Triple-Bond Directed Csp2?N Bond Formation with N-Fluorobenzenesulfonimide as Aminating Source: One-Step Transformation of Aldehydes into Amines

Article abstract of DOI:10.1002/chem.201903495

A metal-free, versatile triple-bond directed approach for the decarbonylative C?H amination of ortho-alkynyl quinoline/pyridine aldehydes using N-fluorobenzenesulfonimide as nitrogen source under mild reaction conditions has been described. The designed reaction strategy was triggered by trapping of fluorine by base with subsequent attack of bis(phenylsulfonyl)-λ²-azane on the carbonyl carbon of a heterocycle, which was gradually converted into the corresponding amine through a Curtius type rearrangement. This protocol provides a one-step approach for the conversion of aldehydes into amines in good yields. The synthesized amines were successfully transformed into biologically important pyrroloquinolines/pyridines.

Full text of DOI:10.1002/chem.201903495

A Journal of
Accepted Article
Title: Triple bond Directed Csp2-N Bond Formation through N-
Fluorobenzenesulfonimide as Aminating Source: One-Step
Transformation of Aldehyde into Amine
Authors: Akhilesh Kumar Verma, Sushmita ., Trapti Aggarwal, and
Norio Shibata
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201903495
Link to VoR: http://dx.doi.org/10.1002/chem.201903495
Supported by

10.1002/chem.201903495
Chemistry - A European Journal
COMMUNICATION
Triple bond Directed Csp2-N Bond Formation through N-
Fluorobenzenesulfonimide as Aminating Source: One-Step
Transformation of Aldehyde into Amine
Sushmita,† Trapti Aggarwal,† Norio Shibata and Akhilesh K. Verma*
Dedication ((optional))
Abstract: A metal-free versatile triple bond directed approach for the
decarbonylative C-H amination of ortho-alkynyl quinoline/pyridine
aldehyde using N-Fluorobenzenesulfonimide as nitrogen source
under mild reaction conditions has been described. The designed
reaction strategy was triggered by trapping of fluorine through the
base with subsequent attack of bis(phenylsulfonyl)-λ2-azane on
carbonyl carbon of heterocycle which gradually converted to amine
via Curtius type rearrangement. This protocol provides one-step
approach for the conversion of aldehyde to amine in good yields.
The synthesized amines compounds were successfully transformed
into biologically important pyrroloquinolines/pyridines.
date (Figure 1).
Figure 1. Organic functional group transformation
Interestingly, in 2012, Zhang and co-workers described a
highly selective benzylic C-H amination reaction by copper
catalysis.11 Later in 2013, Ritter and co-workers disclosed the
Pd-catalyzed amination of unactivated aryl ring using N-
fluorobenzenesulfonimide as a nitrogen source (Scheme 1c).12
Afterwards, various groups have reported amination using N-
Fuorobenzenesulfonimide (NFSI) and it emerged as a powerful
nitrogen source in C-H activation/amidation reactions.13 In 2017,
Ji14 and Jiang15 group reported the alkyne oxidation of ortho-
alkynyl aldehydes in presence of a silver catalyst (Scheme 1d-e).
However, decarbonylative amination using NFSI in presence of
alkynes remains elusive.
Owing to the importance of amine molecules in natural
products1 and drug molecules,2 numerous approaches have
been developed for their synthesis.3 The C-N bond forming
reaction attracts the interest of synthetic chemist from the last
century as the introduction of amino groups tune the
physicochemical properties of the molecule and made them a
biologically important structure.4 Traditionally, metal-catalyzed
C-N cross-coupling reactions such as Buchwald-Hartwig5 and
Ullmann-type coupling6 have been exploited for the C-N bond
formations. Previously, decarboxylative cross-coupling reactions
such as Curtius, Schmidt, Hoffman and Lossen rearrangements
using carboxylic acids and its derivatives have been reported for
the synthesis of amines7 (Figure 1). Curtius rearrangement was
vitally used for the generation of amines from carboxylic acids,
however; safety concern associated with azides restricts the use
of Curtius rearrangement, leading to the pursuit of new
strategies for this organic functional group transformation.8 In
2012, Mainolfi group reported the synthesis of secondary
anilines from substituted benzoic acid and amides through Cu-
catalyst at high temperature (Scheme 1a).9 Later, Ilangovan and
co-workers synthesize primary anilines from substituted benzoic
acid (scheme 1b).10 However, to the best of our knowledge,
metal-free synthesis of amines from aldehydes through in situ
generated isocyanate intermediate has not been explored till
[a]
Sushmita,† Dr. Trapti Aggarwal† and Prof. Akhilesh K. Verma*
Department of Chemistry, University of Delhi,
Delhi 110007, India
E-mail: : averma@acbr.du.ac.in
Prof. Norio Shibata
Department of Nanopharmaceutical Sciences and Department of
Life Science and Applied Chemistry, Nagoya Institute of
Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan
Scheme 1. Previous reports v/s present work
Inspired from our ongoing research on ortho-alkynyl
aldehydes,16 herein we hypothesized the synthesis of fluorinated
heterocycles through NFSI via metal-free strategy (Scheme 1f).
