Palladium-catalyzed C(carbonyl)-C bond cleavage of amides: a facile access to phenylcarbamate derivatives with alcohols

Article abstract of DOI:10.1039/c8cc03954b

A sulfur-containing auxiliary enabled palladium-catalyzed C(carbonyl)-C bond activation of amides was reported to form phenylcarbamate derivatives with alcohols. Both alkyl and benzyl alcohols could be employed well with yields up to 85%. Derivations from phenylcarbamates to ureas and thiocarbamates illustrated the potential applications of this sequential C-C cleavage/C-O coupling reaction.

Full text of DOI:10.1039/c8cc03954b

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Palladium-Catalyzed C(carbonyl) –C Bond Cleavage of Amides: A
Facile Access to Phenylcarbamate Derivatives with Alcohols
Xufei Yan,a Huihui Sun,a Haifeng Xiang,a Da-Gang Yu,a Daibing Luob and Xiangge Zhou*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
sulfur-containing auxiliary enabled palladium-catalyzed significant attention due to their prevalence in natural products and
C(carbonyl)–C bond activation of amides was reported to form pharmaceuticals.13 To the best of our knowledge, most of the
phenylcarbamate derivatives with alcohols. Both alkyl and benzyl reports related to C–C functionalizations of amides focused on the
alcohols could be engaged in well with yields up to 85%. decarbonylative C–C activation of aryl amides (Scheme 1a).14
Derivations from phenylcarbamates to ureas and thiocarbamates Meanwhile,
an
elegant
nickel-catalyzed
retro-
illustrated the potential applications of this sequential C–C hydroamidocarbonylation process by activation of aliphatic amides
cleavage/C–O coupling reaction.
was disclosed by Shi and co-workers in 2017 (Scheme 1b).15 Despite
this significant progress, selective C–C functionalizations of amides
to construct carbamate scaffolds with alcohols have thus far
remained elusive.16 In continuation of our work on C–H activation
and synthesis of sulfur-containing compounds,17 herein we report a
Transition metal-catalyzed C–H bond activation has emerged as
an efficient and promising strategy for the construction of carbon–
carbon and carbon–heteroatom bonds over the past few decades.1
Analogous to C–H bonds to some extent, C–C bonds are more
thermodynamically stable and far less reactive compared with polar
σ-bonds. Nonetheless, selective C–C functionalization has been the
subject of intensive research, which paved the way for more
powerful and straightforward pathways to construct the target
carbon skeletons, dispensing with tedious prefunctional groups.2
Groundbreaking C–C bond cleavage reaction dates back to 1955
contributed by Tipper and Chatt independently, who reported the
oxidative addition of cyclopropane onto a Pt(II) complex.3 A set of
seminal research advances was achieved subsequently. Normally,
C–C single bond cleavage was assumed to be driven by the factors
including: 1) strain release-driven oxidative addition; 2) ligand
aromatization; 3) directing group strategy.4 Another elementary
step involved in C–C single bond cleavage, referred to β-carbon
elimination, was pioneered by Watson and co-workers in 1982.5
Tremendous progress regarding C–C bond functionalization has
been made recently,6 whereas further extension is limited by the
substrate scope within small-membered ring compounds,7 nitriles,8
secondary/tertiary alcohols,9 carboxylic acids,10 esters11 or ketone
analogs.12 In this context, activation of amide bonds has received
sulfur-containing
auxiliary
enabled
palladium-catalyzed
C(carbonyl)–C bond activation of amides to form phenylcarbamate
derivatives with alcohols (Scheme 1c). Preliminary studies showed
that
a palladium-catalyzed amide-directed C–H arylation prior
occurred to form a multi-substituted bulky amide, thus facilitating
the subsequent β-carbon elimination process.
Previous work:
Ar
Het
R1
r
R4
e
f
.
