction proceeds via a
desilylation route, wherein arylalkynyl silanes are
successfully utilized as surrogates for terminal
alkynes.
active
molecules.[2,3]
Proximal
ortho-C-H
functionalization of arylbenzamides is a well-
explored area under Cp*M catalyst systems.[4]
Arylacetamides are challenging substrates for the
distal C-H bond functionalization using a directing
group strategy due to (i) the intrinsic ability of the
arylacetamide to undergo tautomerization, (ii) the
formation of unfavorable six-membered metallacycle,
and (iii) the weak coordinating ability of acetamide
group. The pioneering work by Yu[5] marks the
beginning of distal C-H bond functionalization of
arylacetamides using Pd-catalyst, which was
persuaded by others.[6] Nevertheless these reactions
require a stoichiometric or super stoichiometric
amount of oxidants or special ligands. Generally,
Cp*M-catalysed C-H activation reactions proceed via
a concerted metalation-deprotonation pathway, which
does not require a terminal oxidant, unless the overall
process is an oxidative one.[1] However, the distal C-
We began our initial studies to investigate the
compatibility of terminal alkynes[10] and its synthetic
equivalents.[13,14] The reaction of arylacetamide 1a
with phenylacetylene under C-H activation conditions,
with Rh-, Ru-, and Co-catalysts, the expected ortho-
alkenylated aryl acetyamide 3aa was not detected
(Scheme 1a and see the SI, Table SI-1). As
arylalkynyl carboxylic acids can also be used as a
surrogate for terminal alkynes,[14] the reaction of 1a
with phenylpropiolic acid in the presence of Rh-, Ru-,
1
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10.1002/adsc.201900307
Advanced Synthesis & Catalysis
Scheme 1. Studies on the compatibility of
phenylacetylene and its synthetic equivalents for
ortho alkenylation of acetamides.
Table 1. Optimization studies[a]
silver salt
(20 mol%) (1 equiv)
additive
solvent
(2 mL)
NMR
yield 3aa
(%)[b]
entry
1
2
3
4
5
6
7
8
9
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgBF4
AgNTf2
AgOAc
none
AdCO2H
AdCO2H
AdCO2H
AdCO2H
PivOH
AcOH
NaOAc
PivOH
PivOH
PivOH
PivOH
PivOH
DCE
TFE
THF
50
nd
45
20
55
44
nd
26
50
dioxane
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
10
11[c]
12[d]
nd
37
and Co-catalysts were performed. However, these
reactions did not lead to the expected alkenylation
product 3aa (Scheme 1b and see SI, Table-SI-2).
Next, the reaction of styrene with arylacetamide 1a in
the presence of Rh(III)-catalyst under oxidative
conditions, furnished the expected ortho-akenylated
product 3aa in 35% yield (Scheme 1c). However, the
yield of the product 3aa could not be improved
beyond 35% (for details see the SI, Table-SI-3).
none
AgSbF6
traces
75(72)[f]
13[e]
PivOH
[a]
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol),
[Cp*RhCl2]2 (5 mol%), Silver salt (20 mol%), additive (1
o
equiv), Solvent (2 mL), 100 C for 12 h. [b] 1H NMR yield
[c]
(using 1,3,5-trimethoxybenzene as an internal standard).
[RhCp*(CH3CN)3][SbF6]2 was used.
[d]
[RhCp*(OAc)2]
was used. [e] 0.4 mmol of 1a and 0.2 mmol of 1a were used.
[f]
As oxidative process often requires a stoichiometric
amount of metal oxidants and leads to the formation
of a large amount of metal waste in the large scale
synthesis, we turned our attention to find another
surrogate for terminal alkynes under redox-neutral
process.[13] To our delight, the reaction of
phenylalkynyl silane 2a (0.24 mmol), with
arylacetamide 1a (0.2 mmol) in the presence of
[RhCp*Cl2]2 (5 mol%) as a catalyst, AgSbF6 (20
mol%) as an activator, and AdCO2H (1 equiv) as an
Isolated yield. nd = not detected. AcOH= acetic acid,
PivOH= pivalic acid.
