Photoassisted Charge Transfer Between DMF and Substrate: Facile and Selective N,N-Dimethylamination of Fluoroarenes

Article abstract of DOI:10.1002/cssc.202100761

A reversible Van der Waals complex formation between the electron-deficient fluorinated aromatic ring and N,N-dimethylformamide (DMF) molecules followed by light irradiation resulted in charge transfer (CT) process. The complex was stabilized by ammonium formate and further decomposed to form the C?N bond. Control experiments revealed that the simultaneous S_NAr pathway also contributes to product formation. This methodology is mild, metal-free, and effective for the amination of a variety of substrates. The reproducibility of this methodology was also verified on gram-scale reactions. The CT states were supported by control UV/Vis spectroscopy and computational studies.

Full text of DOI:10.1002/cssc.202100761

Chemistry–Sustainability–Energy–Materials
Accepted Article
Title: Photoassisted Charge Transfer Between DMF and Substrate:
Facile and Selective N,N-Dimethylamination of Fluoroarenes
Authors: Tharique N Ansari, Sudripet Sharma, Pranjal P Bora, Deborah
Ogulu, Saurav Parmar, Fabrice Gallou, Pawel M Kozlowski,
and Sachin Handa
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: ChemSusChem 10.1002/cssc.202100761
Link to VoR: https://doi.org/10.1002/cssc.202100761
01/2020

10.1002/cssc.202100761
ChemSusChem
COMMUNICATION
Photoassisted Charge Transfer Between DMF and Substrate: Facile
and Selective N,N-Dimethylamination of Fluoroarenes
Tharique N. Ansari,‡,[a] Sudripet Sharma,‡,[a] Pranjal P. Bora,‡,[a] Deborah Ogulu,‡,[a] Saurav Parmar,[a]
Fabrice Gallou,[b] and Pawel M. Kozlowski,*,[a] Sachin Handa*,[a]
[a]
[b]
Mr. T. N. Ansari, Mr. S. Sharma, Dr. P.P. Bora, Ms. D. Ogulu, Mr. S. Parmar, Prof. P. M. Kozlowski, Prof. S. Handa
Department of Chemistry
University of Louisville
Louisville, Kentucky 40292, United States
*E-mail: sachin.handa@louisville.edu, pawel.kozlowski@louisville.edu
Dr. F. Gallou
Novartis Pharma
AG, CH-4056, Basel, Switzerland
‡These authors contributed equally.
Supporting information for this article is given via a link at the end of the document.
Abstract: A reversible Van der Waals complex formation between the
of DMF under such conditions needs specialized equipment (such
as sealed-tube) to ensure dimethylamine gas surrounds the
reaction atmosphere. A rapid decay increases the risk of process
and worker’s safety. Therefore, alternative methods for
dimethylamination are preferred, e.g., precious-metal catalyzed
electron-deficient
fluorinated
aromatic
ring
and N,N-
dimethylformamide (DMF) molecules followed by light irradiation
results in charge transfer (CT) process. The complex is stabilized by
ammonium formate and further decomposed to form the C–N bond.
Control experiments revealed that the simultaneous SNAr pathway
also contributes to product formation. This methodology is mild, metal-
free, and effective for the amination of a variety of substrates. The
reproducibility of this methodology is also verified on gram-scale
reactions. The CT states are supported by control UV-Visible
spectroscopy and computational studies.
reductive N-methylation
of
amines[34,35]
and
direct
dimethylamination of aryl halides.[36]
Me
Me
F
F
N
N
Me
Me
F
F
NH
F
O
F
F
H
N
Me
NH2
O
N
N
H
F
F
F
HN
Me
Me
Si
2X–
N,N-Dimethylformamide (DMF) is a popular organic solvent, first
reported by Verley in 1893.[1] It is a dipolar-aprotic solvent, mainly
used in organic synthesis due to its excellent dissolution ability
and impact on reaction equilibria. It stands as a highly useful
chemical entity due to its unique properties, such as, dehydrating
agent[2] and stabilizer for metal nanoparticles.[3-6] Besides, it
assists substrate-catalyst interaction and participates in hydrogen
bonding to lower the transition state-energy in some catalytic
pathways.[7] Generally, it is stable at an ambient environment.
