An Efficient Heterobimetallic Lanthanide Alkoxide Catalyst for Transamidation of Amides under Solvent-Free Conditions

Article abstract of DOI:10.1002/adsc.201600373

A practical heterobimetallic lanthanide-catalyzed transamidation of primary, secondary and tertiary amides with aliphatic and aromatic amines has been developed. The methodology was also applied to the weakly reactive thioamides to demonstrate its versatility and wide substrate scope. The heterobimetallic lanthanide catalysts showed high catalytic activity and a wide scope of substrates with good to excellent yields under solvent-free conditions. Efficient activation of the transamidation can be realized by the above complexes acting as cooperative acid–base bifunctional catalysts, which are proposed to be responsible for the higher reactivity in comparison with simple monometallic catalysts. (Figure presented.).

Full text of DOI:10.1002/adsc.201600373

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DOI: 10.1002/adsc.201600373
An Efficient Heterobimetallic Lanthanide Alkoxide Catalyst for
Transamidation of Amides under Solvent-Free Conditions
Hongting Sheng,a,* Ruijie Zeng,a Wenjuan Wang,a Shuwen Luo,a Yan Feng,a,*
Jing Liu,a Weijian Chen,a Manzhou Zhu,a and Qingxiang Guob
a
School of Chemistry and Chemical Engineering & Center for Atomic Engineering of Advanced Materials, Anhui
University, Hefei 230039, Peopleꢀs Republic of China
Fax : (+86)-551-6386-1487; e-mail: shenght@ahu.edu.cn or anhuifengyan@ahu.edu.cn
Department of Chemistry, University of Science and Technology of China, Hefei 230026, Peopleꢀs Republic of China
b
Received: April 7, 2016; Revised: November 8, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600373.
Abstract: A practical heterobimetallic lanthanide- tions. Efficient activation of the transamidation can
catalyzed transamidation of primary, secondary and be realized by the above complexes acting as cooper-
tertiary amides with aliphatic and aromatic amines ative acid–base bifunctional catalysts, which are pro-
has been developed. The methodology was also ap- posed to be responsible for the higher reactivity in
plied to the weakly reactive thioamides to demon- comparison with simple monometallic catalysts.
strate its versatility and wide substrate scope. The
heterobimetallic lanthanide catalysts showed high Keywords: acid–base bifunctional catalyst; heterobi-
catalytic activity and a wide scope of substrates with metallic complexes; lanthanides; solvent-free condi-
good to excellent yields under solvent-free condi- tions; transamidation
Introduction
building blocks. The exchange of the amine moiety
with an amide is a simple but rare organic transforma-
The ability to interconvert functional groups is impor- tion, primarily due to the modest reactivity of amides
tant in synthetic chemistry and many biological pro- being a result of the strength of the resonance-stabi-
cesses. Metal-catalyzed organic transformations have lized amide C–N bond.[46] Recent examples of the
drawn great attention in the past several decades transamidation reaction have been described, includ-
owing to their advantages compared to conventional ing using heterogeneous[17–26] and homogeneous cata-
organic transformations, including higher atom-, step- lysts[27–42] (Supporting Information, Tables S1–S4).
and cost-economy and the avoidance of tedious pre- However, some of methods suffer from one or more
functionalization and waste emission.[1–8] One particu- disadvantages
such
as
limited
substrate
lar interest is the transformation of the amide func- scope,[20–22,24–25,27–38] and harsh reaction conditions
tional group, which is the key building block of pro- (high temperature or large catalyst loading or signifi-
teins and is present in a broad range of other natural cant excess of substrates).[18,22–23,26–29,31,37–39] In addition,
and synthetic compounds.[9–15]. Recently, there have thioamides are core units in heterocyclic chemistry
been a few developments in this field, including the and they are useful intermediates in many organic
conversion of amides to esters,[16] the transamidation transformations. The transamidation reaction is re-
of amides with amines[17–42] and the deoxygenation of garded as a more efficient method for the synthesis of
amides to amines, etc.[43,44] The American Chemical thioamides than thionation of the corresponding
Societyꢀs Green Chemistry Institute Pharmaceutical amides from an economical point of view, but only
Roundtable (ACS GCIPR) voted ꢁamide formation three reports are available on the transamidation of
avoiding poor atom economy reagentsꢀ as the top thioamides to date due to the high stability of the thi-
challenge for organic chemistry in 2007.[45] Transami- oamides.[47–49] Thus, there is a lack of an efficient cata-
dation not only provides a powerful strategy for syn- lytic system for the transamidation of amides and
thesizing amides with exceptional atomic efficiency, thio
but also lays the foundation for further studies aiming
ACHTUNGTRENNUNG
at the strategic manipulation of amides as synthetic functional groups can be achieved in most enzymatic
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reactions.[50–55] Many enzymes containing two or more Results and Discussion
metal centers in close proximity, activate simultane-
ously substrates through non-covalent interaction as The complexes Ln2Na8(OCH2CF3)14(THF)6 [Ln=Nd
bifunctional catalysts, which makes them more reac- (A), Sm (B), Y (C) and Yb (D)] and the correspond-
tive in the transition state of reactions, leading to the ing monometallic lanthanide complex [Nd(OR)3]
enhancement of catalytic performance.[56,57] Inspired (OR=OCH2CF3) were synthesized according to the
by these biocatalysts, great efforts have been made to reported literature method.[71] The X-ray crystal struc-
develop multimetallic catalysts enabling synergistic ture is shown in Figure 1. To the best of our knowl-
and cooperative activation.[58–66] Hence, when a single edge, heterobimetallic lanthanide complexes as
metal fails to promote an efficient transformation, the a single-composition catalyst have not yet been re-
synergistic cooperation of two coexisting and distinct ported in the transamidation process.
catalyst sites – multimetallic catalysis – can be used
instead.
Acid–base bifunctional catalysis is one of important
reaction mechanisms in multimetallic catalytic sys-
tems.[61,67–69] As a part of our recent studies on multi-
metallic catalysts, we reported that heterobi
ACHTUNGTRENNmUNG etallic
lanthanide alkoxide complexes
[Ln2Na8{(OCH2CH2NMe2)}12(OH)2] as catalysts were
successfully applied to the transesterification based
on the above reaction mechanism.[70] In the above
system, the catalysts acted as not only Lewis acid cen-
ters to activate the electrophile esters, but also as
multi-Brønsted base centers to activate the nucleo-
phile alcohols, which was the crux to achieve high ac-
tivity (Scheme 1). Encouraged by these results, we en-
Figure 1. Molecular structure of Ln2Na8(OCH2CF3)14 (THF)6
with all the CH2CF3 groups deleted for clarity.
Our initial studies focused on developing a more ef-
ficient catalytic system for transamidation with the
well-defined heterobimetallic lanthanide alkoxide
complexes in hand, and we used the reaction of ben-
zamide (1a) with benzylamine (2a) as a model system
(Table 1). Because the transamidation reaction is in
equilibrium, a driving force is needed to push this
equilibrium towards the desired products. In most of
the cases described above, an excess of one kind of
substrates is expected to be necessary. For example,
the D. Gamba-Sꢃnchez group reported that they used
a greater excess of amide (1.7 equiv.) which resulted
in a perfect yield on utilizing Fe(III) as catalyst in the
transamidation.[39] In our case, we commonly used
a slight excess of amine (1.1 equiv.) due to the fact
that the amine is usually less expensive than the
amide. In addition, this excess amine is easily re-
Scheme 1. Dual activation by the heterobimetallic lantha-
nide complex as an acid–base bifunctional catalyst.
visioned that dual activation of amides and amines by moved from the desired product by washing with acid
the heterobimetallic lanthanide alkoxide complexes in the work-up. This condition has practical advantag-
would probably exist in the catalysis of transamida- es over other approaches with amides in excess or re-
tion. Ideally, heterobimetallic alkoxide complexes can quiring a significant excess of amines. As depicted in
be used as highly active catalysts to promote the Table 1, the reaction could be catalyzed by the
transamidation reaction of amides, phthalimides and heteroACHTNUTRGNEbNUG imetallic complexes (A–D) giving the desired
much less reactive thioamides with primary and sec- 3aa in moderate to good yields at 1208C for 16 h with
ondary amines. This strategy opens a new window to 2.0 mol% catalyst loading (Table 1, entries 2–5),
approach the desirable reactions to synthesize amides whereas no product was isolated in the absence of the
from transamidation. Herein, we report the results of catalyst (Table 1, entry 1). It was observed that rare
this efficient method for transamidation reactions of earth metals had a remarkable effect on the catalytic
amides and thioamides.