Changing the catalyst to cationic rhodium complex
[RhCp*(CH3CN)3][SbF6]2 or acetate complex of
rhodium [RhCp*(OAc)2] was also not useful (entries
11 and 12). Finally, the optimal conditions were
achieved by performing the reaction of 0.4 mmol of
1a with 0.2 mmol of 2a, using AgSbF6 (20 mol%),
and PivOH (1 equiv) in DCE (2 mL) at 100 oC for 12
h, which furnished the product 3aa in 75% yield
(entry 13, and see the SI, Table-SI-4 to 10 for a
detailed optimization studies). It is important to note
that the excess of unreacted arylacetamide 1a was
recovered successfully.
o
additive in DCE (2 mL) at 100 C for 12 h, furnished
the expected product 3aa in 50% yield (Table 1, entry
1). It is worth noting that the product 3aa was
obtained through desilylation route. Since
phenylalkynyl silane 2a has furnished a better yield
of 3aa than styrene, further optimization studies were
carried out using phenylalkynyl silane 2a as a
coupling partner. The solvent screening studies
revealed that 1,2-dichloroethane (DCE) is a suitable
solvent for this reaction (entries 1-4). Changing the
additives from AdCO2H to PivOH improved the yield
of the product 3aa to 55%, whereas AcOH brought a
slight dip in the yield of 3aa to 44% (entries 5 and 6).
The reaction using NaOAc as an additive was not
useful as the product 3aa was not detected in the
reaction (entry 7). Changing the activator to AgBF4
or AgNTf2 or AgOAc did not improve the yield of 3a
(entries8-10).
Having established the optimal reaction conditions
for ortho-alkenylation of arylacetamides (entry 13,
Table 1), the scope of the reaction was explored by
employing a variety of arylacetamide derivatives
(Scheme 2). Thus, N-isopropyl, N-tert- butyl, N-
methyl and N,N-dimethyl groups substituted
arylacetamides reacted smoothly with 2a under the
optimal reaction conditions furnishing the products
3aa, 3ba, 3ca and 3da in 72, 54, 58, and 60% yields,
respectively. Arylacetamide derivatives with halogen
substitution on the para-position of the
arylacetamides also underwent a smooth reaction
with 2a yielding the products 3ea-3ha in moderate
yields. 4-Methyl substituted arylacetamide furnished
2
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10.1002/adsc.201900307
Advanced Synthesis & Catalysis
Scheme 2. Substrate scope for arylacetamide
Scheme 3. Scope for alkynyl silane derivatives
derivatives[a,b]
[a] NMR yield.
[a] 1 equiv of AdCO2H was used instead of PivOH.
the product 3ia in 64% yield, whereas 2-methyl
substituted arylacetamide afforded the product 3ja in
43% yield. The low yield of 3ja could be attributed to
the steric crowding exerted by the presence of a
methyl group at the ortho-position. 4-Methoxy and 4-
trifluoromethoxy substituted arylacetamides showed
good reactivity with 2a and rendered the products
3ka and 3la in 65 and 62% yields, respectively. The
reaction of 2-naphthylacetamide with 2a furnished
the product 3ma in 55% yield. The substrates with
electron-withdrawing groups such as NO2 and CF3 on
aylacetamides at the para-position afforded the
products 3na and 3oa in 50 and 55% yields,
methyl substituted arylalkynyl silane under the
optimal reaction conditions afforded the product 4pa
in 51% yield. The reactions of 1a with 2-thipophene
and 4-anisole derived arylakynyl silane derivatives
were less productive affording the corresponding
alkenylated products 4ai and 4aj in 20 and 32%
yields, respectively. Electron-withdrawing group
bearing arylalkynyl silane and alkylalkynyl silanes
are found to be ineffective under the reaction
conditions. Moderate yields obtained in most of the
cases are due to the incomplete consumption of
alkynylsilane.
respectively.
