An Electrochemical Cinnamyl C—H Amination Reaction Using Carbonyl Sulfamate

Article abstract of DOI:10.1002/cjoc.201900028

An electrochemical cinnamyl C—H amination reaction in the absence of transition metal catalyst and oxidant was reported. The choice of carbonyl sulfamate as nitrogen source is the key to achieve desired chemoselectivity. A series of terminal amine derivat

Full text of DOI:10.1002/cjoc.201900028

Accepted Article
Title: An Electrochemical Cinnamyl C-H Amination Reaction Using Carbonyl
Sulfamate
Authors: Shuai Liu, Jin Li, Dalin Wang, Feng Liu, Xu Liu, Yongyuan Gao, Dai Jie, Xu
Cheng*
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An Electrochemical Cinnamyl C-H Amination Reaction Using Carbonyl
Sulfamate
Shuai Liu, Jin Li, Dalin Wang, Feng Liu, Xu Liu, Yongyuan Gao, Dai Jie, Xu Cheng*
a Institute of Chemistry and Biomedical Sciences, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering,
National Demonstration Center for Experimental Chemistry Education, Nanjing University, Nanjing, 210023, China
Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
An electrochemical cinnamyl C-H amination reaction in the absence of transition metal catalyst and oxidant was reported. The choice of carbonyl
sulfamate as nitrogen source is the key to achieve desired chemoselectivity. A series of terminal amine derivatives are prepared using this protocol and
the sulfonyl group can be removed with basic hydrolysis. The reaction is suggested to proceed via a continuous anodic oxidation, deprotonation, anodic
oxidation, and intermolecular nucleophilic addition pathway, demonstrating the first example of electrochemical cinnamyl C-H amination.
Background and Original Content
Scheme 1 Intermolecular electrochemical functionalization of alkene.
Introducing amine group into molecules is an important task
in pharmaceutical [1] and material applications.[2] In this class of
transformation, besides the well-established coupling strategy,
direct C-H amination reaction emerged as one efficient protocol
[3]
with atom and step economy.
In a number of successful
examples, the collaboration of transition metal catalyst and
oxidant could convert the various C-H bonds to valuable
functional amino derived groups.[4]
Electrochemical synthesis is undergoing
a substantial
development, exhibiting unique reactivity towards inert
molecules.[5] In these waves of innovative electrochemical
discoveries, transitional metal complex found tremendous
applications with divergent functions.,In combination with redox
process, transition metals drive the formation of C-C,[6] C-N,[7]
C-O,[8] C-halogen,[9] hetero-hetero,[10] and multiple bonds.[11] As
dehydrogenative process takes place at cathode, the
stoichiometric oxidant is not required. This chemistry witnesses
impressive growth in electrochemical amination, in the
intramolecular [12] or intermolecular manner.[13] Typically, in order
to avoid the cathodic reduction of transitional metal species, a
divided cell was employed to separate reagents from the cathodic
reaction. Regarding the convenience of an experiment,
developing a protocol utilizing undivided cell is beneficial. [14]
Among these novel transformations, alkenes are reactive
starting material with  bonds opened to form new bonds. One
pathway starts with an oxidation of alkene in single electron
transfer (SET) manner, giving cationic radical as highly reactive
intermediate that could be trapped by a nucleophile. (Scheme 1a)
We speculated that if a deprotonation and a second SET occurred
instantly afterwards, a cinnamyl cation could be present. A
nucleophile nitrogen source could trap this intermediate and
furnish an allylic C-H amination product.(Scheme 1b) The suitable
nitrogen source is critical to realize the proposed chemoselectvity.
It needs to be inert enough toward continuous anodic oxidation,
do not add to the cationic radical, and react intermolecularly with
the cinnamyl cation selectively. Herein, we reported the first
example of electrochemical cinnamyl C-H amination, which was
fulfilled in an undivided cell in the absence of transition metal and
oxidant.[15]
Results and Discussion
At the onset of this work, tetra substituted alkene 1a was
chosen as model substrate.(Scheme 2) This compound could host
enough steric repulsion to side reaction like the functionalization
of alkene, and demonstrate chemo- and regioselectivity clearly. In
the view of synthetic application, a protocol could provide the
fully substituted cinnamyl amine from alkene also remain elusive.
After optimization of reagents and conditions, we found when
methoxy carbonyl sulfamate 2a was used as nitrogen source, the
cinnamyl C-H amination product 3a could be prepared in 81%
NMR yield and 70% isolated yield with a Faradaic efficiency of
39%. Other nitrogen sources were evaluated for comparison.
HfsNH2 2b led to the conversion of 1a to amine derivative 3b and
aziridine 3b’ in 10% and 20% NMR yields respectively, suggesting
the steric effect was important to selectivity of C-H amination.
When saccharin 2c was applied, the amination product was
obtained in 25% yield. In a reaction employing phthalimide 2d as
nucleophile, corresponding product was not detected.
*E-mail: chengxu@nju.edu.cn
This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
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article as doi: 10.1002/cjoc.201900028