However, its violent decomposition to dimethylamine and carbon
monoxide is reported at 153 oC, and above 120 oC under strongly
basic conditions.[8] Due to its decomposition properties, it has
been employed as a precursor in various transformations, such
as formylation,[9-13] aminocarbonylation,[14,15] amination,[16]
amidation,[17] cyanation,[18-22] etherification,[23] etc.[24,25] In these
transformations, significantly elevated temperatures and
specialized glassware are required to address the potential safety
hazards from DMF decomposition. A photocatalytic decay of DMF
using TiO2 and ultraviolet (UV) light is precedented, and the
protocol has been employed on palladium-catalyzed
carbonylative Suzuki-Miyaura couplings.[26] Notably, such
procedures require extreme precautions due to the use of high-
energy UV radiations.
CO2Me
N
F
N
F
F
F
Me
Me
Me
N
N
O
Me
N
F
F
Me
Me
Me
Me
fluorescent probe
meso-tetra(tetrafluorophenyl)porphyrin
(for live-cell imaging)
(photodynamic therapeutics)
Me
N
Me
Me
Me
Me
N
Me
H
N
Me
N
Me
N
N
O
O
N
Me
Me
Me
Me
O
N
N
O
Me
CO2H
HO
HO
OH
Me
OH
(t-Bu)2P
HO
n-Bu
dimethirimol
(plant fungicide)
orthoformimycin
(antibacterial)
[N(Me)2]2naphthalene
(proton sponge)
P,N-ligand
(cross-coupling)
Figure 1. N,N-Dimethylamino residue in useful molecules.
N,N-Dimethylamino aromatics represent a wide variety of useful
compounds (Figure 1), e.g., medicinal compounds[37-39]
agrochemicals[40], ligands[41,42] as well as fine chemicals, such as,
dimethylamino pyridines,[43] proton sponge[44] etc.[45] In
,
,
biochemical and bioengineering research, such aromatic amines
are used as live-cell fluorescent probes.[39] Along the same lines,
fluorinated or partially fluorinated aromatic amine fragments can
be found in medicinal compounds (ciprofloxacin, norfloxacin,
trovafloxacin,
levofloxacin,
linezolid),[46]
photodynamic
therapeutics, and optoelectronics.[47,48]
One exciting application of DMF is the N,N-dimethylamination of
aromatics and heteroaromatics via the SNAr pathway.[27-33]
However, this transformation is not practical from a preparative
standpoint. A catalyst, strong base, and high temperature are
required for the generation of dimethylamine. Fast decomposition
Due to broad applications of dimethylamino functional group and
a lack of safe, selective, clean, and sustainable methodology for
the in-situ generation of dimethylamine and its installation in
aromatics, we propose
a
photo-assisted and controlled
1
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10.1002/cssc.202100761
ChemSusChem
COMMUNICATION
decomposition of DMF via charge transfer phenomenon and its
subsequent application in N,N-dimethylamination of electron-
deficient aromatics and heteroaromatics. We hypothesized that
the reversible formation of Van der Waals (VdW) complex
between electron-deficient arene and DMF molecule triggers the
photo-assisted electron transfer (ET) from electron-pair of DMF
nitrogen atom to arene molecule, forming a charge transfer
complex, that further assists dimethylamination of arene via two
plausible pathways as depicted in Figure 2. With the
accomplishment of the proposed pathway, only DMF, aryl halide,
light, and buffer are required for formation of desired product.
conversion to the desired product 2 was observed in GC-MS
analysis (entry 8). Under green LED irradiation, while keeping
other parameters the same as in the optimized conditions, 50%
desired product was isolated (entry 9). Blue LED irradiation was
slightly less effective, and 69% desired product 2 was obtained
(entry 10). The reaction mixture also contains 11% byproduct 3.
Switching solvent from DMF to N,N-dimethylacetamide (DMA)
only provides traces of desired product 2 (entry 11). Likewise, no
reaction was observed when N,N-diphenylformamide was used
as an amine source in acetonitrile solvent (entry 12).