2-(4-Methoxyphenyl)-N-
To gain insight into the reaction mechanism, a few
control experiments were performed (Scheme 4). 4-
Methoxy arylacetamide 1k was reacted with D2O (10
equiv) under the optimal reaction conditions to obtain
70% deuterium incorporation at the ortho- position of
the arylacetamide. This reaction indicates that the C-
H activation may be a reversible process (Scheme 4,
eq 1). The competitive reaction between 4-methoxy
arylacetamide 1k and 1k-d2 with 2a (in the same
vessel) furnished a mixture of 3ka and deuterio-3ka
in a ratio of 1.63:1 in 62% of yield (Scheme 4, eq 2)
suggesting that the C-H activation step may not be
involved in the rate determining step. Most
importantly, the reaction of 1k with 2a under the
methylacetamide reacted with 2a under optimal
reaction conditions furnishing the product 3pa in
62% yield.
A
scale up experiment of
trimethyl(phenylethynyl)silane 2a (5.74 mmol, 1g)
with 1a afforded the corresponding product 3aa in
65% isolated yield.
Next, we turned our attention to explore the scope
of the reaction with arylalkynylsilane derivatives
(Scheme 3). Thus, arylalkynyl silane derivatives with
methyl and tert-butyl substitution on the various
positions of the aryl ring of arylalkynyl silane reacted
smoothly with 1a affording the products 4aa-4ac in
good to moderate yields. The arylalkynyl silane
derivatives with halogen substitution on the aryl ring
reacted with 1a furnishing the products 4ad-4ag in
moderate yields. 1-Naphthyl derived alkynyl silane
underwent a smooth reaction with 1a rendering the
product 4ah in 64% yield. Further the reaction of 2 -
(4-methoxyphenyl)-N-methylacetamide with 4-
optimal reaction conditions furnished
a
non
desilylated ortho-alkenylated product 3ka’ in 6%
yield along with the expected product 3ka in 65%
yield (Scheme 4, eq 3). These experiments indicate
that 3ka’ could be a possible intermediate in the
reaction. Additionally, these experiments reveal that
desilylation is taking place after the alkyne insertion
3
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10.1002/adsc.201900307
Advanced Synthesis & Catalysis
to the metallacycle rather than prior to the alkyne
insertion step. It is noteworthy to mention that the
silylated product 3ka’ was observed only in the case
of aryacetamide 1k. Whereas, other arylacetamides
did not furnish any silylated intermediates, which
may be attributed to the concomitant desilylation.
Next, we turned our attention to find out the reagent
which is responsible for the desilylation. We
hypothesized that acid present in the medium could
be responsible for desilylation. Therefore, we treated
the intermediate 3ka’ with PivOH, which did not
furnish the corresponding desilylated product 3ka
(Scheme 4, eq 4a), suggesting that PivOH has no role
in the desilylation step. Next, the reaction of 3ka’
with AgSbF6 in DCE at 100 oC for 12 h furnished the
corresponding desilylated product 3ka in 70% yield
(Scheme 4, eq 4b). These experiments suggest the
probable involvement of AgSbF6 in the desilylation
step. However, under the reaction conditions, no
AgSbF6 would remain, as 20 mol% of AgSbF6 is
required to generate the active Rh-species A from
[RhCp*Cl2]2 (5 mol%). Therefore, the compound
3ka’ was subjected to the standard reaction
conditions (which in situ forms a cationic species,
[RhCp*(OPiv)] [SbF6], and promotes the desilylation).
As expected, this reaction afforded the desilylated
product 3ka in 98% yield (eq 5a). Additionaly,
treating the compound 3ka’ with the cationic
rhodium complex such as [RhCp*(CH3CN)3][SbF6]2,
also furnished the desilylated product 3ka in 73%
yield (eq 5b). These two experiments (eqs 5a and 5b)
indicate that Rh-species A is likely to be Lewis
acidic, which is responsible for the desilylation. Next,
we treated arylalkynyl silane 2a with AgSbF6, which
failed to furnish the phenylacetylene (corresponding
desilylated product), suggesting that AgSbF6 can
desilylate only the vinylsilane 3ka’ and not an
alkynyl silane 2a (Scheme 4, eq 6). We hypothesized
that phenylalkynyl silane 2a can form silver
phenylacetylide 5 in the presence of AgSbF6 and can
lead to the corresponding alkenylated product.