Our preliminary studies revealed that the reaction failed to afford
[b]
† Both authors contribute equally
Supporting information for this article is given via a link at the end of
the document.
1
This article is protected by copyright. All rights reserved.

10.1002/chem.201903495
Chemistry - A European Journal
COMMUNICATION
the proposed fluorinated product 5, however, an aminated
product 3 was isolated. The structure of 3b was unambiguously
established as 2-(m-tolylethynyl)quinolin-3-amine by X-ray
crystallographic studies (see ESI, Figure S1). Importantly, the
developed methodology provides 3-amino N-heterocycles which
various other bases were investigated. K2CO3 was proved
to be ineffective for the reaction, while lower yield was
obtained with t-BuONa and KOH (entries 7-9). However in
the absence of base no reaction was observed (entry 10).
Next, we screened the different solvents for the designed
reaction and interestingly the reaction proceeds in DMF and
DMSO while Dioxane was failed to give the desired product
(entries 11-13). When EtOH was employed as a solvent,
further cyclized to give
the medicinally
important
pyrroloquinolines/ pyrrolopyridines.
To identify the optimal reaction conditions, we have
screened various bases and solvents at different
temperature.
Ethyl
2-(phenylethynyl)quinoline-3-carboxylate
was
formed16e instead of designed product 3a (entry 14).
Increasing the amount of NFSI and Cs2CO3 made no
improvement in the yield of product 3a (entry 15). The
substrate remains unreacted in the absence of NFSI (entry
16). While other fluorinating agents like selectfluor and KF
were failed to give the desired product (entry 17-18).
O
Table 1. Optimization of reaction conditions.a
NH2
O
S
F
O
S
Base
+
N
entry
solvent
Base
temp
(°C)
t (h)
yieldb
(% )
Solvent
N
N
O
O
R1
R1
3
2
1
1
DMA
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
K2CO3
25
24
24
24
24
30
18
24
24
24
24
24
24
24
24
24
24
24
24
trace
NH2
NH2
2
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMF
DMSO
Dioxane
EtOH
DMA
DMA
DMA
DMA
50
80
50
72
N
N
Me
3
3ba
NH2
3a; 72%
NH2
3b; 73%
c
4
-
100
80
3c: R1 = Me; 74%
3d: R1 = Et; 70%
3e: R1 =OMe; 75%
5
70
50
N
N
6
80
80
80
80
80
80
80
80
80
3f: R1
=
tBu; 68%
3g; 63%
R1
7
NR
50
NH2
NH2
8
tBuONa
KOH
NH2
N
N
9
45
N
10
11
12
13
14
15
16
17
18
-
NR
62
3j; 72%
3h; 69%
3i; 62%
S
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
NH2
3l: R2 = Ph; 65%
3m: R2
-MeC H ; 67%;
Me
NH2
=
o
55
6
4
N
3n: R2 = cyclohexyl; 62%;
N
3o: R2 = cyclopropyl; 55%;
R2
NR
00d
66e
NRf
NRg
NRh
3k; 50%
CF3
MeO
NH2
MeO
NH2
Cl
NH2
80
80
80
80
N
N
N
R
Me
3r; 58%
3s; 52%
R = t-Bu; 3p; 68%
R = H; 3q; 62%
[a] Reactions were performed using 0.50 mmol of 1a, 0.60 mmol of
NFSI 2 , 3.0 equiv of base in 2.0 mL solvent unless otherwise noted.
