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Recent advances of 1,2,3,5-tetrakis(carbazol-9-yl)-

4,6-dicyanobenzene (4CzIPN) in photocatalytic
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Cite this: DOI: 10.1039/c9cc01047e

transformations
Tian-Yi Shang,a Ling-Hui Lu,b Zhong Cao,c Yan Liu,ad Wei-Min He *b and
Bing Yu *e

1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) is a typical donor–acceptor fluorophore,

Received 4th February 2019, with carbazolyl as an electron donor and dicyanobenzene as an electron acceptor. It has emerged as a
Accepted 8th April 2019 powerful organophotocatalyst since 2016. Excellent redox window, good chemical stability and broad
DOI: 10.1039/c9cc01047e applicability make 4CzIPN an attractive metal-free photocatalyst. In this review, the recent advances of
the application of 4CzIPN as a photoredox catalyst in the past three years (2016–2018) for various
rsc.li/chemcomm organic reactions are summarized.

1. Introduction and industry.1 Over the past few decades, radical chemistry has
emerged as a powerful tool for the rapid construction of
From the standpoint of green and sustainable chemistry, complicated organic molecules due to the formation of versatile
the development of clean, economical and efficient chemical open shell reactive species.2 Accordingly, a plethora of methods
processes has attracted extensive interest from both academia could be applied to trigger radical reactions, such as thermo-
lysis, radiation, photolysis, electrolysis and redox systems.3
Among these strategies, photocatalysis has been regarded as
a
College of Biological and Pharmaceutical Engineering,
one of the most clean and promising methods, which has been
Xinyang Agriculture & Forestry University, Xinyang, 464000, China
b
Department of Chemistry, Hunan University of Science and Engineering,
extensively applied in radical chemistry.4 In particular, the past
Yongzhou 425100, China. E-mail: [email protected] few years have witnessed the significant renaissance of photo-
c
Hunan Provincial Key Laboratory of Materials Protection for Electric Power and catalysis in the field of organic chemistry since the pioneer
Transportation, Changsha University of Science and Technology, Wanjiali Road works reported by MacMillan5 and Yoon6 in 2008. Despite the
No. 960, Changsha, 410114, China
d
classic photoredox catalysts like ruthenium and iridium poly-
School of Chemistry and Chemical Engineering, Hunan University of Science and
Technology, Taoyuan Road No. 9, Xiangtan 411201, China
pyridyl complexes displaying tremendous potential in organic
e
College of Chemistry and Molecular Engineering, Zhengzhou University, synthetic chemistry,7 inexpensive and transition-metal-free
Zhengzhou 450001, China. E-mail: [email protected] organic photocatalysts also revealed extensive utilities. Notably,

Wei-Min He was born in Anqing, Bing Yu obtained his PhD degree

China, on November 22, 1982, and from the Nankai University in
received his PhD degree from the 2014. He then moved to the
Hunan University in 2012. He was Beijing Institute of Technology
a research scholar at the University (2014–2015), the Seoul National
of California, Santa Barbara before University (2015–2016) and the
joining the Hunan University, as Tokyo Institute of Technology
an assistant professor in 2013. He (2016–2017) as a postdoctoral
moved to Hunan University of researcher. He joined Zhengzhou
Science and Engineering in 2016 University in 2017. His research
and is currently an associate interest is developing novel
professor. His research focuses approaches for green and efficient
Wei-Min He on green organic synthesis. Bing Yu organic synthesis.

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remarkably distorted from the dicyanobenzene ring with a large