Table 1. Optimization of reaction conditionsa
Me
Me
F
F
F
F
F
F
F
F
F
N
Me
HN
H
Me
N
Me
F
F
F
F
F
F
NH2
F
N
F
F
visible-light
Me
Me
F
F
F
F
F
F
F
F
F
H
+
Me
F
+
O
Me
additive
N
F
F
F
F
F
F
F
Me
50 oC, 0.25 M
B
F
O
F
F
F
F
F
F
1
2
3
F
F
F
F
CO
B•HF
hν
entry
1
light source
White LED
none
additive
HCO2NH4
HCO2NH4
none
2/3 ratio
9:1
% 2b
90 (80)c
F
Me
N
B = buffer
F
F
Me
B
B•HF
2
8:2
38
Me
F
N
F
F
Me
3
none
NR
NR
H
4
White LED
White LED
White LED
White LED
White LED
Green LED
Blue LED
White LED
White LED
none
NR
NR
DMF
DMF
5
HCO2Na
KOH
NR
NRd
NR
NRd
80e (51)c
DMF
DMF
DMF
DMF
6
DMF
DMF
F
DMF
7
MeCO2NH4
NH4OH
9:1
DMF
F
8
1:1.05
9:1
7
F
70 (50)c
90f (69)c
tracesg
NRh
DMF
9
HCO2NH4
HCO2NH4
HCO2NH4
HCO2NH4
F
DMF
DMF
F
10
11
12
9:1
-
NR
NH4HCO2
aReaction condition: Octafluoronaphthalene 1 (0.25 mmol), additive (2.5 mmol),
DMF (1.0 mL), white LED (300 W, 4000 lumens), 24 h. bformation of 2 based
on GC-MS using 1,1,2,2-tetrachloroethane as an internal standard; cisolated
yield; dno desired reactivity but 1 was completely consumed; eincludes traces of
diamination byproduct as a mixture of regioisomers; fGC-MS analysis shows 9%
diamination byproduct as a mixture of regioisomers; gDMA was used as a
solvent instead of DMF; hN,N-diphenylformamide (1.25 mmol) as an amine
source and CH3CN (1.0 mL) instead of DMF were used; NR = no reaction.
(Me)2
N
(Me)2
N
N(Me)2
N(Me)2
Figure 2. Proposed hypothesis of photo-assisted DMF cleavage and its
subsequent application.
Table 2. Substrate scopea
Me
F
N
DMF
Me
F(n-1)
F(n-1)
HCO2NH4
white LED, 50 o
Herein, we report a photo-assisted protocol for the selective
mono N,N-dimethylamination of fluoroarenes with a particular
emphasis on perfluoroarenes utilizing DMF as an amine source
under mild conditions. Our study began with optimizing reaction
parameters that include a light source, global concentration,
additives, and temperature. White LED irradiation, 0.25 M global
concentration, ammonium formate additive, and 50 oC reaction
temperature were found to be optimal (Table 1). Using optimized
conditions, an 80% isolated yield of 2 was obtained (entry 1); in
GC-MS analysis of reaction mixture, 10% byproduct 3 was also
detected. In the absence of light, while keeping the other reaction
variables the same, only 38% of 2 was observed, and the reaction
was not highly selective (entry 2). This kind of reactivity is most
likely due to very slow decomposition of DMF under dark and
participation of resulting N,N-dimethylamine in SNAr pathway. No
reaction was observed in the absence of light and ammonium
formate (entry 3). Likewise, no desired product 2 was observed in
the absence of ammonium formate or when it was replaced with
sodium formate or KOH (entries 4-6). The consumption of 1 in the
presence of ammonium acetate additive was fast, although the
isolated yield of 2 was only 51% (entry 7). Additive ammonium
hydroxide results in poor conversion and selectivity, and only 7%
C
F
F
F
F
Me
N
F
Me
F
F
Me
N
Me
F
F
F
N
F
N
Me
Me
Me
Me
N
N
F
F
F
O2N
O
F
O
2
80% (24 h)
4
82% (20 h)
5
68% (72 h)
6
50% (72 h)
F
Me
N
F
Me
N
F
Me
F
Me
F
F
F
N
F
N
Me
O
Me
Me
Me
H
N
N
Me
MeO
F
F
F
F
O
F
O
F
O
F
O
F
7
46% (5 d)
8
84% (50 h)
9
51% (44 h)
Me
10 68% (48 h)
F
Me
F
Me
F
N
Me
N
F
N
Me
N
Me
H
N
Me
H
N
Me
F
N
F
N
O
F
Br
O
F
F
Me
11 65% (4 d)
12 67% (48 h)
13 80% (12 h)
14 52% (5 d)
F
Me
F
Me
Me
Me
F
N
F
N
Me
Me
F3C
O2N
16 72% (24 h)
N
Me
Br
N
H
N
Me
Me
N
F
F
CN
O
F
O
F
Br
Me
18 79% (22 h)
15 74% (24 h)
17 55% (48 h)
aReaction condition: (Poly)fluoroarene (0.25 mmol), HCO2NH4 (2.5 mmol), DMF
(1.0 mL), white LED (300 W, 4000 lumens), 50 oC. All yields are isolated.