Scheme 2. Scope of ortho-alkynylaldehyde. Reaction condition: alkynyl
quinoline aldehydes (0.50 mmol), NFSI (0.60 mmol), 3.0 equiv
Cs2CO3 in 2.0 mL DMA at 80 °C for 24 h. [a] The CCDC no. of
1
2
[b]
Isolated
yield.[c]
Complex
mixture.
[d]
Ethyl
2-
(phenylethynyl)quinoline-3-carboxylate was formed16e [e] Using 1.0
mmol of NFSI and 4.0 equiv of Cs2CO3.[f] Without using NFSI. [g]
Using Selectfluor (0.6 mmol) instead of NFSI. [h] Using KF (0.6 mml)
instead of NFSI. N.R.= No reaction, DMA = Dimethylacetamide
compound 3b is 1814897.
With the optimized reaction conditions, we explored the
viability of differently substituted ortho-alkynyl quinoline
carbaldehyde 1a–s (Scheme 2). The substrates having an
electron-donating group at the phenyl ring on distal end of
the triple bond reacted smoothly to give the desired
We began our study with 0.50 mmol of substrate 1a
,
0.60 mmol of
2, 3.0 equiv of Cs2CO3 in DMA at 25 °C,
resulted in the formation of trace amount of product 3a after
24h (Table 1, entry 1). On increasing the reaction
temperature to 50 °C and then to 80 °C provided the
desired product 3a in 50 and 72% yield, respectively
(entries 2 and 3). Further elevating the temperature to 100
°C leads to the decomposition of the reaction (entry 4). No
significant effect was observed when the reaction was
stirred for longer time (entry 5). While monitoring the
reaction for a short interval of time at 80 °C, the product 3a
was obtained in 50% yield along with starting material
(entry 6). After obtaining successful results with Cs2CO3,
aminated products 3b
substrates bearing aliphatic and cyclic alkynes were also
compatible to afford the designed products 3g in good
–f in 68-75% yields. Interestingly, the
–i
yields. The reaction with 2-(thiophen-2-ylethynyl)quinoline-
3-carbaldehyde 1j gave the desired product 3j in 72% yield.
The electron-deficient -CF3 embedded alkyne 1k provided
the desired product 3k in 50% yield. The above results
encouraged us to explore substituted quinoline aldehydes
as substrate. Therefore, next we investigated 6-methyl, 6-
methoxy and 6-chloro substituted alkynyl quinoline-3-
2
This article is protected by copyright. All rights reserved.

10.1002/chem.201903495
Chemistry - A European Journal
COMMUNICATION
many drugs like molecules, camptothecin,17a Lutonin A,17
carbaldehydes 1l–s having cyclohexyl and variety of
electron-rich alkynes. The substitution on quinoline ring
made no considerable effect on the progress of reaction
Crytolepine18.
The
potential
biological
activity
of
pyrroloquinolines captivates the organic chemist to design a
facile route for their synthesis. The unsubstituted and OMe-
substituted quinoline amines 3f, 3h and 3p were cyclized in the
t-BuOK in NMP at 40 °C19 and gave the corresponding
pyrroloquinolines 6a–c in 87–89% yield (Scheme 4). Next,
pyrrolopyridines 6d–g were obtained in good yields from
aminopyridines under base-mediated conditions. The viability of
aminoquinolines was further extended through the synthesis of
iodo-substituted pyrroloquinoline/ pyridines 7a–c using
molecular iodine in DCE (Scheme 4). The iodo compounds were
obtained through iodocyclization20 in good to excellent yield.
Iodo-substituted quinolines and pyridines are noteworthy as
and the corresponding products 3l–r was obtained in 55-
68% yields. While moderate yield of product 3s was
obtained when chloro substituted quinolin-aldehyde 2s was
used as substrate.
halogen atoms play an important role in
a compound’s
bioactivity and provide handle for further structural elaboration.
(i)
Role of o-alkynyl Pyridyl Nitogen
R1
O
NFSI, Cs2CO3
DMA, 80 °C
S.M. recovered
S.M. recovered
8
Ph
Scheme 3. Synthesis of 2-alkynyl-pyridin-3-amine. Reaction condition:
Alkynyl pyridine aldehydes 1 (0.50 mmol), NFSI 2 (0.60 mmol), Cs2CO3 (3.0
equiv) in 2.0 mL DMA at 80 °C for 24 h.