1
R1
Ar
R1
Ar
4
a
Ar
,
b
f
,
h
,
,
e
c
R4
CN
g
4
1
1
,
4
O
p
d
R1
Ar
4
1
14i,j
NR2R3
R1
Ar
Ar
R1
Ar
Ar
o
4
1
Bnep
R1
O
1
(a)
R2
R2
4
k
R1
Ar
1
4
l
n
P
4
1
R1
H
S
NH2
R1
R2
Ar
R1
Ar
R2
O
R2
R1
H
cat. [Ni]
(b)
(c)
R4
Me
R1
N
R3 R4
R3
This work:
Boc
O
O
cat. [Pd]
HO R4
N
H
R4
R2 R3
N
O
S
R1
H
S
R1
O
-C
β
PhI
NH
N
Pd
elimination
R2
R3
S
R4O
S
R1 Pd
O
R1
L
Ph
Scheme 1 Examples of catalytic C–C activation reactions of amides
Our investigation commenced with the reaction between 2-
methylthio-N-pivaloylaniline 1a and iodobenzene in tert-amyl
alcohol 2a. 2-Methylthio phenyl amide 1a was formerly reported as
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(1.0 mL). l 2a (5.0 equiv), DMF (1.0 mL). m no AgOAc.
an effective directing group in C(sp3)–H arylation by Daugulis and
co-workers.18 As shown in Table 1, both of C(sp3)–H arylation
products 3 and C(carbonyl)–C activation product 4a were obtained.
After screening different metal catalysts, Ni(II), Ru(II), Rh(III), Cu(II),
and Fe(III) were found not beneficial to the reaction with none or
only a trace amount of 4a being obtained (Table 1, entries 2-6).
Increasing the loading of PhI from 2.0 to 4.0 equiv did not give
better results (Table 1, entry 7). To our delight, the reaction was
significantly improved to give 4a in 61% yield, when the amount of
AgOAc was increased to 4.0 equiv, together suppressing the
formation of 3 (Table 1, entry 1 and entries 8-9). Moreover,
prolonging the reaction time to 24 h facilitated the formation of 4a
in 72% yield with only a trace amount of 3 (Table 1, entry 10). Other
aryl iodides bearing steric substituents were also investigated;
however, no better results were obtained compared with
iodobenzene (Table 1, entries 11-12). Screening of different
solvents showed that 1,2-dichloroethane was better than toluene,
delivering 4a in 70% and 37% yields respectively, whereas MeCN
and DMF gave inferior yields (Table 1, entries 13-16). At last, the
control experiments indicated the necessity of Pd(OAc)2, AgOAc and
PhI, and no 4a was obtained in the absence of any component
(Table 1, entries 17-19). Therefore, 10 mol% of Pd(OAc)2, 4.0 equiv
of AgOAc and 2.0 equiv of PhI in tert-amyl alcohol (1.0 mL) reacting
at 120oC for 24 h were selected as the optimal reaction conditions.
With the optimized reaction conditions in hand, different sulfur-
substituents were first explored. As shown in Table 2, mercapto
group (–SH) was not compatible in this reaction. Phenyl or electron
rich phenyl substituents performed well to give similar yields
around 70% regardless of steric effects (4b-4e), whereas electron
deficient phenyl substituent (4f) showed some suppression for this
reaction. At last, 2-methoxy phenyl was employed as S-substituent
partially due to the easier purification by column chromatography.
Table 2 Survey on S-substituentsa,b
a 1 (0.2 mmol), 2a (1.0 mL), Pd(OAc)2 (10 mol%), AgOAc (4.0 equiv) and PhI (2.0
equiv) were stirred at 120 °C for 24 hours in the air. b Isolated yields.
Next, the scope of leaving groups on amides was examined in
Table 3. The desired C–C bond cleavage products could be smoothly
obtained either with secondary, tertiary or quaternary carbons, and
the highest yield 85% was achieved in the case of 1l bearing
sterically bulky substituent.
Table 1 Optimization of reaction conditionsa
Table 3 Survey on the leaving groupsa,b
Yield (%)b
Entry
Catalyst
ArI
Solvent
3 = 3a+3b+3c
4a
1
2
Pd(OAc)2
Ni(OAc)2
PhI
PhI
PhI
PhI
PhI
PhI
PhI
PhI
PhI
PhI
ArI
-
48
12
0
10
trace
0
-
3
[RuCl2(p-cymene)]2
[Cp*RhCl2]2
Cu(OAc)2
Fe2(SO4)3
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
-
-
a 1 (0.2 mmol), 2a (1.0 mL), Pd(OAc)2 (10 mol%), AgOAc (4.0 equiv) and PhI
(2.0 equiv) were stirred at 120 °C for 24 hours in the air. b Isolated yields.