2
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10.1002/cssc.202100761
ChemSusChem
COMMUNICATION
With the optimized conditions, substrate scope with an emphasis
on selectivity was next explored (Table 2, 2-18). Perfluoro,
difluoro, monofluoroarenes and heteroarenes were well tolerated.
Amides (5-8, 11, 14, 15, 18), ester (10), and ketone (9) displayed
moderate-to-excellent reactivity and selectivity. Notably, using
non-dry DMF and ammonium formate did not cause imine
formation in 9 and transamidation in substrates containing amide
functional groups (5-8, 11, 14, 15, 18). No diamination byproduct
was observed in these examples. No transamidation was
observed in the perfluorinated substrate containing N-tosyl
functional group; however, no desired reaction was observed in
this example (for details, see Supporting Information, pages S13-
15), most likely due to lack of formation of the charge-transfer
adduct. The moderate yields in some cases are due to the scale
and volatile nature of substrates. The substrate containing pyridyl
residue showed excellent reactivity and selectivity (12, 13). The
free NH group of amide functional groups did not interfere in the
reaction in any cases (7, 11, 14, 18).
(entry 4). These control experiments suggest that the dominant
pathway was not the SNAr without charge transfer effect, which
causes formation of more byproducts.
visible-light or dark
1
2
HCO2NH4, DMF, 0.25 M
50 oC, 18 h
No hydrodehalogenation was observed in the substrates
containing the bromo functional group (12, 17, 18). This is most
likely due to dominance of SNAr pathway. The limitation of this
protocol includes no reaction when fluoro group is replaced by
chloro, that further suggests the synergy of charge-transfer effect.
Besides, perfluorinated aromatic rings-containing electron-
donating substituents did not participate in desired reactivity (for
details of failed substrates, see SI, page S13).
Reaction condition: 1 (0.25 mmol), HCO2NH4 (2.5 mmol), DMF (1.0 mL), white
LED (300 W, 4000 lumens) or dark, 50 oC. Conversions based on GC-MS
analysis using mesitylene as an internal standard.
Scheme 1. Reaction kinetics in dark versus light.
To understand how much product can be formed due to SNAr and
the pathway involving CT, we conducted a kinetic study for
reactions under complete dark and light, respectively (Scheme 1).
The reaction was complete in 18 h when conducted under photo-
assisted conditions, while 40% desired product formed when the
reaction was performed in the dark. Notably, the reaction
temperature was the same under both darkness and light.
Therefore, these experiments support the role of light in reaction
efficiency. Besides, the on-off study was also performed; only ca.
31% conversion to 2 was observed with respect to unreacted 1.
These results reveal that light has a synergistic role in the reaction
pathway (for details, see SI, page S12).
Table 3. Summary of control experimentsa
F
Me
N
F
F
Me
N
F
F
F
F
conditions
Me
H
+
+
+
3
2
F3
Me
F
O
Me
N
Me
F
F
F
1
19
entry
deviation from optimized conditions
reaction time 3 days instead of 24 h
% conversionb
1
85 (2:3:19 = 8.5:1.3:0.2)
83 (2:3:19 = 8:1.8:0.2)
96 (2:3:19 = 9.5:0:0.5)
2
3
reaction under air instead of argon
To confirm the presence of charge transfer states, we conducted
the control UV-Vis study (Figure 3; for details, see SI, page S10).
The solution of 1 in DMF did not display a CT band after white
light irradiation for 6 h. The same was true for a solution of
ammonium formate in DMF. A solution of 1 and ammonium
formate in DMF under dark also did not show a significant band
above 400 nm. However, when the same solution was irradiated
under the white LED for 6 h, a broad band ca. at 400-450 nm
appeared in its UV-Vis spectrum, indicating the presence of
charge transfer states. These experiments suggest that
ammonium formate and light are required to form a charge
transfer complex between 1 and DMF. Most likely, ammonium
formate stabilizes the complex.