8a: R1 = H; 8b: R1= Br
O
NFSI, Cs2CO3
DMA, 80 °C
(ii)
N
After obtaining successful results with alkynyl quinoline-3-
carbaldehydes, we were intrigued to extend the scope of
reaction on ortho-alkynyl nicotinaldehyde 1t–z and 1aa (Scheme
3). The optimized reaction conditions were compatible with
pyridine substrates and afforded the targeted product 4a–h in
58–68% yield. The phenyl and electron-rich substituted alkynes
provided the corresponding product 4a–e, in good yields. The
reaction also tolerates the heteroaromatic substituted alkynes
and afforded the desired product 4f in 62% yield. While,
moderate yield of products 4g–h was obtained when cyclic
alkyne was employed as substrate.
1ab
Ph
(iii)
Role of Alkynyl Group
NFSI, Cs2CO3
DMA, 80 °C
O
S.M. recovered
S.M. recovered
N
R
9a: R = Cl; 9b: R = Ph
NFSI, Cs2CO3
DMA, 80 °C
O
(iv)
N
9c
Me
NH2
TEMPO
O
(v)
H
H
NH2
N
Method A
N
Cs2CO3, NFSI
DMA, 80 °C
Method B
N
N
R1
R1
Ph
Ph
1a
Ph
Ph
N
N
6a-g
3a, 60%
N
R1
H
I
3/ 4
7a-c
NH2
O
Cs2CO3, NFSI
Method A
(vi)
(vii)
H
N
H
H
dry DMF, 80 °C
under inert atm.
MeO
N
N
N
N
tBu
tBu
1a
3a, 10%
N
N
N
6c; 88%
6a; 89%
6b; 87%
Role of N-Fluorobenzenesulfonimide
Me
H
N
H
H
H
N
N
N
tBu
O
Cs2CO3
S
O
N
N
N
N
S.M. recovered
NH2
+
S
6f; 80%
6e; 84%
6d; 90%
6g; 85%
DMA, 80 °C
N
O
Ph
Method B
10
1a
Me
H
H
H
N
N
(viii) Formation of Six-memebered Ring
N
tBu
S
NSO2Ph
O
N
N
MeO
N
Cs2CO3,
NFSI, DMA
O
MeO
I
I
I
7a; 90%
7c; 82%
7b; 86%
N
N
80 °C, 8 h
11, 10 %
tBu
Scheme 4. Structural elaboration for the synthesis of pyrrolo quinolines.
Reaction conditions: Method A: 3/4 (0.5 mmol), t-BuOK (3.0 equiv) in 2.0 mL
NMP at 40 °C for 8 h. Method B: 3/4 (0.5 mmol), I2 (1.0 equiv) in 2.0 mL DCE
at 70 °C for 3 h.
1p
tBu
Isolated side-product
confirmed by 1H NMR
Scheme 5. Control experiments
To illustrate the synthetic utility of the synthesized amines,
we have designed the synthesis of biologically important
pyrroloquinolines/pyridines. Pyrroloquinolines are present in
To study the mechanistic pathway for the synthesis of
aminoquinolines various preliminary experiments have been
3
This article is protected by copyright. All rights reserved.

10.1002/chem.201903495
Chemistry - A European Journal
COMMUNICATION
instability of allene fluoride species iii, it will reorganize to attain
aromaticity and alkynyl group by removal of CsF. Further the
CsF triggers the exclusion of PhSO2F21 (confirmed by 19F NMR,
See ESI) and gave intermediate v. Now, two pathways are
possible; path a leads to the formation of side-product by
releasing through 6-endo dig cyclization. In Path b, reaction
proceeds through Curtius type rearrangement to generate
isocyanate species vi. Then in the presence of H2O present in
DMA22 generates carbamic acid intermediate vii which on
removal of CO2 generated the targeted aminated compound 3/4.