4
-
8
trace
0
5
-
trace
0
6
-
0
7c
-
56
32
12
trace
23
trace
8
12
42
61
The substrate scope of alcohols was then explored. As depicted in
Table 4, various alkyl and benzyl alcohols reacted smoothly to
generate the corresponding products in moderate to good yields
(52%-83%). Tertiary alcohols seemed to be more beneficial to the
reactions than primary and secondary analogs. For example,
tertiary alcohols with diverse side chains afforded the
corresponding products in yields ranging from 72% to 83% (4c, 4l-
4o), whereas primary alcohol gave product 4g in 52% yield and
secondary alcohols gave products in 64%-69% yields (4h-4k).
Furthermore, benzyl alcohols with either electron-withdrawing (e.g.,
F and Cl) or electron-donating (e.g., Me and OMe) groups were
applicable, delivering the C–C functionalization products in
moderate to good yields (4p-4w). Steric effect seemed to have little
influence on this transformation as 4r was obtained in 71% yield.
Di-substitued benzyl alcohol was also suitable in this protocol (4u).
Notably, benzyl alcohols containing fluoride or chloride group (4v
and 4w) participated in this reaction as well, which might be
8d
-
9e
-
10e,f
11e,f,g
12e,f,h
13e,f,i
14e,f,j
15e,f,k
16e,f,l
17
-
-
72(69)
20
ArI
-
trace
PhI
PhI
PhI
PhI
1,2-DCE
toluene
MeCN
DMF
70(65)
35
19
5
37
9
5
0
0
-
-
-
18m
PhI
10
0
0
19
PhI
-
0
a General conditions: 1a (0.2 mmol), 2a (1.0 mL), catalyst (10 mol%), AgOAc
(1.5 equiv) and ArI (2.0 equiv) were stirred at 120 °C for 12 hours in the air.
b NMR yields using CH2Br2 as the internal standard and isolated yields were
shown in the parenthesis. c PhI (4.0 equiv). d AgOAc (3.0 equiv). e AgOAc (4.0
equiv). f 24 h. g ArI = 2-Iodocumene. h ArI = 2-Iodo-1,3-dimethylbenzene. i 2a (5.0
equiv), 1,2-DCE (1.0 mL). j 2a (5.0 equiv), toluene (1.0 mL). k 2a (5.0 equiv), MeCN
2 | J. Name., 2012, 00, 1-3
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potential for further derivation. The structure of 4c was confirmed would undergo proton abstraction and β-C(sp3)–H metalation
by X-ray single crystal determination. during the reaction. Furthermore, substrates without β-carbon or
The scope of amides was also investigated in Table 5. Amides with a quaternary β-carbon gave no desired product as expected,
bearing electron-withdrawing groups such as Cl (4y and 4aa), Ac which suggested the involvement of β-C(sp3)–H metalation during
(4ab), or electron-donating moieties (4x and 4z) all gave moderate the reaction (eq. 5 and 6). Later, we explored the role of PhI in this
to good yields. Di-substitued amide (4ac) was also a suitable reaction. As shown in eq. 7 and 8, 1l afforded product 4c in 85%
substrate for this transformation.
yield under standard conditions, while 1n gave a 83% yield without
addition of PhI. Combined with the fact of importance of PhI in
entry 17 of Table 1, it is assumed that β-C(sp3)–H arylation would
occur prior to C–C single bond activation in the reaction.21
Table 4 The scope of alcoholsa,b
Table 6 Product transformations a
a Reaction conditions from 4ad to 5, 6, 7 and 8: (1) 2-Cl-pyridine (3.0 equiv), Tf2O
(1.5 equiv), DCM, r.t., 1 h; (2) Nucleophile reagents (3.0 equiv), rt., 1 h. a) Nu:
Aniline; b) Nu: Morpholine; c) Nu: Phenol; d) Nu: p-OMe-thiophenol.
a
1l (0.2 mmol), 2 (5.0 equiv), Pd(OAc)2 (10 mol%), AgOAc (4.0 equiv) and
PhI (2.0 equiv) were stirred in 1,2-DCE (1.0 mL) at 120 °C for 24 hours in the
air. b Isolated yields.