performance. The activity order of YbꢀY<Sm<Nd
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Table 1. Optimization of the conditions for the reaction of
to coordination of solvents to lanthanide center, di-
minishing the Lewis acidity of the heterobimetallic
catalyst. Pleasingly, when the reaction was performed
under solvent-free conditions, it reached 92% conver-
sion (Table 1, entry 16).
benzamide with benzylamine.[a]
With the optimized system in hand, the transamida-
tion reactions of benzamide with various amines were
explored. As shown in Table 2, it is clear that various
primary amines and secondary amines are applicable
for transamidation with benzamide to achieve the de-
sired amides in reasonable to excellent yields upon
isolation. Heteroaromatic primary amine (2b) as well
as benzylamine (2a) was successfully reacted with
benzamide in high yields (Table 2, entries 1 and 2).
Meanwhile, since the p-p conjugated effect of aromat-
ic amine lowered the nucleophilicity of amine group,
the reactions with aniline and substituted anilines af-
forded moderate yields of corresponding products
under the same conditions (Table 2, entries 5, 6, 8). It
was also observed that aliphatic primary amines (2c
and 2d) exhibited higher reactivity than aromatic pri-
mary amines (2e and 2f), and these reactions gave the
yields of 94% and 93% for aliphatic primary amines,
83% and 86% for aromatic primary amines, respec-
tively (Table 2, entries 3–6). Compared with primary
Entry
Catalyst
mol% of
Catalyst
Solvent
Yield
[%][b]
1
2
3
4
5
6
7
8
–
A
B
C
–
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
n-heptane
DMF
n.r.
80
72
64
62
n.r.
n.r.
69
85
88
89
63
58
55
67
92
2.0
2.0
2.0
2.0
2.0
2.0
1.0
3.0
4.0
5.0
4.0
4.0
4.0
4.0
4.0
D
[c]
Nd(OR)3
NaOR[c]
A
A
A
A
A
A
A
A
A
9
10
11
12
13
14
15
16
DMSO
dioxane
solvent-free
[a]
Reaction conditions: benzamide 1a (1 mmol), benzyl- amines, secondary amines such as N-methylaniline
ACHTUNGTRENNUNGamine 2a (1.1 mmol), solvent (1 mL) and catalyst at
(2h), dibutylamine (2i) and morpholine (2j) proceed-
ed less smoothly and got lower yields (Table 2, en-
tries 9–11), which may result from steric hindrance.
The electronic nature and steric factor effects ob-
served here may be explained by the nucleophilic ad-
1208C under an argon atmosphere for 16 h.
Isolated yield; n.r.=no reaction.
OR=OCH2CF3.
[b]
[c]
is consistent with the increase in ionic radius. Com- dition of nitrogen atom in an amine to a C=O double
pared with the heterobimetallic lanthanide/sodium bond, similar to that observed in other transamidation
alkoxide complexes, the monometallic lanthanide systems. In general, primary amines are more active
complex Nd(OCH2CF3)3 cannot catalyze effectively than secondary amines, and aliphatic amines have
the transamidation reaction under the same condi- higher reactivity than aromatic amines in most cases.
tions, neither can the sodium alkoxide complex Herein, we conducted the transamidation of benz-
NaOCH2CF3 (Table 1, entries 6 and 7). These results
ACHTUNGTRENUNaNG mide with 2f by 1 mol% catalyst A under 1408C in
clearly suggest the crucial dual activation role of the order to compare with the Fe-monocatalyzed system,
heterobimetallic lanthanide/sodium alkoxide com- which is of the higher activity than other described
plexes in the transamidation. The lanthanide metal methodologies for transamidation so far.[24] The result
ions act as Lewis acids to activate the oxygen atom of indicated that catalyst A is comparable of Fe-monoca-
the amide, while sodium metal alkoxides function as talyzed system for the transamidation reaction under
a Brønsted base to bring the amine into close proxim- the same conditions (Table 2, entry 7).
ity (Scheme 1). The above acid–base bifunctional cat-
Subsequently, a variety of amides and amines was
alytic mechanism was also mentioned for other reac- screened to demonstrate the generality and efficacy
tions.[61,67–69] Then, experiments were conducted to op- of this heterobimetallic lanthanide-catalyzed transa-
timize the catalyst loading and it was found that the midation protocol and the results are summarized in
use of 4.0 mol% is sufficient to give a yield of 88% of Table 3. Transamidation of 2-phenylacetamide (1b)
the product N-benzylbezamide (3aa) in 16 h (Table 1, with benzylamine (2a) and dodecylamine (2d) afford-
entries 2, 8–11). Furthermore, other solvents were ed the corresponding products with high yields
also examined in order to increase the conversion in (Table 3, entries 1 and 2). Similarly, when heteroaro-
the model reaction catalyzed by catalyst A (Table 1, matic amide (1c) was used as a substrate, the reac-
entries 10, 12–16). No improvement was observed tions with 2a and 2d also proceeded smoothly
when the reaction was carried out in n-heptane and (Table 3, entries 3 and 4). Steric aliphatic amides such
polar aprotic solvents (DMF, DMSO, dioxane) which as dodecanamide (1d) underwent transamidation with
may inhibit the reaction to some degree probably due amines to form the desired products (Table 3, en-
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Table 2. Transamidation of benzamide with various amines
catalyzed by catalyst A.[a]
tries 5 and 6). Compared to aromatic amides and
steric aliphatic amides, acetamide could be reacted
much faster with different amines to give the corre-
sponding amides with high yields in 10 h (Table 3, en-
tries 7–9). We then used formamide to achieve the N-
formylation of amines under the catalytic system. The
N-formylation of amines is one of the most important
reactions in organic and industrial chemical synthesis,
which is performed typically using hazardous, toxic,
and unstable reagents.[1,72–76] Formamides have been
used as intermediates for the synthesis of many phar-
maceutical compounds such as fluoroquinolones, sub-
stituted arylimidazoles, 1,2-dihydroquinolines, and ni-
Table 3. Transamidation of different amides with amines cat-
alyzed by catalyst A.[a]
[a]
Reaction conditions: benzamide 1a (1 mmol), amine 2
(1.1 mmol)
and
Nd2Na8(OCH2CF3)14(THF)6
(A)
(4.0 mol%) at 1208C for 16 h under an argon atmosphere
and solvent-free conditions.
Isolated yield.
[b]
[c]
[cat.]=1.0 mol% at 1408C for 30 h.
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Table 3. (Continued)
were obtained from corresponding amines in 5 h. The
shorter time may be due to the high electrophilicity
of formamide. Transamidation of secondary amide
and tertiary amides such as N-methylacetamide (1k),
N,N-dimethylformamide (1g) and N,N-dimethylacet-
AHCTUNGTREGaNNUN mide (1h) were also active, which resulted in moder-
ate yields compared to primary amides (Table 3, en-
tries 14–18). So far, only a few of reported methodol-
ogies are described with an active catalyst for this
transamidation. In addition, the transamidations of
phthalimide with three kinds of primary amines were
also investigated. The reaction could provide
a method for protecting primary amines, which is of
great significance in organic synthesis. All primary
amines reacted smoothly to provide corresponding N-
substituted phthalimides in good to excellent yields as
depicted in Table 4.
