Rhodium-catalyzed synthesis of amides from aldehydes and azides by chelation-assisted C-H bond activation

Article abstract of DOI:10.1002/chem.201301168

C-H activation: A Rh^III-catalyzed direct aldehyde C-H amidation has been achieved with sulfonyl, aryl, and alkyl azides as the amine sources, and release of N₂ as the only byproduct (see scheme). More importantly, this catalytic reaction proceeds in the absence of external oxidants or additives, under mild conditions, at neutral pH under air. This reaction represents a new avenue for practical intermolecular C-N bond formation by aldehyde C-H bond activation. Cp=1,2,3,4,5-Pentamethylcyclopentadiene Copyright

Full text of DOI:10.1002/chem.201301168

COMMUNICATION
Rhodium Catalysis
B. Zhou,* Y. Yang, J. Shi, H. Feng,
Y. Li* ........................... &&&& — &&&&
Rhodium-Catalyzed Synthesis of
Amides from Aldehydes and Azides
III
À
C H activation: A Rh -catalyzed
absence of external oxidants or addi-
tives, under mild conditions, at neutral
pH under air. This reaction represents
a new avenue for practical intermolec-
À
direct aldehyde C H amidation has
À
by Chelation-Assisted C H Bond
Activation
been achieved with sulfonyl, aryl, and
alkyl azides as the amine sources, and
release of N2 as the only byproduct
(see scheme). More importantly, this
catalytic reaction proceeds in the
À
ular C N bond formation by aldehyde
À
C H bond activation. Cp*=1,2,3,4,5-
Pentamethylcyclopentadiene
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DOI: 10.1002/chem.201301168
Rhodium-Catalyzed Synthesis of Amides from Aldehydes and Azides by
À
Chelation-Assisted C H Bond Activation
Bing Zhou,* Yaxi Yang, Jingjing Shi, Huijin Feng, and Yuanchao Li*[a]
The amide bond is one of the
most
abundant
functional
groups
in pharmaceuticals,
agrochemicals, and natural
products.[1] Amide bonds are
routinely generated by conden-
sation of carboxylic acids and
amines through stoichiometric
activation, under harsh condi-
tions, or both.[2]
A milder,
atom-economic alternative ap-
proach is the direct amidation
of aldehydes. Recent examples
of this strategy include N-heter-
ocyclic
(NHC)-catalyzed,[3]
metal-catalyzed,[4] or metal-
free[5] oxidative amidation of al-
dehydes with amines, the
Schmidt amidation of aldehydes
with azides,[6] base-mediated
À
À
Scheme 1. Coupling reactions involving C C bond formation by C H activation through a) an oxidative addi-
À
À
tion pathway, b) a deprotonation pathway, and c) C N bond formation through a C H activation pathway.
amidation of aldehydes with azides,[7] direct organocatalytic
oxidative amidation of aldehydes with amines through stoi-
chiometric activation,[8] and cross-coupling of acyl and
aminyl radicals.[9] Although significant progress has been
made in this field, the development of catalytic and effective
methods of amide bond formation under mild reaction con-
ditions remains highly desirable.
In this context, and attracted by recent successes in arene
[13]
À
C H bond amination reactions, we surmised that an alde-
À
À
hyde C H amidation by a C H bond activation strategy
Table 1. Optimization of the Rh-catalyzed amide synthesis.[a]
À
In addition, transition-metal-catalyzed aromatic C H
bond functionalization is currently a “hot topic” in organic
chemistry.[10] In sharp contrast to arene C H bonds, the se-
À
À
lective functionalization of aldehyde C H bonds is limited
À
to coupling with alkenes and alkynes forming C C bonds
Catalyst
AHCTUNGTRENN(GUN [mol%])
Solvent
T
Yield
[8C] [%][b]
and yielding ketone derivatives through oxidative addition
of low-valent transition-metal complexes (especially RhI) to
1
2
3
4
5
N
CH2Cl2
CH2Cl2
85
0
[11,12]
À
aldehyde C H bonds (Scheme 1a).
To the best of our
knowledge, direct catalytic C N bond formation resulting
from chelation-assisted aldehyde C H bond activation re-
mains undeveloped, with no examples reported to date.
