Copper catalyzed aryl amidation between Nα-Fmoc-protected amino-acid azides and aryl boronic acids

Article abstract of DOI:10.1080/00397911.2019.1704008

A simple and efficient method for the synthesis of aryl amides via oxidative copper-catalyzed coupling of commercially available aryl boronic acids and bench stable N^α-protected amino-acid azides is reported. The potential utility of this protocol is demonstrated through a survey of diversely substituted aryl boronic acids and several side-chain functionalized amino-acid azides, leading to the preparation of the desired amidated products in good to excellent yields. This amide synthesis is suitable for the preparation of amides (such as peptide aryl amides and sterically hindered amino acids) that are not or hardly accessible via classical approaches.

Full text of DOI:10.1080/00397911.2019.1704008

Synthetic Communications
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ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: https://www.tandfonline.com/loi/lsyc20
Copper catalyzed aryl amidation between Nα-
Fmoc-protected amino-acid azides and aryl
boronic acids
L. Roopesh Kumar, Vishwanatha Thimmalapura, Veladi Panduranga,
Mandipogula Mahesh, P. Venkata Ramana & Vommina V. Sureshbabu
To cite this article: L. Roopesh Kumar, Vishwanatha Thimmalapura, Veladi Panduranga,
Mandipogula Mahesh, P. Venkata Ramana & Vommina V. Sureshbabu (2019): Copper catalyzed
aryl amidation between Nα-Fmoc-protected amino-acid azides and aryl boronic acids, Synthetic
Communications, DOI: 10.1080/00397911.2019.1704008
To link to this article: https://doi.org/10.1080/00397911.2019.1704008
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https://doi.org/10.1080/00397911.2019.1704008
Copper catalyzed aryl amidation between Na-Fmoc-protected
amino-acid azides and aryl boronic acids
L. Roopesh Kumara, Vishwanatha Thimmalapuraa, Veladi Pandurangaa,
Mandipogula Maheshb, P. Venkata Ramanab, and Vommina V. Sureshbabua
aPeptide Research Laboratory, Department of Studies in Chemistry, Bangalore University, Central
b
College Campus, Bangalore, India; Department of Chemistry, Sri Krishnadevaraya University,
Anantapur, India
ABSTRACT
ARTICLE HISTORY
Received 25 May 2019
A simple and efficient method for the synthesis of aryl amides via
oxidative copper-catalyzed coupling of commercially available aryl
boronic acids and bench stable Na-protected amino-acid azides is
reported. The potential utility of this protocol is demonstrated
through a survey of diversely substituted aryl boronic acids and sev-
eral side-chain functionalized amino-acid azides, leading to the prep-
aration of the desired amidated products in good to excellent yields.
This amide synthesis is suitable for the preparation of amides (such
as peptide aryl amides and sterically hindered amino acids) that are
not or hardly accessible via classical approaches.
KEYWORDS
Amide bond; aryl boronic
acid; copper(I) bromide
dimethyl sulfide; Na-Fmoc-
amino-acid azides
GRAPHICAL ABSTRACT
Introduction
The amide bond is the most abundant functional group in organic chemistry.[1] It is an
important component in peptides, proteins, natural products, and pharmaceuticals.[2]
The classical means of preparing amides are the dehydrative coupling of carboxylic
acids with amines by the use of coupling reagents (Route 1 in chemical toolbox).[3] This
method often possesses various drawbacks such as long duration, expensive reagents,
the formation of byproduct and several others.[4] Thus, a universal method for the for-
mation of amides is not feasible. Over the past few years, chemists have extensively
investigated new methods to construct the amide linkage, aiming at a more efficient
and environmentally benign pathway.[5] Interesting approaches include the reaction of
CONTACT Vommina V. Sureshbabu
sureshbabuvommina@rediffmail.com; hariccb@gmail.com
Peptide Research
Laboratory, Department of Studies in Chemistry, Bangalore University, Central College Campus, Dr. B. R. Ambedkar
Veedhi, Bangalore, Karnataka 560001, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsyc.
Supplemental data for this article can be accessed on the publisher’s website
ß 2019 Taylor & Francis Group, LLC