First author et al.
Report
Scheme 2 Optimization of electrochemical cinnamyl C-H amination.a
Scheme 3 Substrate scope of electrochemical cinnamyl C-H amination.
a) 1a (0.3 mmol), 2a (0.2 mmol), lutidine (0.2 mmol), LiClO4 (0.1 mmol),
1
5.0 mL MeCN, graphite felt electrodes, 5 V, rt, 3 - 4 h, H NMR yield using
CH2Br2 as internal standard. b) Isolated yield in bracket. c) K3PO4 (0.2 mmol)
instead of lutidine.
As the optimal regent, 2a was subject to this transition
metal-free electrochemical C-H amination reaction of a variety of
alkenes using the standard conditions. (Scheme 3) At first, the
analogues of 1a were screened. The methyl substituents on
phenyl rings survived the oxidative condition and corresponding
product 3d and 3e were prepared in moderate yield. Then,
substrate bearing methoxy groups was evaluated, and lower
potential was required to achieve the target molecule 3f in 56%
yield. Halogen atoms F, Cl and Br were well tolerated in this
process and compounds 3g, 3h and 3i were obtained smoothly.
Subsequently, unsymmetry alkenes were investigated. If only one
para-methoxy group was installed, a mixture of E/Z isomers 3j and
3j’ with a 1.4:1 dr ratio was produced in 46% yield. In the case of
3k and 3k’, the yield was 56% with a 4:1 dr ratio. A thienyl group
kept intact during the electrochemical process, and the major
isomer 3l with E configuration was obtained together with its Z
isomer 3l’ in a 53% overall yield and a 3.8:1 dr ratio. Subsequently,
a reaction of 2,2-dimethyl styrene giving 3m showed the presence
of two aryl groups was not necessary. However, the low yield of
30% prompted us to introduce methoxy group at para positon on
phenyl ring and the yield of 3n increased to 51%. It was
unexpected additional electron-donating group in 3o and 3p
leaded to the decomposition of alkenes instead of benefit the
yields. Substrates bearing a variety of alkoxyl groups were
prepared and examined. As expected, 3q, 3r, and 3s were
obtained in decent yields. It was glad to observe benzyl, allyl,
propargyl group in products 3t – 3w were well compatible, and
yields ranged from 40% to 66%. The following experiments gave
two products 3x and 3y with para alkyl substitution. Finally, the
size of carbonyl sulfamate was fine tuned with several secondary
alcohol, the yields of corresponding product 3z, 3aa, 3ab and 3ac
fell in the similar level as 3a.
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Chin. J. Chem. 2019, 37, XXX－XXX