85 66
85 14
85 70
85 77
85 60
ACHTUGNTERN(NUGN p-cymene)Cl2}2] (3)/AgSbF6 (12) CH2Cl2
À
E
G
CH2Cl2
DCE
THF
À
E
6
A
7
G
E
N
tert-amylOH 85 35
8
9
N
G
G
PhMe
PhMe
PhMe
PhMe
85 85
100 84
70 66 (83)
85 84
[a] Dr. B. Zhou, Dr. Y. Yang, Dr. J. Shi, H. Feng, Prof. Y. Li
Shanghai Institute of Materia Medica, Chinese Academy of Sciences
555 Zu Chong Zhi Road, Shanghai 201203 (P. R. China)
Fax : (+86)21-50807288
10
11[c]
E-mail: zhoubing2012@hotmail.com
[a] Reaction conditions: 1a (0.2 mmol), 2a (0.22 mmol), catalyst
(0.006 mmol), and solvent (1 mL) at the indicated temperature for 12 h.
[b] yield of isolated product; Yield in parentheses is based on recovered
starting material. [c] 1 g of 1a was used. DCE=1,2-dichloroethane.
ycli@mail.shcnc.ac.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201301168.
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Rhodium-Catalyzed Amide Synthesis
COMMUNICATION
could provide a new approach to amide-bond synthesis. Re-
cently, several investigations revealed that RhIII complexes
undergo chelation-assisted electrophilic metalation of ortho
ering the temperature led to a slightly lower conversion
(Table 1, entry 10). Finally, we were pleased to find that this
reaction was scalable to gram amounts of substrate without
decreasing the yield, and the product 3a could be isolated
by a simple purification process (recrystallization) with N2
as the sole byproduct (Table 1, entry 11).
An array of azides and aldehydes were screened under
the conditions established above (Table 2). Arenesulfonyl
azides substituted with electron-donating groups, such as Me
(2a) and MeO (2b), and -withdrawing groups, such as NO2
2
[14]
À
C
(sp ) H bonds to form arylrhodium complexes,
which
may be coupled to a variety of reagents such as aldehydes,[15]
imines,[16] isocyanates,[17] diazomalonates,[18] azides,[19] al-
kenes, and alkynes (Scheme 1b).[20] Therefore, herein, we
report the first example of RhIII-catalyzed amidation of al-
dehydes with azides as an amine source in the presence of
À
air (Scheme 1c). This catalytic aldehyde C H amidation
proceeds in the absence of ex-
Table 2. Substrate scope.[a]
ternal oxidants and additives,
under mild and neutral reac-
tion, conditions with high func-
tional group tolerance, and re-
leases N2 as the single byprod-
uct. Moreover, in addition to
alkyl azides,[6,7] aryl and sulfon-
yl azides are tolerated, provid-
ing N-alkyl amides, acylsulfona-
mides, and N-aryl amides in ex-
cellent yields.
Initially, the reaction condi-
tions were optimized by using
8-quinolinecarbaldehyde (1a)
and para-toluenesulfonyl azide
(2a) as cross-coupling partners
(Table 1). Although 3 mol% of
[(Cp*RhCl2)2] did not catalyze
this reaction (Table 1, entry 1),
[(Cp*RhCl2)2] (3 mol%) in the
presence
of
AgSbF6
(12 mol%)[21] in THF at 858C
provided the desired product,
3a, in 66% yield (Table 1,
entry 2). The ruthenium com-
plexes known to be highly ef-
À
fective in direct C H bond
functionalization, was relatively
ineffective in this reaction
(Table 1, entry 3). The RhIII
precursor
[SbF6]2 led to similar reactivity
to that observed with
[Cp*RhACTHNGUTRENNU(G MeCN)3]-
ACHTUNGTRENNUNG
[(Cp*RhCl2)2] and AgSbF6
(Table 1, entry 4). Therefore,
[Cp*Rh
G
G
was
used for all subsequent optimi-
zation studies. Solvent screen-
ing showed that an improved
chemical yield could be ob-
tained with toluene as the sol-
vent, providing the product 3a
in 85% yield (Table 1, entry 8).
Raising the temperature did
not result in any reduction in
[a] Reaction conditions: 1 (0.2 mmol), 2 (0.22 mmol), Rh catalyst (0.006 mmol) and solvent (1 mL) at 858C for
yield (Table 1, entry 9) and low- 12 h. Yield of isolated product. Bn=Benzyl.