Therefore, we performed a reaction of 1k with 5
under the optimal reaction conditions, which failed to
furnish the product 3ka, suggesting that silver
phenylacetylide 5 may not be an intermediate in this
reaction (Scheme 4, eq 7). As seen in eq 8, a reaction
of arylacetamides 1k and 1n indicates that the
electronic factors may not influence the outcome of
the reaction.
Based on the control experiments, our previous
work[13d] and literature precedence,[5,6] a plausible
mechanism has been proposed (Scheme 5). An in situ
generated catalytically active species A reacts with 1a
forming a 6-membered rhodacycle B through a
Scheme 4. Control experiments
concerted
metalation-deprotonation
pathway.
Insertion of arylalkynyl silane 2a to the rhodacycle B
forms an 8-membered intermediate C, which
undergoes protodemetallation promoted by PivOH
forming the corresponding non desilylated
alkenylated product 3aa’ and regenerates the active
catalyst A. Probably, the intermediate 3aa’ undergoes
protodesilylation triggered by the complex
A
(Scheme 4, eq 5a,b), forming the corresponding
alkenylated product 3aa.
Scheme 5. Proposed mechanism
In conclusion, we have developed a challenging
Rh(III)-catalyzed distal C-H alkenylation reaction
using weakly coordinating arylacetamide group under
redox-neutral
process.
To
overcome
the
incompatibility of a terminal alkyne, and its synthetic
4
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10.1002/adsc.201900307
Advanced Synthesis & Catalysis
equivalents in Rh(III)-catalysis, we successfully
utilized arylalkynyl silane as a surrogate. Control
experiments suggest that in situ generated Rh-species,
which is likely to be Lewis acid, plays a vital role in
the desilylation step. The methodology offers a broad
substrate scope furnishing products in moderate to
good yields. The Cp*M-catalyzed distal C-H
functionalization of arylacetamide derivatives are less
common, and the present result is one of the limited
successful examples.
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Experimental Section
Procedure for ortho alkenylation of
arylacetamide derivatives
In a 8-mL screw-cap reaction vial, aryl acetamide
derivatives
(0.4
mmol),
1-phenyl-2-
trimethylsilylacetylene derivatives (0.2 mmol),
rhodium catalyst [RhCp*Cl2]2 (6.2 mg, 5 mol%),
PivOH (20.4 mg, 1 equiv), AgSbF6 (13.7 mg, 20
mol%) in DCE (2 mL) were taken. The vial was sealed
with a screw cap and placed in a pre-heated metal
block at 100 °C and the reaction mixture was stirred at
the same temperature for 12 h. After completion of the
reaction (monitored by TLC), the reaction mixture was
cooled to room temperature and concentrated under
vacuum. The crude products were purified on a silica
gel column using EtOAc/ petroleum ether mixture or
EtOAc/DCM mixture.
[8] a) M. Sen, N. Rajesh, B. Emayavaramban, B.
Sundararaju, Chem. Eur. J. 2018, 24, 342; b) S. S.
Bera, S. Debbarma, A. K. Ghosh, S. Chand, M. S.Maji,
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Ackermann, Org. Lett. 2012, 14, 6318.
Acknowledgements
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This work was supported by SERB (EMR/2016/006358),
New-Delhi, CSIR (No. 02(0226)15/EMR-II), New-Delhi, Indian
Institute of Science and R. L. Fine Chem. We thank Dr. A. R.
Ramesha (R. L. Fine Chem) for useful discussion. A. K. and N. M.
thanks UGC, New-Delhi for a fellowship..
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10.1002/adsc.201900307
Advanced Synthesis & Catalysis
COMMUNICATION
Rh(III)-Catalyzed Distal C-H Alkenylation of
Weakly Coordinating Acetamides Via
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Adv. Synth. Catal. Year, Volume, Page – Page
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