Among the thiocarboxylic derivatives, thioamides
have proven to be of great interest, as thioamides are
used as plant protection agents, drugs, flotation and
vulcanization agents, additives to lubricating oils and
greases, and important ligands in coordination
chemistry.[82–87] Hence, the synthesis of thioamides
constitutes a demanding goal. Thioamides are gener-
ally prepared by the thionation of the corresponding
Table 4. Transamidation of phthalimide with amines by cata-
lyst A.[a]
[a]
Reaction conditions: amide
1
(1 mmol), amine
2
(1.1 mmol)
and
Nd2Na8(OCH2CF3)14(THF)6
(A)
(4.0 mol%) at 1208C under an argon atmosphere and sol-
vent-free conditions.
Isolated yield.
[b]
trogen-bridged heterocycles.[77–81] The transamidation
reactions of formamide with amines were carried out
under the standardized conditions, giving high yields
of the N-formyl products (Table 3, entries 10–13). Fur-
thermore, it should be noted that N-formyl products
[a]
Reaction conditions: phthalimide (1 mmol), amine
(1.1 mmol) and Nd2Na8(OCH2CF3)14(THF)6 (A)
(4.0 mol%) at 1208C for 24 h under an argon atmosphere
and solvent-free conditions.
Isolated yield.
2
[b]
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Table 5. Transamidation of thioacetamide and thiobenz-
AHCTUNGTRENNUNG
amide with amines by catalyst A.[a]
amides in the presence of phosphorus pentasulfide or
the Lawesson reagent, which suffers from many limi-
tations.[88–95] To further evaluate the scope of our pro-
tocol and compare our results with those from the lit-
erature, transamidation reactions of thioacetamide
and thiobenzamide were examined with some amines
including primary and secondary amines (Table 5).
Gratifyingly, our catalytic system proved to be active
for this transformation too. Firstly, we found that the
transamidation of thioacetamide with benzylamine
(2a), pyridin-2-ylmethanamine (2b), dodecylamine
(2d) as well as morpholine (2j) proceeded efficiently
and furnished all types of thioacylation products in
good to excellent yields under the catalytic conditions
(Table 5, entries 1–4). Then, the transamidation of
thioACHTUNGTRENNUNGbenzamide with primary and secondary amines
was also examined (Table 5, entries 5–9). Primary
amines 2a, 2b, 2c and 2d can work well with thiobenz-
ACHTUNGTRENNUNGamide. The reaction conversions can reach 81% for
5a’, 75% for 5b’, 79% for 5c’ and 84% for 5d’, respec-
tively. For secondary amine 2j, the yield can still
reach 51% for 5j’. The results indicated that the com-
plex Ln2Na8(OCH2CF3)14(THF)6 as a novel homoge-
neous catalyst has the desirable capability for catalyz-
ing the transamidation of thioamides.
The bimetallic cooperative catalysts could utilize
many different types of metals, such as alkali metals,
transition metals and lanthanides.[96] The important
role of lanthanides in the bimetallic catalysts, was
studied by X-ray and NMR analysis.[97–100] According
to our experimental results, both Ln(OCH2CF3)3 and
NaOCH2CF3 species, which can be regarded as mono-
metallic
fractions
of
catalyst
Ln2Na8(OCH2CF3)14(THF)6 failed to catalyze the
transamidation of amides under otherwise identical
conditions (Table 1, entries 8 and 9). Thus, it is of
great significance to investigate whether our hetero-
metallic structure is essential for the high activity.
Firstly, the 1H NMR spectra of diamagnetic
Y2Na8(OCH2CF3)14(THF)6 (catalyst C) indicated that
the polynuclear structure was retained in solution at
room temperature (Supporting Information, Fig-
1
ure S1). Then, variable-temperature H NMR spectra
of Y2Na8(OCH2CF3)14(THF)6 in DMF-d7 demonstrat-
ed that the heterometallic structure of catalyst C re-
mained invariant in the presence of excess DMF as
substrate and under elevated temperatures from 30 to
1208C. At the same time, when the temperature re-
1
covered from 120 to 308C, the H NMR spectra of
catalyst C also returned to the orginal state (Support-
ing Information, Figure S2). Interestingly, we found
that ligand protons in catalyst C were sensitive to the
environmental temperature and the signals of
OCH2CF3 gave an obvious upfield shifts along with
the increase of temperature. On the contrary, the
other two groups of protons from THF were com-
pletely unchanged with changes of temperature. Final-
[a]
Reaction conditions: thioacetamide (1 mmol), amine 2
(1.1 mmol) and Nd2Na8(OCH2CF3)14(THF)6 (A)
(4.0 mol%) at 1208C for 24 h under an argon atmosphere
and solvent-free conditions.
Isolated yield.
[b]
[c]
Thiobenzamide (1 mmol), amine
2 (1.1 mmol) and
Nd2Na8(OCH2CF3)14(THF)6 (A) (4.0 mol%) at 1208C for
24 h with the use of toluene (0.5 mL) for solubility.
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Scheme 2. Proposed catalytic cycle for the transamidation of amides with amines.
ly, we have conducted a more telling experiment for Conclusions
illuminating whether our heterometallic complex
Y2Na8(OCH2CF3)14(THF)6 may undergo dynamic In summary, heterobimetallic lanthanide alkoxide
equilibria in the presence of DMF and benzylamine complexes were used as a new class of acid–base bi-
as substrates. The similar variable-temperature functional catalyst for the transamidation of primary,
1H NMR spectra of Y2Na8(OCH2CF3)14(THF)6 in the secondary and tertiary amides with aliphatic and aro-
presence of DMF and benzylamine in DMSO-d6 (Sup- matic amines in good to excellent yields under milder
porting Information, Figures S3 and S4) are in line reaction conditions than those previously reported.
with the results of the Y2Na8(OCH2CF3)14(THF)6 in The methodology was also applied to the weakly reac-
DMF-d7 binding study above. Therefore, we speculat- tive thioamides to demonstrate its versatility and wide
ed that Y as the Ln centers worked as Lewis acids for substrate scope. The efficient activation of transesteri-
activating the carbonyl oxygen atom of DMF at fication was endowed by the cooperative catalyst
higher temperature, which induced the upfield shifts comprising soft Lewis acid and hard Brønsted base.
of ligand protons due to the reduced electron-with- The transamidation can be catalyzed efficiently by
drawing ability of Ln. Based on these results and a heterobimetallic lanthanide complex with a clear X-
other mechanism studies of acid–base bifunctional ray crystal structure that may be regarded as an evi-
catalysis in the literature, a plausible mechanism for dence for the proposed dual activation mechanism
the transamidation reaction is illustrated in Scheme 2. and this bifunctional concept may be applicable to
Firstly, heterobimetallic lanthanide/sodium alkoxide the design of new multimetal-catalyzed organic trans-
complex Ln2Na8(OCH2CF3)14(THF)6 activates both formations.
the amides and amine to generate the adduct (II),
wherein lanthanide metal ions work as Lewis acid
centers for activating the carbonyl oxygen atom of
amide while the sodium alkoxide moieties function as
Experimental Section
the Brønsted bases to bring the nucleophile amine in
close proximity. Then the formation of a sp3 hybrid-
ized tetrahedral intermediate (III) is followed by the
nucleophilic attack of the activated amine on the elec-
trophilic carbon center of the carbonyl moiety. Subse-
quently, the sterically congested (III) collapses to re-
generate the sp2 hybridized carbonyl unit and the
active species (I) is resurrected along with the release
of the amide and amine products, respectively.
General Methods
All manipulations and reactions were performed under an
atmosphere of argon with standard Schlenk techniques. The
amides and amines were purchased commercially. Heterobi-
metallic
lanthanide/sodium
alkoxide
complexes
Ln2Na8(OCH2CF3)14(THF)6 [Ln=Nd (A), Sm (B), Y (C)
and Yb (D)] and the corresponding monometallic complex
Nd(OCH2CF3)3 were prepared according to the literature.[73]
1H and 13C NMR spectra were recorded with a Bruker
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Avance 400 MHz spectrometer using CDCl3, DMSO-d6 or
DMF-d7 as the solvent with tetramethylsilane (TMS) as the
internal standard. Column chromatography was performed
using silica gel (100–200 mesh). Petroleum ether (PE) used
was the fraction boiling in the range 60–908C.
(101 MHz, DMSO-d6): d=165.6, 138.6, 134.7, 131.7, 131.4,
128.4, 127.6, 122.2, 115.3.