In conclusions, we have demonstrated a novel triple bond
directed approach for the direct conversion of ortho- alkynyl
quinoline/pyridyl-3-aldehydes into ortho-alkynyl quinoline/pyridyl-
3-amine using N-fluorobenzenesulfonamide as nitrogen source
under basic condition. The designed transition-metal-free
strategy was directed through triple bond and well-tolerated by a
variety of electron-rich and electron-deficient alkynes. The
preliminary studies suggested the importance of pyridyl nitrogen
and alkyne in this reaction. Further, the synthesized amino-
quinolines/pyridines were elaborated to give biologically
important pyrrolquinolines and iodo-pyrroloquinolines. The iodo-
substituted compounds will provide a handle for structural
elaboration.
performed (Scheme 5). We began our study with the importance
on the role of ortho-alkynyl heteroatom. When 2-(phenylethynyl)
benzaldehydes 8a–b were treated with NFSI, no desired product
was observed after 24 h, only starting material was recovered
(Scheme 5(i)). Similarly, no progress in the reaction was
observed when 3-((4-methoxyphenyl)ethynyl) isonicotinaldehyde
(1ab) was employed as the substrate, only starting material was
recovered in 70% yield (Scheme 5 (ii)). The result of above
experiments validates the presence of nitrogen adjacent to the
alkyne group was essential. The role of the alkynyl group was
justified, when the reaction of chloro and phenyl substituted
quinolin-3-aldehyde 9a–b under-designed reaction condition
was failed to give the aminated product (Scheme 5iii). Next, we
employed alkenyl substituted quinolin-aldehyde 9c under the
optimized reaction condition, but we failed to obtain the desired
product (Scheme 5iv). This result supported the importance of
alkynyl group in the substrate. We also perform the reaction
using TEMPO along with NFSI, 60% yield of product 3a cancels
the probability of radical formation in this reaction (Scheme 5v).
Furthermore, when substrate 1a was subjected for the reaction
using dry DMF under inert atmosphere, the reaction was
significantly inhibited and afforded the desired product only in
10% yield. This experiment suggests that H2O present in DMA is
involved in the conversion of isocyanate into the product 3a
(Scheme 5vi). The role of N-fluorinating reagent was supported
by the failure of reaction between benzenesulfonamide 10 and
1a (Scheme 5vii). Further to support the formation of six-
membered intermediate, we have stirred the reaction for 8 h and
isolated the side-product 11 in 10% yield, which later gets
degraded during the course of reaction (Scheme 5viii).
Acknowledgments
The work was supported by DST (SERB) and DRDO
(ARMREB/STE/2018/210). Sushmita is thankful to the UGC for
JRF and T.A. is thankful to UGC for women postdoctoral
fellowship.
Keywords: Curtius Rearrangement
•
Pyrroloquinoline
•
N-
fluorobenzenesulfonamide
Amination
•
ortho-alkynyl aldehyde
•
CH-
References
[1] a) A. L. Harvey, Drug Discovery Today 2008, 13, 894; b) D. J. Newman,
G. M. Cragg, J. Nat. Prod. 2012, 75, 311; c) A. S. Travis, Anilines:
Historical background In Patai’s Chemistry of Functional Groups, Online;
John
Wiley
&
Sons,
Ltd.:
New
York,
2009,
DOI:
10.1002/9780470682531.pat0383.
[2] a) H. G. Bonacorso, L. B. Silva, J. B.T. Rocha, P. A. Nogara, E. P.
Waczuk, F. D’A. Silva, D. C. Bueno, Y. N. A. M. Kader, M. A. P.
Martins, N. Zanatta, Tetrahedron Lett. 2015, 56, 7024; b) J. A. Bikker, N.
Brooijmans, A. Wissner, T. S. Mansour, J. Med. Chem. 2009, 52, 1493.
[3] a) R. Hili, A. K. Yudin, Nat. Chem. Biol. 2006, 2, 284; b) S. Uno, M.
Kamiya, T. Yoshihara, K. Sugawara, K. Okabe, M. C. Tarhan, H. Fujita, T.
Funatsu, Y. Okada, S. Tobita, S.; Urano, Y. Nat. Chem. 2014, 6, 681.
[4] a) J. E. Ney, J. P. Wolfe, J. Am. Chem. Soc., 2006, 128, 15415; b) J.
Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev., 2002,
102, 1359; c) A. K. Mailyan, J. A. Eickhoff, A. S. Minakova, Z. Gu, P. Lu, A.
Zakarian, Chem. Rev., 2016, 116, 4441; d) Bariwal, J.; Eycken, E. V.
Chem. Soc. Rev., 2013, 42, 9283.