2
L. ROOPESH KUMAR ET AL.
Figure 1. Amidations from various azides.
either activated carboxylic acid derivatives or activated amino derivatives (Route 2 in
chemical toolbox).[6] The potential utility of this route has been well established for the
synthesis of a variety of complex amides, peptides and natural products. Several of these
methods have been effectively transformed as chemoselective ligation reactions for the
protein chemical synthesis.[7] Many amide-containing pharmaceuticals and active drugs
are small molecules and thus require large scale preparation.[8] In this context, unnat-
ural substrates other than acid and amine as coupling agents, are useful to transform
into amides (Route 3 in chemical toolbox). However, these processes often work at high
temperature and requirement of metal catalysts.[9]
1
3
2
Chemical toolbox. Amidation reactions in literature.
Route 2 in the chemical toolbox for amide bond formation also includes azides which
have been shown to exhibit advantages in certain amidation reactions, for example, acid
azide-amine reaction,[10] Staudinger ligation,[11] thio acid-azide amidation,[12] seleno
acid-azide amidation,[13] alkyne-sulfonylazide coupling,[14] alcohol-azide amide synthe-
sis,[15] and azide-aldehyde amidation (Figure 1).[16] Most of these amidation reactions
are redox neutral and involving only the release of volatile side products (toxic HN3 in
case of acid azide-amine coupling, sulfur in thio acid-azide amidation reaction and all
other reactions involve the release of N2 as the sole byproduct). Therefore, the use of an
acid azide and boronic acids as substrates for amide formation is an attractive process.

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Table 1. Optimization of aryl amidation reaction.
Entry
Catalyst
Solvent (0.1 M)
MeOH
Time (h)
Yield 3ah (%)
Yield 4a (%)
1a
CuCl
CuCl
CuCl
CuCl
4
5
5
5
1
1
2
5
4
70
68
52
62
81
92
60
71
45
53
6
65
60
45
35
39
81
51
69
5e
18e
28e
15e
–
2b
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
EtOH
Trifluoroethanol
THF
CH3CN
MeOH
MeOH
MeOH
3c
4d
5b
CuBrꢀS(Me)2
CuBrꢀS(Me)2
CuBr
6d
–
7c
–
8d
CuBr2
5e
9d
Cu(OAc)2
CuI
22e
30e
80e
–
10d
11d
12d
13d
14d
15d
16d
17c,i
18b
19d
4
none
CuSO4
24
24
24
24
24
24
3
CuBrꢀS(Me)2
CuBrꢀS(Me)2
CuBrꢀS(Me)2
CuBrꢀS(Me)2
CuBrꢀS(Me)2
Cu(OAc)2ꢀH2O
CuSO4ꢀ5H2O
30f
25g
–
–
–
4
24
20e
–
a1.0 eq. of 1a, 2a and 10 mol % of catalyst;
b1.0 eq. of 1a, 1.5 eq. 2a and 10 mol % of catalyst;
c1.0 eq. of 1a, 2.0 eq. 2a and 10 mol % of catalyst;
d1.0 eq. of 1a, 1.5 eq. 2a and 5 mol % of catalyst;
eX ¼ Me;
fX ¼ Et;
gX ¼ CH2CF3;
h
¼ Isolated yield;
i
¼ control reaction under argon atmosphere (without O2).
Boronic acid, which is thermally and air-stable, is one of the important coupling part-
ners in the Suzuki cross-couplings.[17] In the context, of industrial applications and large
scale preparations, aryl amines are difficult to form amide under classical approaches
because of the less nucleophilicity of aryl amines. Thus, numerous non-classical sub-
strates are found to be highly inviable for the aryl-amidation process.[18]
Results and discussion
Recently, the copper-catalyzed Chan-Lam coupling has been discovered as a promising
greener alternative employed for the synthesis of aryl ethers,[19] carbamates or ureas[20]
and aryl sulfonyl amides.[21] In 2013, Watson and coworkers reported the first example
of the Chan-Lam coupling of alkyl boronic acids and primary amides catalyzed by a
copper(I) source.[22] It should be noted that high temperature and use of di-tert-butyl
peroxide as oxidant are not tolerable to stereochemically labile amino acids. Kim and
coworkers reported the synthesis of N-aryl carbamates via copper-catalyzed Chan-Lam
coupling of azidoformate and arylboronic acids.[20] We, therefore, targeted an oxidative
Chan-Lam coupling procedure that would form amide bond under mild conditions
with the use of alternative and reactive acid azides (Table 1 and Scheme 1). Herein, we