N-Methyl-N-phenylbenzamide (3ah):[104] White solid;
yield: 169 mg (80%); mp 60–628C. 1H NMR (400 MHz,
CDCl3): d=7.28 (dd, J=7.6, 6.3 Hz, 2H), 7.25–7.18 (m,
3H), 7.18–7.09 (m, 3H), 7.03 (d, J=7.6 Hz, 2H), 3.49 (s,
3H); 13C NMR (101 MHz, CDCl3): d=170.7, 144.9, 135.9,
129.6, 129.1, 128.7, 127.7, 126.9, 126.5, 38.4.
N,N-Dibutylbenzamide (3ai):[105] Colorless oil; yield:
195 mg (82%). 1H NMR (400 MHz, CDCl3): d=7.39–7.33
(m, 5H), 3.34 (m, 4H), 1.80–1.18 (m, 8H), 1.15–0.70 (m,
6H); 13C NMR (101 MHz, CDCl3): d=171.7, 137.3, 129.0,
128.3, 126.5, 48.8, 44.5, 30.8, 29.7, 20.3, 19.7, 13.9, 13.6.
Morpholino(phenyl)methanone (3aj):[106] White solid;
yield: 145 mg (76%); mp 72–748C. 1H NMR (400 MHz,
CDCl3): d=7.45–7.35 (m, 5H), 4.10–3.03 (m, 8H); 13C NMR
(101 MHz, CDCl3): d=170.4, 135.4, 129.8, 128.5, 127.1, 66.9,
48.1, 42.6.
Typical Procedure for the Transamidation (3aa as an
example)
A mixture of Nd2Na8(OCH2CF3)14(THF)6 (A) (0.04 mmol),
benzamide (1 mmol) and benzylamine (1.1 mmol) in a 10-
mL Schlenk tube was stirred at 1208C for 16 h under argon.
The resulting mixture was diluted with CH2Cl2 (8 mL) and
then filtered through a small plug of silica gel to remove the
catalyst. The crude product was purified by silica gel column
chromatography (EtOAc/PE=1:1, v/v) to provide the title
compound as a white solid: yield: 194 mg (92%).
N-Benzyl-2-phenylacetamide (3ba):[107] White solid; yield:
N-Benzylbenzamide (3aa):[39] White solid; yield: 194 mg
(92%); mp 101–1038C. 1H NMR (400 MHz, CDCl3): d=
7.79 (d, J=7.8 Hz, 2H), 7.54–7.46 (m, 1H), 7.46–7.35 (m,
2H), 7.35–7.30 (m, 4H), 7.30–7.28 (m, 1H), 6.39 (br, s, 1H),
4.66 (d, J=5.5 Hz, 2H); 13C NMR (101 MHz, CDCl3): d=
167.3, 138.2, 134.4, 131.6, 128.8, 128.6, 128.0, 127.7, 127.0,
44.2.
1
202 mg (90%); mp 116–1198C. H NMR (400 MHz, CDCl3):
d=7.38–7.22 (m, 8H), 7.17 (d, J=6.7 Hz, 2H), 5.78 (br, s,
1H), 4.41 (d, J=5.8 Hz, 2H), 3.62 (s, 2H); 13C NMR
(101 MHz, CDCl3): d=171.0, 138.1, 134.8, 129.4, 129.0,
128.6, 127.5, 127.4, 127.4, 43.7, 43.6.
N-Dodecyl-2-phenylacetamide (3bd):[108] White solid;
yield: 270 mg (89%); mp 80–828C. 1H NMR (400 MHz,
CDCl3): d=7.40–7.23 (m, 5H), 5.41 (br, s, 1H), 3.57 (s, 2H),
3.19 (dd, J=13.3, 6.9 Hz, 2H), 1.41 (dd, J=13.8, 7.0 Hz,
2H), 1.32–1.16 (m, 18H), 0.88 (t, J=6.8 Hz, 3H); 13C NMR
(101 MHz, CDCl3): d=170.9, 135.1, 129.5, 129.0, 127.3, 43.9,
39.7, 31.9, 29.6, 29.5, 29.5, 29.4, 29.4, 29.2, 26.8, 22.7, 14.1.
N-Benzylisonicotinamide (3ca):[109] White solid; yield:
184 mg (87%); mp 88–908C. 1H NMR (400 MHz, CDCl3):
d=8.59 (d, J=4.0 Hz, 2H), 7.60 (d, J=4.2 Hz, 2H), 7.40
(br, s, 1H), 7.36–7.31 (m, 5H), 4.58 (s, 2H); 13C NMR
(101 MHz, CDCl3): d=165.5, 150.3, 141.6, 137.6, 128.8,
127.9, 127.8, 121.1, 44.2.
N-(Pyridin-2-ylmethyl)benzamide (3ab):[101] White solid;
yield: 189 mg (89%); mp 56–588C. 1H NMR (400 MHz,
CDCl3): d=8.55 (d, J=4.5 Hz, 1H), 7.92–7.86 (m, 2H), 7.81
(s, 1H), 7.71 (m, 1H), 7.53–7.46 (m, 1H), 7.46–7.41 (m, 2H),
7.37 (d, J=7.8 Hz, 1H), 7.24 (m, 1H), 4.77 (d, J=5.0 Hz,
2H); 13C NMR (101 MHz, CDCl3): d=167.5, 156.5, 148.7,
137.0, 134.2, 131.5, 128.5, 127.1, 122.5, 122.3, 44.7.
N-Butylbenzamide (3ac):[102] Colorless liquid; yield:
167 mg (94%). 1H NMR (400 MHz, CDCl3): d=7.82–7.70
(m, 2H), 7.50–7.38 (m, 3H), 6.54 (br, s, 1H), 3.48–3.44 (s,
2H), 1.66–1.52 (m, 2H), 1.47–1.32 (m, 2H), 0.94 (t, J=
7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3): d=167.8, 134.7,
131.3, 128.4, 127.0, 39.9, 31.7, 20.1, 13.8.
N-Dodecylisonicotinamide (3cd):[110] White solid; yield:
255 mg (88%); mp 70–728C. 1H NMR (400 MHz, CDCl3):
d=8.76 (d, J=5.2 Hz, 2H), 7.92 (d, J=5.2 Hz, 2H), 7.02
(br, m, 1H), 3.47 (q, J=6.8 Hz, 2H), 1.65–1.57 (m, 2H),
1.42–1.19 (m, 18H), 0.88 (t, J=6.7 Hz, 3H); 13C NMR
(101 MHz, CDCl3): d=164.8, 148.6, 143.8, 121.9, 40.4, 31.9,
29.7, 29.6, 29.6, 29.6, 29.5, 29.4, 29.3, 27.0, 22.7, 14.1.
N-Benzyldodecanamide (3da):[111] White solid; yield:
260 mg (90%); mp 82–838C. 1H NMR (400 MHz, CDCl3):
d=7.38–7.22 (m, 5H), 5.84 (br, s, 1H), 4.44 (d, J=5.0 Hz,
2H), 2.22 (t, J=7.7 Hz, 2H), 1.71–1.59 (m, 2H), 1.32–1.23
(m, 16H), 0.88 (t, J=6.7 Hz, 3H); 13C NMR (101 MHz,
CDCl3) d 173.0, 138.5, 128.7, 127.8, 127.5, 43.6, 36.8, 31.9,
29.6, 29.5, 29.4, 29.3, 25.8, 22.7, 14.1.
N-Dodecylbenzamide (3ad):[102] White solid; yield: 269 mg
1
(93%); mp 66–688C. H NMR (400 MHz, CDCl3): d=7.78–
7.72 (m, 2H), 7.52–7.42 (m, 3H), 6.19 (br, s, 1H), 3.45 (dd,
J=12.5, 6.9 Hz, 2H), 1.67–1.55 (m, 2H), 1.42–1.23 (m,
18H), 0.88 (t, J=6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3):
d=167.6, 134.8, 131.3, 128.5, 126.9, 40.2, 31.9, 29.7, 29.6,
29.6, 29.6, 29.4, 27.0, 22.7, 14.1.