Scheme 6. Plausible mechanism
On the basis of preliminary results, we have proposed a
plausible mechanism for the decarbonylative amination
(Scheme 6). Accordingly, the reaction was initiated through the
complex formation between NFSI and Cs2CO3 which generates
F+ that was immediately trapped by oxygen of carbonyl group
present in the substrate 1 and subsequently attack of N(SO2Ph)2
anion on the carbonyl carbon generates reactive species ii, that
immediately rearrange to give allene intermediate iii. Due to the
[5] a) J. F. Hartwig, in Handbook of Organopalladium Chemistry for Organic
Synthesis, ed. E. I. Negishi, Wiley-Interscience, New York, 2002, vol. 1.
b) N. Marion, S. P. Nolan, Acc. Chem. Res., 2008, 41, 1440; c) J. F.
Hartwig, Acc. Chem. Res., 2008, 41, 1534; d) F. Monnier, M. Taillefer,
Angew. Chem. Int. Ed. 2009, 48, 6954; e) D. S. Surry, S. L. Buchwald,
Chem. Sci., 2011, 2, 27.
[6] a) S. M. Kelly, C. Han, L. Tung, F. Gosselin, Org. Lett. 2017, 19, 3021; b)
W. Xu, Y. Jin, H. Liu, Y. Jiang, H. Fu, Org. Lett. 2011, 13, 1274; c) Z.-Y.
4
This article is protected by copyright. All rights reserved.

10.1002/chem.201903495
Chemistry - A European Journal
COMMUNICATION
Ge, X.-D. Fei, T. Tang, Y.-M. Zhu, J.-K. Shen J. Org. Chem. 2012, 77,
5736.
[14] F.-H. Li, Z.-J. Cai, L. Yin, J. Li, S.-Y. Wang, S.-J. Ji, Org. Lett., 2017, 19,
1662.
[7] a) H. Yue, L. Guo, H.-H. Liao, Y. Cai, C. Zhu, M. Rueping, Angew. Chem.
Int. Ed. 2017, 56, 4282; b) T. Qin, J. Cornella, C. Li, L. R. Malins, J. T.
Edwards, S. Kawamura, B. D. Maxwell, M. D. Eastgate, P. S. Baran,
Science, 2016, 352, 801; c) J. Aube, C. Fehl, R. Liu, M. C. McLeod, H. F.
Motiwala, In Comprehensive Organic Synthesis; Knochel, P., Molander, G.
A., Eds.; Elsevier: Amsterdam, 2015; Vol. 6, pp 598; d) Z. Zuo, D. T.
Ahneman, L. Chu, J. A. Terrett, A. G. Doyle, D. W. C. MacMillan, Science
2014, 345, 437; e) S. Sunami, T. Sagara, M. Ohkubo, H. Morishima,
Tetrahedron Letters, 1999, 40, 1721; f) R. G. Wallace, J. M. Barker,
M. L. Wood, Synthesis 1990, 1143; g) K. Shoji, A. Kohichi, F. Shizuo, K.
Takaaki, O. Tsuyoshi, Chemistry Letters, 1989, 3, 463-464
[15] Y.-L. Zhu, A.-F. Wang, J.-Y. Du, B.-R. Leng, S.-J. Tu, D.-C. Wang, P. Wei,
W.-J. Hao, B. Jiang, Chem. Commun., 2017, 53, 6397.
[16] a) P. K. Mishra, S. Verma,
M. Kumar,
A. K.Verma, Org.
Lett., 2018, 20, 7182; b) S. Verma, P. K. Mishra, M. Kumar, S. Sur,
and A. K.Verma, J. Org. Chem., 2018, 83, 6650; c) D. Brahmachari, A. K.
Verma, S. Mehta, J. Org. Chem., 2018, 83,
3339; b) P.
Kumar, T. Aggarwal, A. K. Verma, J. Org. Chem., 2017, 82, 6388; d) T.
Aggarwal, S. Kumar, D. K. Dhaked, R. K. Tiwari, P. V. Bharatam, A. K.