Running title
Chin. J. Chem.
2a
2a + lutidine
0.0
-5.0x10-3
-1.0x10-2
-1.5x10-2
-2.0x10-2
-2.5x10-2
-3.0x10-2
1a + 2a + lutidine
1a + lutidine
1a
Coditions: a) 1 (0.3 mmol), 2a (0.2 mmol), lutidine (0.2 mmol), LiClO4 (0.1
mmol), 5 mL MeCN, graphite felt electrodes, 5 V, rt, 3 - 4 h, isolated yield
after chromatography.
0
1
2
To demonstrate the synthetic application of this
electrochemical protocol, a gram scale reaction of 1a (7.5 mmol)
and 2a (5.0 mmol) was carried out using the standard conditions.
(Scheme 4) The reaction completed in 10 hours and produced
3a in 55% yield. The product 3a was subject to basic hydrolysis
using NaOH in a mixture of water and dioxane. After being heated
at 140 oC, free amine 4 was obtained in 90% isolated yield.
Polental / V vs SCE
According to experimental results,
a plausible reaction
pathway was proposed in Scheme 6. At first, anodic oxidation of
alkene 1a gives rise to a cationic radical A. In analogy to toluene’s
cationic radical,[16] A was estimated to be highly acidic with a pKa
around -45. In this step, 2a, a secondary imide with bulkiness,
prevents its nucleophilic addition to A, and leaves the opportunity
to lutidine B to neutralize A via deprotonation. The resulting
neutral radical C undergoes the second anodic oxidation and
yields a conjugated cation D which was attacked by nucleophile 2a
at terminal in turn. After the second deprotonation with lutidinie,
final product 3a was obtained from this tandem anodic oxidation
process. At cathode, the recycle of electron can be achieved by
releasing hydrogen or partially hydrogenation of lutidine B.
Scheme 4 Synthetic exploration of cinnamyl C-H amination reaction
Scheme
6 A plausible pathway of electrochemical cinnamyl C-H
amination
To gain further information on this amination process, the
electrochemical properties of alkene, carbonyl sulfamate, and
corresponding mixture were investigated with cyclic voltammetry
experiments. (Scheme 5) It was observed that the alkene 1a
readily underwent the anodic oxidation along (green curve, Ep/2
=
+1.7 V vs SCE) or in the mixture with lutidine (magenta curve, Ep/2
= +1.6 V vs SCE). In contrast, carbonyl sulfamate 2a was totally
inert along (blue curve) or in the presence of stoichiometric
lutidine (red curve). In the reaction mixture in the mixture of 1a
and lutidine, a second weak peak was observed (black curve, Ep/2
= + 1.5 V vs SCE), implying another oxidative process toward 1a or
an intermediate derived from 1a.
Conclusions
In summary, we have developed a transition metal free
cinnamyl C-H amination reaction with electrochemical approach.
Using carbonyl sulfamate is the key to achieve the
chemoselectivity toward terminal C-H amination reaction. The
reaction works with 1,1-diphenyl alkene and styrene type of
substrates. The reaction could readily scale up and the free amine
could be achieved via basic hydrolysis. A continuous anodic
oxidation and deprotonation process was suggested to account
for this transformation.
Scheme 5 Cyclic voltammetry experiment of reactants
Experimental
A 10 mL two-necked heart-shaped flask was charged with
substrate 1 (0.3 mmol), 2a (0.2 mmol), 2.6-lutidine (0.2 mmol),
LiClO4 (0.1 mmol) and a magnetic stir bar. The flask was equipped
with a rubber septum, through which graphite felt anode and
cathode (2 cm x 1 cm x 0.5 cm for each) were installed. Two
electrodes were separated with a Teflon film. The whole cell was
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3

First author et al.
Report
an undivided cell. The graphite felt anode attached to a platinum
wire and cathode attached to a copper wire. A Teflon wire tied
around two electrodes. The flask was evacuated and backfilled
with argon for three times and 5 mL anhydrous CH3CN was added
via syringe. The controlled potential electrolysis was carried out at
room temperature. After completion of reaction as monitored with
TLC and GC-MS analysis, the mixture was concentrated under
reduced pressure. The residue was purified by chromatography on
silica gel to afford the desired product 3.
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
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Acknowledgement
This work was supported by the National Science Foundation
of China (nos. 21572099), , and the Open Project of State Key
Laboratory Cultivation Base for TCM Quality and Efficacy, Nanjing
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
This article is protected by copyright. All rights reserved.
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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Running title
Chin. J. Chem.
Entry for the Table of Contents
Page No.
An Electrochemical Cinnamyl C-H Amination
Reaction Using Carbonyl Sulfamate
A direct cinnamyl C-H amination using carbonyl sulfamate as nitrogen source is reported with
electrochemical procedure using carbon material as electrodes. The reaction proceeds in the
absence of catalyst and oxidant. A continuous steps involving anodic oxidation, deprotonate,
anodic oxidation, and nucleophilic addition of nitrogen source is proposed as the reaction
pathway.
Shuai Liu, Jin Li, Dalin Wang, Feng Liu, Xu Liu,
Yongyuan Gao, Jie Dai, Xu Cheng*
This article is protected by copyright. All rights reserved.
Chin. J. Chem. 2019, 37, XXX－XXX © 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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