N-Phenylbenzamide (3ae):[101] White solid; yield: 163 mg
(83%); mp 161–1638C. 1H NMR (400 MHz, CDCl3): d=
7.91 (br, s, 1H), 7.89–7.82 (m, 2H), 7.64 (d, J=7.7 Hz, 2H),
7.58–7.50 (m, 1H), 7.47 (t, J=7.4 Hz, 2H), 7.36 (t, J=
7.9 Hz, 2H), 7.15 (t, J=7.4 Hz, 1H); 13C NMR (101 MHz,
CDCl3): d=165.8, 137.9, 135.0, 131.8, 129.1, 128.8, 127.0,
124.6, 120.3.
N-Dodecyldodecanamide (3dd):[112] White solid; yield:
323 mg (88%); mp 78–808C. 1H NMR (400 MHz, CDCl3):
d=11.48 (br, s, 1H), 3.44–3.33 (m, 1H), 2.63–2.53 (m, 1H),
2.35 (t, J=7.5 Hz, 2H), 1.69–1.51 (m, 4H), 1.40–1.18 (m,
34H), 0.88 (t, J=6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3):
d=180.2, 39.8, 34.1, 31.9, 29.7, 29.6, 29.6, 29.6, 29.5, 29.5,
29.4, 29.4, 29.4, 29.3, 29.3, 29.1, 29.1, 27.5, 27.0, 24.7, 22.7,
14.1.
N-(p-Tolyl)benzamide (3af):[102] White solid; yield: 181 mg
(86%); mp 152–1548C. 1H NMR (400 MHz, CDCl3): d=
7.87 (d, J=6.8 Hz, 2H), 7.82 (br, s, 1H), 7.56–7.44 (m, 5H),
7.17 (d, J=8.2 Hz, 2H), 2.34 (s, 3H); 13C NMR (101 MHz,
CDCl3): d=165.7, 135.4, 135.1, 134.2, 131.7, 129.6, 128.7,
127.0, 120.3, 20.9.
N-(4-Bromophenyl)benzamide (3ag):[103] White solid;
yield: 184 mg (74%); mp 200–2038C. 1H NMR (400 MHz,
DMSO-d6): d=10.36 (br, s, 1H), 7.95 (d, J=7.5 Hz, 2H),
7.78 (d, J=8.5 Hz, 2H), 7.63–7.49 (m, 5H); 13C NMR
N-Benzylacetamide (3ea):[107] White solid; yield: 139 mg
1
(93%); mp 60–628C. H NMR (400 MHz, CDCl3): d=7.46–
7.08 (m, 5H), 5.95 (br, s, 1H), 4.41 (d, J=5.5 Hz, 2H), 2.01
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8
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(s, 3H); 13C NMR (101 MHz, CDCl3): d=170.1, 138.2, 128.7,
127.8, 127.5, 43.7, 23.2.
(400 MHz, DMSO-d6): d=10.52 (br, s, 1H), 8.54 (d, J=
4.7 Hz, 1H), 7.77 (td, 1.8 Hz, 1H), 7.34–7.26 (m, 2H), 4.85
(d, J=5.6 Hz, 2H), 2.49 (s, 3H); 13C NMR (101 MHz,
DMSO-d6): d=200.2, 156.4, 149.0, 136.7, 122.4, 121.7, 50.4,
32.8.
N-Dodecylacetamide (3ed):[113] White solid; yield: 204 mg
1
(90%); mp 53–558C. H NMR (400 MHz, CDCl3): d=5.62
(br, s, 1H), 3.24–3.22 (m, 2H), 1.99 (s, 3H), 1.49 (m, 2H),
1.28–1.26 (m, 18H), 0.88 (t, J=6.0 Hz, 3H); 13C NMR
(101 MHz, CDCl3): d=170.3, 39.8, 31.9, 29.6, 29.6, 29.6,
29.6, 29.3, 29.3, 26.9, 23.2, 22.7, 14.1.
N-Dodecylethanethioamide (5d): White solid; yield:
221 mg (91%); mp 85–978C. 1H NMR (400 MHz, CDCl3):
d=7.31 (s, 1H), 3.64 (q, J=6.8 Hz, 2H), 2.56 (s, 3H), 1.71–
1.60 (m, 2H), 1.38–1.22 (m, 18H), 0.88 (t, J=6.6 Hz, 3H);
13C NMR (101 MHz, CDCl3): d=200.6, 46.5, 34.3, 31.9, 29.6,
29.6, 29.5, 29.5, 29.3, 29.2, 28.0, 27.0, 22.7, 14.1; HR-MS
(EI): m/z=244.2090, calcd. for [C14H29NS+H]+: 244.4530.
1-Morpholinoethane-1-thione (5j):[122] White solid; yield:
123 mg (85%); mp 90–918C. 1H NMR (400 MHz, CDCl3):
d=4.34 (t, J=4.9 Hz, 2H), 3.79 (t, J=6.1 Hz, 2H), 3.77–
3.69 (m, 4H), 2.67 (s, 3H); 13C NMR (101 MHz, CDCl3):
d=198.9, 66.4, 66.2, 50.2, 49.6, 32.1.
N-(p-Tolyl)acetamide (3ef):[114] White solid; yield: 127 mg
(85%); mp 148–1508C. 1H NMR (400 MHz, CDCl3): d=
7.37 (d, J=7.7 Hz, 2H), 7.28 (br, s, 1H), 7.11 (d, J=7.8 Hz,
2H), 2.31 (s, 3H), 2.16 (s, 3H); 13C NMR (101 MHz,
CDCl3): d=168.3, 135.3, 134.0, 129.5, 120.0, 24.5, 20.9.
N-Benzylformamide (3fa):[42] Colorless oil; yield: 128 mg
1
(95%). H NMR (400 MHz, CDCl3): d=8.26 (d, 1H), 7.34–
7.26 (m, 5H), 5.92 (br, s, 1H), 4.48 (d, 2H) (194 mg, 92%
yield);. 13C NMR (101 MHz, CDCl3): d=160.9, 137.4, 128.8,
127.8, 126.9, 42.2.
N-Benzylbenzothioamide (5a’):[48] White solid; yield:
1
N-(Pyridin-2-ylmethyl)formamide (3fb):[115] Light-yellow
184 mg (81%). H NMR (400 MHz, CDCl3): d=7.77–7.75(d,
1
2H),7.69 (b, 1H), 7.46 (m, 1H), 7.41–7.37 (m, 2H), 5.01–
5.00 (d, 2H); 13C NMR (101 MHz, CDCl3): d=198.0, 140.7,
135.2, 130.2, 128.0, 127.8, 127.6, 127.4, 127.2, 126.9, 126.7,
125.9, 125.7, 50.1.
oil; yield: 122 mg (90%). H NMR (400 MHz, CDCl3): d=
8.49 (d, J=3.5 Hzs, 1H), 8.28 (s, 1H), 7.85 (br, s, 1H), 7.66
(m, 1H), 7.29 (d, J=7.4 Hz, 1H), 7.21 (m, 1H), 4.57 (s,
2H); 13C NMR (101 MHz, CDCl3): d=161.8, 156.5, 148.7,
137.0, 122.4, 121.9, 43.0.
N-(Pyridin-2-ylmethyl)benzothioamide (5b’):[123] White
1
N-Dodecylformamide (3fd):[116] White solid; yield: 200 mg
solid; yield: 171 mg (75%). H NMR (400 MHz, CDCl3): d=
1
9.56 (br, 1H), 8.57 (m, 1H), 7.93 (m, 2H), 7.80 (m, 1H),
7.49–7.33 (m, 5H), 5.13 (d, 2H); 13C NMR (101 MHz,
CDCl3): d=198.2, 153.5, 147.8, 137.9, 131.3, 127.1, 123.1,
49.8.
(94%); mp 33–358C. H NMR (400 MHz, CDCl3): d=8.15
(s, 1H), 5.98 (br, s, 1H), 3.36–3.10 (m, 2H), 1.51 (m, 2H),
1.27–1.23 (m, 18H), 0.88 (t, J=3.0 Hz, 3H); 13C NMR
(101 MHz, CDCl3): d=161.4, 38.3, 31.9, 29.7, 29.6, 29.6,
29.6, 29.5, 29.4, 29.3, 26.9, 22.7, 14.1.