1.5 equiv Me2NH•HCl + standard
conditions
4
100 (2:3:19 = 6:0:4)
conditions: 10 equiv Me2NH•HCl,
10 equiv HCOONH4, 1.0 mL
DMSO, 50 oC, 24 h, dark, sealed
tube
aOptimized/standard condition: 1 (0.25 mmol), HCO2NH4 (2.5 mmol) in 1.0 mL
DMF, white LED (300 W, 4000 lumens), 50 oC, 24 h. bconversions based on
GC-MS using 1,1,2,2-tetrachloroethane as an internal standard.
Control experiments were also performed to understand the
reaction pathway (Table 3). To find whether diamination
byproduct was formed due to prolonged reaction time, the
reaction of 1 was conducted for 3 days instead of 24 h; the
formation of byproduct 19 was observed only in limited amounts
(entry 1). This indicates that the byproduct 19 is only formed
substantially when the SNAr pathway is dominating. The
transformation was equally effective under air, suggesting the
involvement of singlet states of charge transfer (CT) species in
the reaction pathway (entry 2). Using the optimized conditions and
additionally adding 1.5 equiv Me2NH•HCl did not alter the reaction
outcome significantly in terms of selectivity, indicating that the
SNAr pathway is not dominating (entry 3). However, the use of 10
equiv Me2NH•HCl under dark casued complete consumption of 1
and formation of 2 and byproduct 19 in 6:4 ratio, further indicative
of the importance of the pathway involving charge transfer state
Figure 3. Control UV-Vis studies to probe charge transfer phenomenon.
3
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10.1002/cssc.202100761
ChemSusChem
COMMUNICATION
(a)
the plane of perfluoronaphthalene (PFN, Figure 4a). In the
optimized structure, nitrogen of DMF is about 3.35 Å from the PFN
plane and all the C-F bond lengths were 1.34 Å. The HOMO has
predominant π-bonding character, which is based on PFN moiety,
while HOMO-1 has non-bonding character with respect to
nitrogen and oxygen delocalized over DMF moiety. Similarly, both
LUMO and LUMO+1 has predominant π-bond character based
on PFN moiety. The orbital analysis (MO) were carried out
assuming optimized structure of the VdW DMF/PFN complex
(Figure 4b). The TD-DFT excitation energies, nature of electronic
transitions, as well as oscillator strengths are shown in Table S5,
SI. The lowest excited state was found to have CT character
which primarily involves electronic transition from HOMO-1 to
LUMO. The nature of the lowest excited state (S1) has been
explored further by analysis of the difference densities plots (see
Figure S7, SI), which confirms that the S1 state indeed has a CT
character, where PFN has a negative charge (radical anion) and
DMF has a positive charge (radical cation). Thus, the lowest
excited state of the complex can be envisioned as (DMF•)+(PFN•)-.
The nature of the CT state can be further described as n → π*
excitation owing to n-electron density transition from the HOMO-
1 to LUMO.
(b)
Based on the computational and control experiments, a plausible
reaction mechanism is described in Figure 4c. A reversible
formation of the VdW complex between 1 and DMF followed by
light irradiation forms CT complex stabilized by ammonium
formate. The stabilized complex either further slowly decomposed
to generate 1 and dimethylamine that participate in the SNAr
pathway in a controlled fashion to form 2 or participate in forming
a bond between radical cation of DMF nitrogen and carbon of PFN
ring. Most likely, in the presence of ammonium formate, the latter
intermediate rapidly decomposed to 2. Since computational
results indicate the involvement of singlet state, the reaction is not
sensitive to air but definitely needs light. The formation of
byproduct 3 was observed in Table 1 was most likely due to
participation of ammonia nucleophile, which comes from the
decomposition of ammonium formate.
(c)
H
N
Me
F
Me
+
1
Furthermore, the scalability and robustness of this methodology
was verified on gram-scale reactions (Scheme 2; for more details,
see SI, pages S7-S8). Without altering the optimized conditions,
educts 15 and 16 were obtained in 84% and 88% yields,
respectively. The reaction yields were better than that of the
small-scale reactions.