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B. Zhou, Y. Li et al.
Table 3. 2-(Methylthio)benzaldehyde substrate scope.[a]
(3c), were tolerated, providing the desired amides in good
to excellent yields. An aliphatic sulfonyl azide (2d) reacted
equally well, giving the corresponding product (3d) in good
yield. The substrate scope was further extended to a broad
variety of aryl azides. Phenyl azides substituted with elec-
tron-withdrawing or -donating groups at the para-, meta- or
ortho-position (2e–2q) were tolerated, with good to excel-
lent yields of 3e–3q obtained, irrespective of the electronic
nature or position of the substituents on the phenyl ring.
Moreover, the reaction showed good functional group com-
patibility. For example, phenyl azides with ester (2e and
2p), nitro (2j), nitrile (2l), ketone (2k), ethyl (2h), methoxy
(2n and 2q), and chloro (2g and 2m) groups were effective
coupling partners under the optimized conditions. Notably,
the tolerance of the ester, nitro, nitrile, ketone and chloro
groups offers the opportunity for further functionalization.
In addition, 2-naphthyl and 1-naphthyl azides (2r and 2s)
were readily converted to the corresponding products in
good yields. Particularly remarkable is the participation of
alkyl azides in this reaction, providing the corresponding n-
hexyl and phenylmethane amide products (3t and 3u, re-
spectively) in excellent yields. It was found that the elec-
tronic nature of the substituents on the quinoline ring did
not play a key role in this catalytic reaction. Aldehydes with
either electron-donating or -withdrawing groups (1v–1aa)
were readily converted to the corresponding products in
good yields.
[a] Reaction conditions:
4 (0.2 mmol), 2e (0.24 mmol), Rh catalyst
(0.024 mmol), and solvent (0.3 mL) at 1058C for 24 h under argon. Yield
of isolated product; yield in parentheses is based on recovered starting
material.
and mass spectrum analysis of 7 pointed to cyclometalation.
Encouraged by the successful amidation of 8-quinolinecar-
baldehyde, we turned our attention to additional substrates
bearing synthetically useful directing groups. To our delight,
Although a number examples of acyl–rhodium
plexes have been isolated by starting from RhI catalysts,[22]
reports of stable isolated organorhodium(III) intermedi-
ates from RhIII catalysts by deprotonation are still limit-
ed,[14c,16c,e,19a,23] particularly for acyl–rhodium
(III) intermedi-
ACHTUNGTRENN(UNG III) com-
AHCTUNGTRENNUNG
2-(meACHTUNGTRENNUNGthylthio)benzaldehyde also underwent direct amida-
tion with aryl azides (Table 3). Aromatic groups bearing
electron-donating or -withdraw-
ing groups were tolerated (5a–
d) and good yields were ob-
tained, despite the need for a
relatively high catalyst loading.
To obtain further insight into
ACHTUNGTRENNUNG
this catalytic transformation,
preliminary mechanistic experi-
ments were carried out. When
benzaldehyde (6a) was utilized
as the substrate, the corre-
sponding amide was not formed
(Scheme 2a). Therefore, the
presence of a directing group in
the substrate seems to be criti-
À
cal to the initial C H bond-
functionalization event. No
product formation was ob-
served in the presence of
[(Cp*RhCl2)2] or AgSbF6 alone
(Scheme 2b). The stable cyclo-
metalated RhIII complex 7 was
obtained upon treatment of 1a
with [(RhCp*Cl2)2] and NaOAc
(Scheme 2c). 1H and 13C NMR Scheme 2. Preliminary mechanistic studies.
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Rhodium-Catalyzed Amide Synthesis
COMMUNICATION
Experimental Section
General procedure: [Cp*Rh
ACHTUNGTRENNUNG(MeCN)3]-
AHCTUNGTRENNUNG
1 (0.2 mmol), 2 (0.22 mmol, 1.1 equiv),
and toluene (1 mL) were added to a
test tube in air. The reaction mixture
was heated in an oil bath at 858C for
12 h. The resulting mixture was cooled
to room temperature and purified di-
rectly on a silica gel column to give
the product 3.
Keywords: aldehydes · amides ·
À
azides
rhodium
·
C H activation
·
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À
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À
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À
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À
[17] For the rhodium
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Received: March 27, 2013
Published online: && &&, 0000
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