N-Butylbenzothioamide (5c’): Colorless oil; yield: 153 mg
1
Piperidine-1-carbaldehyde (3fj):[117] Colorless oil; yield:
(79%). H NMR (400 MHz, CDCl3): d=7.70–7.70 (d, 2H),
1
7.58 (b, 1H), 7.44 (m, 2H), 7.38–7.35 (m, 2H), 3.82 (m, 2H),
1.74 (m, 2H), 1.45 (m, 2H), 0.98 (t, 3H); 13C NMR
(101 MHz, CDCl3): d=198.2, 141.1, 129.9, 127.5, 125.6, 45.6,
29.2, 19.3, 12.8; HR-MS (EI): m/z=194.0808, calcd. for
[C11H15NS+H]+: 194.0925.
97mg (86%). H NMR (400 MHz, CDCl3): d=8.01 (s, 1H),
3.49 (t, J=1.5 Hz, 2H), 3.33 (t, J=1.2 Hz, 2H), 1.78–1.65
(m, 2H), 1.65–1.46 (m, 4H); 13C NMR (101 MHz, CDCl3):
d=160.6, 46.6, 40.4, 26.4, 24.9, 24.5.
2-Benzylisoindoline-1,3-dione (4a):[118] White solid; yield:
N-Dodecylbenzothioamide (5d’): White solid; yield:
257 mg (84%). 1H NMR (400 MHz, CDCl3): d=7.74 (m,
2H), 7.52 (br, 1H), 7.46–7.37 (m, 3H), 3.83 (m, 2H), 1.76
(m, 2H), 1.26 (m, 2H), 0.88 (m, 3H); 13C NMR (101 MHz,
CDCl3): d=198.9, 142.1, 130.9, 128.4, 126.8, 126.2, 46.8, 29.6,
29.3, 28.2, 27.2, 22.8, 13.8; HR-MS (EI): m/z=306.1953,
calcd. for [C19H31NS+H]+: 306.5240.
1
211 mg (89%); mp 115–1188C. H NMR (400 MHz, CDCl3):
d=7.84 (m, 2H), 7.70 (m, 2H), 7.43 (m, 2H), 7.29 (m, 3H),
4.85 (s, 2H); 13C NMR (101 MHz, CDCl3): d=168.0, 136.3,
134.0, 132.1, 128.7, 128.6, 127.8, 123.3, 41.6.
2-(Pyridin-2-ylmethyl)isoindoline-1,3-dione
(4b):[119]
1
White solid; yield: 203 mg (85%); mp 122–1238C. H NMR
(400 MHz, CDCl3): d=8.54 (d, J=4.3 Hz, 1H), 7.89 (m,
2H), 7.74 (m, 2H), 7.65 (m, 1H), 7.29 (d, J=7.9 Hz, 1H),
7.18 (dd, J=7.1, 5.2 Hz, 1H), 5.04 (s, 2H); 13C NMR
(101 MHz, CDCl3): d=167.9, 154.6, 147.7, 138.8, 134.2,
132.1, 123.6, 123.2, 122.3, 41.9.
Morpholino(phenyl)methanethione (5j’):[49] White solid;
1
yield: 106 mg (51%). H NMR (400 MHz, CDCl3): d=7.41–
7.29 (m, 5H), 4.45 (t, 2H), 3.89 (t, 2H), 3.63–3.61 (m, 4H);
13C NMR (101 MHz, CDCl3): d=200.9, 142.4, 129.9, 129.4,
128.9, 128.5, 127.1, 125.9, 66.7, 52.5, 49.6.
2-Dodecylisoindoline-1,3-dione (4d): White solid; yield:
1
290 mg (92%); mp 62–658C. H NMR (400 MHz, CDCl3) d
7.85–7.83 (m, 2H), 7.71 (dd, J=5.3, 3.1 Hz, 2H), 3.68 (t, J=
7.3 Hz, 2H), 1.72–1.61 (m, 2H), 1.36–1.22 (m, 18H), 0.87 (t,
J=6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3): d=168.5,
133.8, 132.2, 123.1, 38.1, 31.9, 29.6, 29.6, 29.5, 29.3, 29.2, 28.6,
26.9, 22.7, 14.1; HR-MS (EI): m/z=316.2260, calcd. for
[C20H29NO2 +H]+: 316.4570.
Acknowledgements
We acknowledge financial support by NSFC (20902001,
21102001), Natural Science Foundation of Anhui Province
(090416220, 1608085MB39), Natural Science Foundation of
Education Department of Anhui Province (KJ2014A013,
KJ2015A047), and 211 Project of Anhui University.
N-Benzylethanethioamide (5a):[120] White solid; yield:
157 mg (95%); mp 66–678C. 1H NMR (400 MHz, CDCl3):
d=7.36–7.21 (m, 5H), 4.74 (d, J=5.0 Hz, 2H), 2.51 (s, 3H);
13C NMR (101 MHz, CDCl3): d=199.8, 135.0, 127.9, 127.4,
127.2, 49.6, 33.1.
N-(Pyridin-2-ylmethyl)ethanethioamide (5b):[121] White
solid; yield: 149 mg (90%); mp 121–1238C. 1H NMR
Adv. Synth. Catal. 0000, 000, 0 – 0
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References
[30] D. P. Singh, B. K. Allam, K. N. Singh, V. P. Singh, RSC
Adv. 2014, 4, 1155–1158.
[1] C. L. Alle, J. M. Williams, Chem. Soc. Rev. 2011, 40,
3405–3415.
[2] K. Ouyang, W. Hao, W.-X. Zhang, Z. Xi, Chem. Rev.
[31] R. Lanigan, P. Starkov, T. D. Sheppard, J. Org. Chem.
2013, 78, 4512–4523.
[32] S. N. Rao, D. C. Mohan, S. Adimurthy, Org. Lett.
2013, 15, 1496–1499.
2015, 115, 12045–12090.
[3] A. H. Cherney, N. T. Kadunce, S. E. Reisman, Chem.
Rev. 2015, 115, 9587–9652.
[4] L. Souillart, N. Cramer, Chem. Rev. 2015, 115, 9410–
9464.
[5] R. Dorel, A. M. Echavarren, Chem. Rev. 2015, 115,
9028–9072.
[6] I. Bauer, H.-J. Knçlker, Chem. Rev. 2015, 115, 3170–
3387.
[33] R. Vanjari, B. K. Allam, K. N. Singh, Tetrahedron Lett.
2013, 54, 2553–2555.
[34] M. Zhang, S. Imm, S. Bꢄhn, M. Beller, Angew. Chem.
2012, 124, 3971–3975; Angew. Chem. Int. Ed. 2012, 51,
3905–3909.
[35] A. C. Liana, B. N. Atkinson, J. M. J. Williams, Angew.
Chem. 2012, 124, 1412–1415; Angew. Chem. Int. Ed.
2012, 51, 1383–1286.
[7] L. Yang, H. Huang, Chem. Rev. 2015, 115, 3468–3517.
[8] L. Huang, M. Arndt, K. T. Gooßen, H. Heydt, L. J.
Gooßen, Chem. Rev. 2015, 115, 2596–2697.
[9] A. Greenberg, C. M. Breneman, J. F. Liebman, The
Amide Linkage: Structural Significance in Chemistry,
Biochemistry Materials Science, John Wiley & Sons,
2000.
[10] E. Valeur, M. Bradley, Chem. Soc. Rev. 2009, 38, 606–
631.
[11] J. M. Humphrey, A. R. Chamberlin, Chem. Rev. 1997,
97, 2243–2266.
[12] L. Crespo, G. Sanclimens, M. Pons, E. Giralt, M.
Royo, F. Albericio, Chem. Rev. 2005, 105, 1663–1682.
[13] U. Boas, J. Brask, K. J. Jensen, Chem. Rev. 2009, 109,
2092–2118.