F
HCO2NH4
F
F
F
F
DMF
2
-CO
Me
Me
H
N
F
F
HCO2NH4
Me
H
N
Me
F
F
O
O
O
F
F
F
F
H
F
F
F
F
F
N
Me
F
F
F
F
F
F
hν
Me
F
HCO2
F
F
NH4
F
F
F
F
scalability test
Van der Waals complex
charge transfer complex
Me
Figure 4. Computational studies and plausible reaction mechanism. (a)
Optimized structure of VdW complex of DMF and PFN. (b) Frontier MOs
and their energies (in eV) for the DMF/PFN complex (isodensity value of
0.03 au). (c) Plausible reaction pathway.
DMF
HCO2NH4
white LED, 50 o
F
N
Me
F(n-1)
1.0 gram
F(n-1)
C
Next, the existence of CT complex between 1 and DMF and its
role in reaction mechanism was investigated using density
functional theory (DFT) as well as time-dependent DFT (TD-DFT)
employing the B3LYP/6-311++G(d,p) level of theory as
implemented in ORCA.[49] The empirical dispersion correction was
incorporated in all the calculations through Becke-Johnson
damping (DFT-D3BJ),[50] while the conductor-like Polarizable
Continuum Model (PCM) was used to account for the bulk solvent
effect (for details, see SI, page S22, S23). It was found that 1 and
DMF form a VdW complex in which DMF moiety rests directly over
F
Me
Me
F
N
Me
F3C
O2N
N
Me
N
F
O
F
15 1.02 g, 84% (24 h)
16 0.99 g, 88% (24 h)
Scheme 2. Scalability test on gram-scale reactions.
4
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10.1002/cssc.202100761
ChemSusChem
COMMUNICATION
[26] X. Feng, Z. Li, J. Photochem. Photobiol. A Chem. 2017, 337, 19–
24.
[27] A. Kodimuthali, A. Mungara, P. L. Prasunamba, M. Pal, J. Braz.
Chem. Soc. 2010, 21, 1439–1445.
[28] J. Garcia, J. Sorrentino, E. J. Diller, D. Chapman, Z. R. Woydziak,
Synth. Commun. 2016, 46, 475–481.
[29] E. Buncel, E. A. Symons, J. Chem. Soc., Chem. Commun. 1970,
3, 164–165.
In summary, a CT complex between electron-deficient aromatic
ring and DMF could be stabilized by ammonium formate, which
could be further leveraged for C–N bond-forming reaction. The
protocol is applicable on a variety of substrates displaying good
functional group tolerance. The methodology is scalable, and
yields are also reproducible on large-scale reactions. This
technology is safer, selective, and user friendly.
[30] D. L. Comins, S. P. Joseph, N, N-Dimethylformamide. Encycl.
Reagents Org. Synth. 2001, pp 108.
[31] C. Yang, F. Zhang, G. J. Deng, H. Gong, J. Org. Chem. 2019, 84,
181–190.
[32] T. P. Petersen, A. F. Larsen, A. Ritzén, T. Ulven, J. Org. Chem.
2013, 78, 4190–4195.
Acknowledgements
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[34] X. Ge, C. Luo, C. Qian, Z. Yu, X. Chen, RSC Adv. 2014, 4, 43195–
43203.
We thank Dr. Yadagiri Dongari and Dr. Kedong Yuan for providing
assistance in initial reaction optimization.
[35] T. Irrgang, R. Kempe, Chem. Rev. 2020, 120, 9583–9674.
[36] T. Taeufer, J. Pospech, J. Org. Chem. 2020, 85, 7097–7111.
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Monciardini, M. Abbondi, R. Rossi, S. Donadio, C. O. Gualerzi,
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Keywords: N,N–dimethylamination • DMF cleavage • Van der
Waals complex
Polyfluoroarene
•
Substitution Nucleophilic Aromatic
•
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10.1002/cssc.202100761
ChemSusChem
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Entry for the Table of Contents
Photo-assisted cleavage of N,N-dimethylformamide (DMF) was explored for the N,N-dimethylamination of polyfluoroarenes.
Computational studies revealed the formation of a reversible Van der Waals complex between the electron-deficient fluorinated
aromatic ring and DMF, which generate a charge transfer (CT) complex upon light irradiation. This complex decomposes and yields
the desired amination product under mild conditions.
6
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