Verma, J. Org. Chem. 2012, 77, 8562; e) A. K. Verma, V. Rustagi,
T. Aggarwal, A. P. Singh, J. Org. Chem., 2010, 75 , 7691.
[17] a) R. Cincinelli, L. Musso, S. Dallavalle, R. Artali, S. Tinelli, D. Colangelo,
F. Zunino, M. De Cesare, G. L. N. Beretta, N. Zaffaroni, Eur. J. Med.
Chem. 2013, 63, 387; b) M. C. Wani, P. E. Ronman, J. T. Lindley, M. E.
Wall, J. Med. Chem. 1980, 23, 554.
[8] a) N. M. Ahmad, Name Reactions for Functional Group Transformations;
J. J. Li, E. J. Corey, Eds.; John Wiley & Sons: Hoboken, NJ, 2007; pp 438
−450; b) M. A. Marsini, F. G. Buono, J. C. Lorenz, B.-S. Yang, J. T.
Reeves, K. Sidhu, M. Sarvestani, Z. Tan, Y. Zhang, N. Li, H. Lee, J.
Brazzillo, L. J. Nummy, J. C. Chung, I. K. Luvaga, B. A. Narayanan, X.
Wei, J. J. Song, F. Roschangar, N. K. Yee, C. H. Senanayake, Green
Chem. 2017, 19, 1454.
[18] a) J. L. Liang, H. C. Cha, Y. Jahng, Molecules 2011, 16, 4861; b) K.
Bonjean, M. C. D. Pauw-Gillet, M. P. Defresne, P. Colson, C. Houssier, L.
Dassonneville, C. Bailly, R. Greimers, C. Wright, J. Quetin Leclercq, M.
Tits, L. Angenot, Biochemistry, 1998, 37, 5136; c) J. N. Lisgarten, M. Coll,
J. Portugal, C. W. Wright, J. Aymami, Nature Structural Biology, 2002, 9,
57.
[9] Y. Zhang, S. Patel and N. Mainolfi, Chem. Sci., 2012, 3, 3196.
[10] A. Ilangovan, P. Sakthivel, P. Sakthivel, Org. Chem. Front., 2016, 3, 1680.
[11] Z. Ni, Q. Zhang, T. Xiong, Y. Zheng, Y. Li, H. Zhang, J. Zhang, Q. Liu,
Angew. Chem., Int. Ed. 2012, 51, 1244.
[19] A. L. Rodriguez, C. Koradin, W. Dohle, P. Knochel, Angew. Chem Ed.
2000, 39, 2488.
[12] G. B. Boursalian, M.-Y. Ngai, K. N. Hojczyk, T. Ritter, J. Am. Chem. Soc.
2013, 135, 13278.
[20] D. Yue, T. Yao, R. C. Larock, J. Org. Chem., 2006, 71, 62.
[21] A. T. Davies, J. M. Curto, S. W. Bagley, M. C. Willis, Chem. Sci., 2017, 8,
1233.
[13] a) S. Wang, Z. Ni, X. Huang, J. Wang, Y. Pan, Org. Lett. 2014, 16, 5648;
b) S.-S. Weng, J.-W. Zhang, Chem. Cat. Chem. 2016, 8, 3720; c) B. E.
Haines, T. Kawakami, K. Kuwata, K. Murakami, K. Itami, D. G. Musaev,
Chem. Sci., 2017, 8, 988; d) Z. Fang, Y. Feng, H. Dong, D. Li, T. Tang,
Chem. Commun., 2016, 52, 11120. G. Zheng, Y. Li, J. Han, T. Xiong, Q.
Zhang, Nat. Chem. 2015, 6, 7011.
[22] B. L. Li, S. Y. Ding, Y. F. Ren, L. C. Wang, Y. C. Jia, X. Q. Zhang, H. M.
Gu, Bull. Korean Chem. Soc. 2013, 34, 1537.
5
This article is protected by copyright. All rights reserved.

10.1002/chem.201903495
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Sushmita,† Trapti Aggarwal,† Norio
Shibata and Akhilesh K. Verma[a]
*
Page No. – Page No.
Triple bond Directed Csp2-N Bond
Formation through N-
Fluorobenzenesulfonimide as
Aminating Source: One-Step
Transformation of Aldehyde into
Amine
Text for Table of Contents
Transition metal-free decarbonylative C-H amination of ortho-alkynyl quinoline/pyridine aldehyde
using N-Fluorobenzenesulfonimide as nitrogen source under basic medium.
6
This article is protected by copyright. All rights reserved.