[14] M. Hutchby, Novel Synthetic Chemistry of Ureas and
Amides, Springer Science & Business Media, 2012.
[15] J. Kim, H. J. Kim, S. Chang, Eur. J. Org. Chem. 2013,
3201–3213.
[36] B. N. Atkinson, A. R. Chhatwal, H. V. Lomax, J. W.
Walton, J. M. J. Williams, Chem. Commun. 2012, 48,
11626–11628.
[37] E. L. Baker, M. M. Yamano, Y. Zhou, S. M. Anthony,
N. K. Garg, Nat. Commun. 2016, 7, 11554.
[38] M. Srinivas, A. D. Hudwekar, G. L. Reddy, K. A. A.
Kumar, R. A. Vishwakarma, S. D. Sawant, Tetrahe-
dron Lett. 2015, 56, 4775–4779.
[39] L. Becerra-Figueroa, A. Ojeda-Porras, D. Gamba-
Sꢃnchez, J. Org. Chem. 2014, 79, 4544–4545.
[40] R. Z. Fu, Y. Yang, Z. K. Chen, W. C. Lai, Q. Wang,
Tetrahedron 2014, 70, 9492–9499.
[41] R. Vanjari, B. K. Allam, K. N. Singh, RSC Adv. 2013,
3, 1691–1694.
[42] T. B. Nguyen, J. Sorres, M. Q. Tran, L. Ermolenko, A.
Al-Mourabit, Org. Lett. 2012, 14, 3202–3205.
[43] Y. Mikami, A. Noujima, T. Mitsudome, T. Mizugaki,
K. Jitsukawa, K. Kaneda, Chem. Eur. J. 2011, 17,
1768–1772.
[44] S. Das, D. Addis, S. Zhou, K. Junge, M. Beller, J. Am.
Chem. Soc. 2010, 132, 1770–1771.
[45] D. J. Constable, P. J. Dunn, J. D. Hayler, G. R. Hum-
phrey, J. L. Leazer Jr, R. J. Linderman, K. Lorenz, J.
Manley, B. A. Pearlman, A. Wells, Green Chem. 2007,
9, 411–420.
[16] L. Hie, N. F. F. Nathel, T. K. Shah, E. L. Baker, X.
Hong, Y.-F. Yang, P. Liu, K. Houk, N. K. Garg, Nature
2015, 524, 79–83.
[17] P. B. Thale, P. N. Borase, G. S. Shankarling, RSC Adv.
2016, 6, 52724–52728.
[18] C. Durgaiah, M. Naresh, P. Swamy, K. Srujana, B.
Rammurthy, N. Narender, Catal. Commun. 2016, 81,
29–32.
[19] M. Arefi, A. Heydari, RSC Adv. 2016, 6, 24684–24689.
[20] S. L. Yedage, D. S. D’Silva, B. M. Bhanage, RSC Adv.
2015, 5, 80441–80449.
[21] B. Nammalwar, N. P. Muddala, F. M. Watts, R. A.
Bunce, Tetrahedron 2015, 71, 9101–9111.
[22] S. C. Ghosh, C. C. Li, H. C. Zeng, A. Q. Chen, Adv.
Synth. Catal. 2014, 356, 475–484.
[46] L. Pauling, R. B. Corey, Proc. Natl. Acad. Sci. USA
1951, 37, 729.
[47] A. Ojeda-Porras, D. Gamba-Sꢃnchez, Tetrahedron
Lett. 2015, 56, 4308–4311.
[48] J. W. Wu, Y. D. Wu, J. J. Dai, H. J. Xu, Adv. Synth.
Catal. 2014, 356, 2429–2436.
[49] S. N. Rao, D. C. Mohan, S. Adimurthy, RSC Adv.
2015, 5, 95313–95317.
[50] M. Tamura, T. Tonomura, K.-i. Shimizu, A. Satsuma,
Green Chem. 2012, 14, 717–724.
[51] N. J. White, Science 2008, 320, 330–334.
[52] C. Schmidt-Dannert, D. Umeno, F. H. Arnold, Nat.
Biotechnol. 2000, 18, 750–753.
[53] G. J. Schut, M. W. Adams, J. Bacteriol. 2009, 191,
4451–4457.
[23] S. N. Rao, D. C. Mohan, S. Adimurthy, Green Chem.
2014, 16, 4122–4126.
[24] M. A. Ali, S. M. A. H. Siddiki, K. Kon, K. I. Shimizu,
Tetrahedron Lett. 2014, 55, 1316–1319.
[25] S. Pathare, A. Jain, K. Akamanchi, RSC Adv. 2013, 3,
7697–7703.
[26] M. Tamura, T. Tonomura, K. I. Shimizu, A. Satsuma,
Green Chem. 2012, 43, 717–724.
[27] T. M. E. Dine, D. Evans, J. Rouden, J. Blanchet,
Chem. Eur. J. 2016, 22, 5894–5898.
[54] G. Zhao, W. Guan, L. Cai, P. G. Wang, Nat. Protoc.
2010, 5, 636–646.
[55] M. G. Resch, B. S. Donohoe, J. O. Baker, S. R.
Decker, E. A. Bayer, G. T. Beckham, M. E. Himmel,
Energy Environ. Sci. 2013, 6, 1858–1867.
[56] J. Serrano-Plana, I. Garcia-Bosch, A. Company, M.
Costas, Acc. Chem. Res. 2015, 48, 2397–2406.
[28] P. N. Muskawar, K. Thenmozhi, P. R. Bhagat, Appl.
Catal. A. 2015, 493, 158–167.
[29] D. W. Gu, X. X. Guo, Tetrahedron 2015, 71, 9117–
9122.
Adv. Synth. Catal. 0000, 000, 0 – 0
10
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
[57] C. E. Valdez, Q. A. Smith, M. R. Nechay, A. N. Alex-
androva, Acc. Chem. Res. 2014, 47, 3110–3117.
[58] R. M. Haak, S. J. Wezenberg, A. W. Kleij, Chem.
Commun. 2010, 46, 2713–2723.
[59] K. Yamatsugu, L. Yin, S. Kamijo, Y. Kimura, M.
Kanai, M. Shibasaki, Angew. Chem. 2009, 121, 1090–
1096; Angew. Chem. Int. Edit. 2009, 48, 1070–1076.
[60] T. Sone, A. Yamaguchi, S. Matsunaga, M. Shibasaki, J.
Am. Chem. Soc. 2008, 130, 10078–10079.
[61] D. H. Paull, C. J. Abraham, M. T. Scerba, E. Alden-
Danforth, T. Lectka, Acc. Chem. Res. 2008, 41, 655–
663.
[86] Y. Inoue, T. Kanbara, T. Yamamoto, Tetrahedron Lett.
2003, 44, 5167–5169.
[87] N. D. Koduri, Z. Wang, G. Cannell, K. Cooley, T. M.
Lemma, K. Miao, M. Nguyen, B. Frohock, M. Casta-
neda, H. Scott, J. Org. Chem. 2014, 79, 7405–7414.
[88] S. J. Coats, J. S. Link, D. J. Hlasta, Org. Lett. 2003, 5,
721–724.
[89] M. Jesberger, T. P. Davis, L. Barner, Synthesis 2003,
1929–1958.
[90] S. Raucher, P. Klein, J. Org. Chem. 1981, 46, 3558–
3559.
[91] A. B. Charette, M. Grenon, J. Org. Chem. 2003, 68,
5792–5794.
[92] D. L. Priebbenow, C. Bolm, Chem. Soc. Rev. 2013, 42,
7870–7880.
[93] A. K. Yadav, V. P. Srivastava, L. D. S. Yadav, Synth.
Commun. 2014, 44, 408–416.
[94] H. Xu, H. Deng, Z. Li, H. Xiang, X. Zhou, Eur. J.
Org. Chem. 2013, 7054–7057.
[95] T. Guntreddi, R. Vanjari, K. N. Singh, Org. Lett. 2014,
16, 3624–3627.
[96] J. Park, S. Hong, Chem. Soc. Rev. 2012, 41, 6931–6943.
[97] L. Di Bari, M. Lelli, G. Pintacuda, G. Pescitelli, F.