4
L. ROOPESH KUMAR ET AL.
3a (92 %)
3b (86 %)
3c (89 %)
3d (79 %)
3e (83 %)
3f (84 %)
3g (81 %)
3j (20 %)
3h (77 %)
3i (78 %)
3l (26 %)
3k (0 %), 24 h
3m (8 %)
3n (11 %)
3a* (83 %)
Scheme 1. Scope of Na-Fmoc amino-acid azides in the aryl amidation.
report a copper-catalyzed N-protected a-amino-acid azide-aryl boronic acid amidation
reaction which could be carried out under mild conditions to afford aryl amides in
excellent yields.
Our laboratory had reported the synthesis of Na-Fmoc-amino-acid azides and a wide
range of applications in the construction of novel peptidomimetics.[23] Thus, our plan

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was to evaluate the use of acid azides as an alternative to a primary amide source in
Chan-Lam couplings.
Our initial studies focused on the copper-catalyzed coupling between of Na-Fmoc-
Ala-CON3 (1a) [The Fmoc-protected amino-acid azide was prepared by activating the
amino acid using SOCl2 to the corresponding acid chloride in CH2Cl2. When 0.1 eq of
DMF as a catalyst was added, the reaction was completed within an hour at room tem-
perature. To this acid chloride, NaN3 was added to afford the corresponding Fmoc
amino-acid azide] and phenyl boronic acid (2a) at room temperature. An equimolar
amount of 1a and 2a in presence of 10mol % of CuCl gave only a moderate yield of 3a
along with the trace amount of methyl ester 4a derived from the esterification of 1a with
MeOH (Table 1, entry 1). The use of increased stoichiometry of boronic acid 2a such as
1.5, and 2.0 equivalents afford corresponding amide 3a in 68% and 52% yield respectively
along with methyl ester 4a (Table 1, entries 2 and 3). The yield of amide 3a was similar
when the catalyst loading was reduced to 5 mol % (Table 1, entry 4). We further investi-
gated various copper(I) catalysts (Table 1, entries 5–12, 18 and 19). Interestingly, 5 mol %
of CuBrꢀS(Me)2 gave 92% of amide 3a without any methyl ester 4a at room temperature
(Table 1, entry 6). Further screening of copper catalysts CuBr, CuI, CuCl, CuSO4,
Cu(OAc)2, CuBr2, Cu(OAc)2ꢀH2O and CuSO4ꢀ5H2O was found less efficient than
CuBrꢀS(Me)2 in terms of catalyst loading and yield. Other solvent systems such as THF,
CH3CN, trifluoroethanol and ethanol gave only poor yields of 3a (Table 1, entries 13–16).
Additionally, the controlled reaction under an argon atmosphere (without O2) afforded
the desired product in a lower yield of 81% in 3h (Table 1, entry 17 and page 5).
The scope of the reaction is illustrated with respect to various Na-protected amino-acid
azides and aryl boronic acids as well. In general, electron-donating phenyl boronic acids fur-
nished the desired products in good yields ranging from 78% to 92%. When electron-with-
drawing groups were employed as coupling partners, particularly, phenyl boronic acids
bearing chloro or bromo group, we obtained the desired amide in lesser yields. When phenyl
boronic acid bearing nitro (NO2) and cyano (CN) are used, we observed expected amide in
poor yields along with methyl ester 4a. On the other hand, the ortho-substituted methoxy
phenyl boronic acids gave the product in poor yield. This is due to the steric hindrance by
the ortho methoxy group (Scheme 1, 3j). Use of alkyl boronic acid such as n-butyl boronic
acid, afforded the desired product 3l in poor yield. However, cyclohexylboronic acid was
found to be unsuitable as the desired product was not formed even after 24hr. The sterically
hindered amino acids and bifunctional amino-acid azides readily engaged in the amidation
process without compromising the overall yield. All the desired amides were furnished in
good yields at room temperature (Scheme 1).
Test for racemization
ꢁ
The HPLC analysis of enantiomeric amides 3a and 3a showed the retention times
of 16.178 min and 12.197 min, respectively. However, the equimolar mixture of the
isomers showed distinct retention times of 16.180 min and 12.191 min which con-
firms that the present protocol is racemization free and the isomers are optically
pure (method: gradient 0.1% TFA water-acetonitrile; flow rate: 0.5 mL/min, 20 min).