Table 5 The scope of amidesa,b
a
1 (0.2 mmol), 2a (1.0 mL), Pd(OAc)2 (10 mol%), AgOAc (4.0 equiv) and PhI (2.0
equiv) were stirred at 120 °C for 24 hours in the air. b Isolated yields.
To further demonstrate the utility of this sequential C–C
cleavage/C–O formation reaction, several reactions toward the
synthesis of ureas and thiocarbamates were conducted (Table 6).19
Nucleophiles such as aniline, morpholine, phenol and 4-methoxyl
thiophenol could be reacted well with 4ad to generate the
corresponding products 5, 6, 7 and 8 in good yields. These
methodologies came up with practical routes to carbamates and
unsymmetrical ureas, which are widely found in pharmaceuticals
and polymers.20
Scheme 2 Studies of reaction pathway
Based on the above experimental results and literature
reports,14c, 18 a proposed reaction pathway is illustrated in Scheme 3.
At first, palladium complex IM1 is formed via proton abstraction
and β-C(sp3)–H metalation. Then, it is converted to IM2 by oxidative
addition with PhI. Next, the reductive elimination of IM2 affords 1o,
which was confirmed by NMR and HRMS. Later, another
coordination and sequential proton abstraction and β-C(sp3)–H
metalation occurs to form IM3. Subsequently, IM3 goes through β-
C elimination to afford carbamoyl-Pd-type intermediate IM4 with
the simultaneous extrusion of triphenylethylene, which was
isolated and characterized by NMR and GC-MS analysis. At last,
after reductive elimination, the desired product 4 is obtained.
Meanwhile, oxidation of Pd(0) to the reactive Pd(II) species by Ag(I)
completes the catalytic cycle.
To gain insight into the possible reaction pathway, a series of
control experiments were then carried out. As shown in Scheme 2,
N-pivaloylaniline and 2-methoxyl-N-pivaloylaniline were not
suitable for this reaction and failed to give the desired products,
which indicated the importance of –SR group in substrate 1 (eq. 1
and 2). Indeed, the reaction between 1b, Pd(OAc)2 and pyridine in
acetonitrile formed the palladacycle complex 9 (eq. 3). We have
successfully determined the crystal structure of the palladacycle 9
by X-ray single crystal diffraction, and confirmed the important role
of sulfur atom by serving as a coordination site. Then, complex 9
was used as catalyst in the reaction between 1b and 2a, affording
desired product 4b in 40% yield (eq. 4), which suggested substrate 1
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Scheme 3 Plausible mechanistic pathway
In summary, we have developed an unprecedented palladium-
catalyzed C(carbonyl)–C single bonds cleavage reaction of amides to
form new C–O bonds with alcohols, delivering phenylcarbamate
derivatives with pharmacological potential. Both alkyl and benzyl
alcohols can be engaged well in this C–C functionalization reaction.
Further investigation on the mechanism and optimizing the reaction
conditions for C(carbonyl)–C(secondary or tertiary α-carbon) single
bonds cleavage of amides are currently underway in our laboratory.
We are grateful to the National Natural Science Foundation of
China (grant nos. 21472128, J1310008) for financial support. We
also acknowledge Comprehensive training platform of specialized
laboratory, College of chemistry, Sichuan University for HRMS
analysis.
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Conflicts of interest
There are no conflicts to declare.
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Graphic Abstract
Palladium-Catalyzed C(carbonyl) –C Bond Cleavage of Amides: A Facile Access
to Phenylcarbamate Derivatives with Alcohols
Xufei Yan, Huihui Sun, Haifeng Xiang, Da-Gang Yu, Daibing Luo and Xiangge Zhou*