Marchetti, P. Salvadori, J. Am. Chem. Soc. 2003, 125,
5549–5558.
[98] A. J. Wooten, P. J. Carroll, P. J. Walsh, Angew. Chem.
2006, 118, 2611–2614; Angew. Chem. Int. Edit. 2006,
45, 2549–2552.
[99] A. J. Wooten, P. J. Carroll, P. J. Walsh, J. Am. Chem.
Soc. 2008, 130, 7407–7419.
[100] J. Qin, B. Xu, Y. Zhang, D. Yuan, Y. M. Yao, Green
Chem. 2016, 18, 4270–4275.
[101] X. Li, Y. H. Liu, W. J. Gu, B. Li, F. J. Chen, B. F. Shi,
Org. Lett. 2014, 16, 3904–3907.
[62] M. Delferro, T. J. Marks, Chem. Rev. 2011, 111, 2450–
2485.
[63] H. Li, T. J. Marks, Proc. Natl. Acad. Sci. USA 2006,
103, 15295–15302.
[64] M. P. Weberski, C. Chen, M. Delferro, T. J. Marks,
Chem. Eur. J. 2012, 18, 10715–10732.
[65] S. Liu, A. Motta, M. Delferro, T. J. Marks, J. Am.
Chem. Soc. 2013, 135, 8830–8833.
[66] J. P. McInnis, M. Delferro, T. J. Marks, Acc. Chem.
Res. 2014, 47, 2545–2557.
[67] M. Hatano, T. Miyamoto, K. Ishihara, J. Org. Chem.
2006, 71, 6474–6484.
[68] G. Postole, B. Chowdhury, B. Karmakar, K. Pinki, J.
Banerji, A. Auroux, J. Catal. 2010, 269, 110–121.
[69] Y. Hamashima, D. Sawada, M. Kanai, M. Shibasaki, J.
Am. Chem. Soc. 1999, 121, 2641–2642.
[70] R. Zeng, H. Sheng, Y. Zhang, Y. Feng, Z. Chen, J.
Wang, M. Chen, M. Zhu, Q. Guo, J. Org. Chem. 2014,
79, 9246–9252.
[71] H.-T. Sheng, J.-M. Li, Y. Zhang, Y.-M. Yao, Q. Shen,
Polyhedron 2008, 27, 1665–1672.
[72] B. Karami, M. Farahi, F. Pam, Tetrahedron Lett. 2014,
55, 6292–6296.
[73] M. Lei, L. Ma, L. Hu, Tetrahedron Lett. 2010, 51,
4186–4188.
[74] C. J. Gerack, L. McElwee-White, Molecules 2014, 19,
7689–7713.
[75] Z.-g. Wang, M. Lu, RSC Adv. 2014, 4, 1234–1240.
[76] M. Hosseini-Sarvari, H. Sharghi, J. Org. Chem. 2006,
71, 6652–6654.
[77] A. Jackson, O. Meth-Cohn, J. Chem. Soc. Chem.
Commun. 1995, 1319.
[78] B.-C. Chen, M. S. Bednarz, R. Zhao, J. E. Sundeen, P.
Chen, Z. Shen, A. P. Skoumbourdis, J. C. Barrish, Tet-
rahedron Lett. 2000, 41, 5453–5456.
[102] J. Liu, Q. Liu, H. Yi, C. Qin, R. Bai, X. Qi, A. Lei,
Angew. Chem. 2014, 126, 512–516; Angew. Chem. Int.
Edit. 2014, 53, 502–506.
[103] Y. Kuninobu, T. Uesugi, A. Kawata, K. Takai, Angew.
Chem. 2011, 123, 10590–10592; Angew. Chem. Int.
Edit. 2011, 50, 10406–10408.
[104] Q. Xia, X. Liu, Y. Zhang, C. Chen, W. Chen, Org.
Lett. 2013, 15, 3326–3329.
[105] Y. Li, F. Jia, Z. Li, Chem. Eur. J. 2013, 19, 82–86.
[106] T. Ueda, H. Konishi, K. Manabe, Org. Lett. 2012, 14,
5370–5373.
[107] H. Morimoto, R. Fujiwara, Y. Shimizu, K. Morisaki,
T. Ohshima, Org. Lett. 2014, 16, 2018–2021.
[108] H. Lundberg, F. Tinnis, H. Adolfsson, Chem. Eur. J.
2012, 18, 3822–3826.
[109] B. R. Kim, H. G. Lee, S. B. Kang, G. H. Sung, J. J.
Kim, J. K. Park, Y. J. Yoon, Synthesis 2012, 44, 42–50.
[110] T. Ichikawa, T. Kato, H. Ohno, J. Am. Chem. Soc.
2012, 134, 11354–11357.
[111] P. S. Chaudhari, S. D. Salim, R. V. Sawant, K. G. Aka-
manchi, Green Chem. 2010, 12, 1707–1710.
[112] K. Tomioka, T. Sumiyoshi, S. Narui, Y. Nagaoka, A.
Iida, Y. Miwa, T. Handa, J. Am. Chem. Soc. 2001, 123,
11817–11818.
[79] K. Kobayashi, S. Nagato, M. Kawakita, O. Morikawa,
H. Konishi, Chem. Lett. 1995, 575–576.
[80] A. Kakehi, S. Ito, S. Hayashi, T. Fujii, Bull. Chem.
Soc. Jpn. 1995, 68, 3573–3580.
[81] A. Flçrsheimer, M.-R. Kula, Monatsh. Chem. 1988,
119, 1323–1331.
[82] T. S. Jagodzinski, Chem. Rev. 2003, 103, 197–228.
[83] S. K. Alla, P. Sadhu, T. Punniyamurthy, J. Org. Chem.
2014, 79, 7502–7511.
[84] A. Yoshimura, A. D. Todora, B. J. Kastern, S. R.
Koski, V. V. Zhdankin, Eur. J. Org. Chem. 2014, 2014,
5149–5152.
[113] B. Kashyap, P. Phukan, RSC Adv. 2013, 3, 15327–
15336.
[85] M. Kadokura, T. Wada, K. Seio, M. Sekine, J. Org.
Chem. 2000, 65, 5104–5113.
[114] X. Sun, M. Wang, P. Li, X. Zhang, L. Wang, Green
Chem. 2013, 15, 3289–3294.
Adv. Synth. Catal. 0000, 000, 0 – 0
11
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
[115] S. Ko, H. Han, S. Chang, Org. Lett. 2003, 5, 2687–
[119] S. Inoue, H. Shiota, Y. Fukumoto, N. Chatani, J. Am.
Chem. Soc. 2009, 131, 6898–6899.
2690.
[120] F. Shibahara, R. Sugiura, T. Murai, Org. Lett. 2009, 11,
3064–3067.
[116] N. Ortega, C. Richter, F. Glorius, Org. Lett. 2013, 15,
1776–1779.
[121] H. S. El Khadem, J. Kawai, D. L. Swartz, Heterocycles
1989, 28, 239–248.
[122] C. Heyde, I. Zug, H. Hartmann, Eur. J. Org. Chem.
2000, 3273–3278.
[123] F. Shibahara, A. Kitagawa, E. Yamaguchi, T. Murai,
Org. Lett. 2006, 8, 5621–5624.
[117] X. Cui, Y. Zhang, Y. Deng, F. Shi, Chem. Commun.
2014, 50, 189–191.
[118] S. G. Koenig, C. P. Vandenbossche, H. Zhao, P.
Mousaw, S. P. Singh, R. P. Bakale, Org. Lett. 2008, 11,
433–436.
Adv. Synth. Catal. 0000, 000, 0 – 0
12
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
An Efficient Heterobimetallic Lanthanide Alkoxide
Catalyst for Transamidation of Amides under Solvent-Free
Conditions
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Adv. Synth. Catal. 2017, 359, 1 – 13
Hongting Sheng,* Ruijie Zeng, Wenjuan Wang,
Shuwen Luo, Yan Feng,* Jing Liu, Weijian Chen,
Manzhou Zhu, Qingxiang Guo
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ÞÞ
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