6
L. ROOPESH KUMAR ET AL.
Scheme 2. Coupling of dipeptide acid azide and aryl boronic acid.
Scheme 3. Putative mechanism for the amidation reaction.
With the optimized reaction conditions in hand, the scope of peptide acid azides was
investigated next. N-Protected amino-peptide acid azide is coupled with substituted phe-
nyl boronic acid, obtained the desired products in good yields (Scheme 2).
Based on the literature precedents[20,21(a)], [24], a plausible mechanism for amidation
reaction between acid azide and boronic acid has been presented in Scheme 3. The first
step proceeds through the reaction of Cu(I) salt A and an acid azide which yields

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SYNTHETIC COMMUNICATIONSV
7
Cu(II) complex B via copper nitrene formation with the elimination of N2. Methyl bor-
onate ester (arylboronic acid and methyl boronate ester are in equilibrium)[25] under-
goes transmetalation with B to afford Cu(II) complex C. C undergoes oxidation to
afford Cu(III) complex D, and finally target amide E as a stable molecule is obtained by
the reductive elimination of D, regenerating Cu(I) catalyst A in the process. In the
absence of O2, the reductive elimination route from C occurs to give amide E, which is
a slow step (Scheme 3).[26]
Conclusion
In summary, we have developed a facile copper-catalyzed aryl amidation of aryl boronic
acids with acid azides to obtain N-aryl amides. The efficiency and functional group tol-
erance was examined with respect to both acid azide and boronic acid which is satisfac-
tory, allowing for the preparation of a series of functionalized aryl amides in good
yields. This transformation is economical, as it can be carried out effectively in an open
atmosphere at room temperature in the presence of only catalytic amount
of CuBrꢀS(Me)2.
Experimental section
General procedure for the amidation reaction
To a solution of Na-Fmoc amino-acid azide[23] (1.0 mmol) in MeOH (10 ml) was added
CuBrꢀS(Me)2 (5 mol %) and arylboronic acid (1.5 mmol). The mixture was stirred at
room temperature until the reaction was complete (TLC). The solution was filtered
through a pad of Celite and washed with EtOAc (10 mL). The filtrate was diluted with
H2O (10 mL) and the mixture was extracted with EtOAc (3 ꢂ 10 mL). The combined
organic layers were washed thrice with 10% Na2CO3 (3 ꢂ 10 mL), 1 N HCl (3 ꢂ 10 mL)
and H2O (3 ꢂ 10 mL) and dried over anhydrous Na2SO4. Evaporation of the solvent
under vacuo followed by column chromatography on silica gel (mesh 100–200) using
ethyl acetate and hexane as the eluents [Ethyl acetate/Hexane ¼ 3:7], gave the product
in good yields.
Fmoc-Ala-[CONH]-C6H5 [3a]
White solid, yield (92%, 0.355 g), m.p. ¼ 190–192 ꢃC (Lit. 191–193 ꢃC). 1H NMR
(400 MHz, CDCl3): d 9.20 (s, 1 H), 7.60–7.00 (m, 13 H), 6.28 (d, J ¼ 5.2 Hz, 1 H), 4.95-
4.82 (m, 1 H), 4.35 (d, J ¼ 5.2 Hz, 2 H), 4.07 (t, J ¼ 5.2 Hz, 1 H), 1.3 (d, J ¼ 5.6 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d 171.0, 155.8, 143.5, 140.9, 138.1, 130.8, 128.5, 127.4,
126.8, 124.9, 123.7, 119.6, 66.4, 50.9, 46.8, 18.7. HRMS: m/z Calculated for C24H23N2O3
[M þ H]þ 387.1709; found: 387.1706.[27]
1
Full experimental details, characterization data for compounds with copies of H and
13C NMR spectra and HRMS of ALL new compounds. This material can be found via
the “Supplementary Content” section of this article’s webpage.

8
L. ROOPESH KUMAR ET AL.
Acknowledgements
We are grateful to acknowledge the financial support from SERB, New Delhi, Government of
India. One of the authors, Roopesh Kumar, is thankful to DST Nano Mission for the fellowship.
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