dihedral angle of about 601 due to the steric hindrance. Density
functional theory (DFT) calculations reveal that the highest
occupied molecular orbitals (HOMOs) and the lowest unoccupied
molecular orbitals (LUMOs) of 4CzIPN are localized on the donor
moiety Cz and acceptor moiety dicyanobenzene, respectively
(Fig. 1A and B). The separated HOMOs and LUMOs give rise to
a small energy gap (DEST) between S1 and T1 states. Consequently,
the non-overlapping frontier molecular orbitals (FMOs) make
4CzIPN an efficient thermally activated delayed fluorescence (TADF)
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Scheme 1 Structure of 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene material. More importantly, the spatially separated HOMOs and
(4CzIPN). LUMOs allow an independent fine tuning of both orbitals through
the modification of both the electron donor and electron acceptor
moieties of the cyanobenzene scaffold, by which their photophysical
recent reviews on organic photoredox catalysis have summarized and electrochemical properties can be tuned for specific catalytic
the synthetic applications of Eosin Y, 9-mesityl-10-methylacridinium purposes.10
ions, and other organic dyes.8 Recently, 1,2,3,5-tetrakis(carbazol-9- In addition, the ultraviolet-visible absorption spectrum and the
yl)-4,6-dicyanobenzene (4CzIPN) was found to be a versatile photo- photoluminescence spectrum of 4CzIPN in toluene are presented in
catalyst for various reactions (Scheme 1). As this is a fast-growing Fig. 1C, suggesting a maximum emission at 507 nm. Importantly, a
field, a summary of 4CzIPN for organic transformation is highly high photoluminescence quantum yield (up to 94.6%) and a long
desired. In this article, the recent trend of using 4CzIPN as a visible- life-time in the excited state (5.1 ms) were observed. The photoredox
light photocatalyst in organic synthesis is reviewed. potentials of 4CzIPN were also reported9a,11 (see Table 1).
Photocatalysts such as organic dyes (e.g., Eosin Y, Rose
Bengal) and polypyridyl complexes (e.g., fac-Ir(ppy)3, [Ir[dF(CF3)ppy]2-
2. Properties of 4CzIPN (dtbbpy)](PF6), and [Ru(bpy)3](PF6)2) have found tremendous
applications for photocatalytic transformations in recent decades.
The family of carbazoyl dicyanobenzenes (CDCBs), with carbazo- These compounds are excellent photocatalysts for various organic
lyl (Cz) as an electron donor and dicyanobenzene as an electron transformations. They are poor single-electron oxidants/reductants
acceptor, were first reported as highly efficient light harvesters for in the ground states; however, the excited states under visible-light
organic light-emitting diodes by Adachi and co-workers in 2012.9 irradiation are potent single electron transfer reagents. Generally,
Among these, 4CzIPN is one of the most promising compounds wide redox potential windows, long-lived excited states, and
for photocatalysis. As shown in Fig. 1, the carbazolyl groups are high fluorescence quantum yields of the photocatalysts might
be beneficial to their catalytic activities.
As summarized in Table 1, the redox potentials and excited
state lifetime of the above-mentioned photocatalysts were
compared with those of 4CzIPN. Despite being an inexpensive
organic molecule, 4CzIPN shares several common photophysical
features with Ru- and Ir-polypyridyl catalysts such as long excited
state lifetime, wide redox window, and high fluorescence quantum
yield. For example, 4CzIPN bears both oxidation and reduction
potentials similar to that of the Ir-catalyst [Ir[dF(CF3)ppy]2-
(dtbbpy)](PF6), rendering it a highly desirable photocatalyst.

Table 1 Comparison of the redox potentials and excited state lifetime of

common photocatalystsa

E1/2(P+/P*) E1/2(P*/P) E1/2(P+/P) E1/2(P/P)

Name (V) (V) (V) (V) t (ms) Ref.
4CzIPN 1.04 +1.35 +1.52 1.21 5.1 9a
EY 1.11 +0.83 +0.78 1.06 8c
RB 0.99 +0.66 +0.78 1.11 12
Ir-1 1.73 +0.31 +0.77 2.19 1.9 13
Ir-2 0.89 +1.21 +1.69 1.37 2.3 14
Ru-1 0.81 +0.77 +1.29 1.33 1.1 15
a
All potentials are given in volts versus the saturated calomel electrode
Fig. 1 (A) HOMOs of 4CzIPN; (B) LUMOs of 4CzIPN; (C) UV-visible and (SCE). Measurements were performed in acetonitrile at room temperature.
photoluminescence spectra of 4CzIPN. Reprinted in part with permission EY = Eosin Y. RB = Rose Bengal. Ir-1 = fac-Ir(ppy)3. Ir-2 = [Ir[dF(CF3)ppy]2-
from ref. 9a. Copyright 2012 Springer Nature Publishers Limited. (dtbbpy)](PF6). Ru-1 = [Ru(bpy)3](PF6)2. t = excited state lifetime.

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Moreover, the redox properties of 4CzIPN analogues could also

be easily tuned by deliberate molecular design and modifications
of the electron donor and acceptor moieties according to the
established structure–property relationships.10b Overall, the
above-mentioned unique properties make 4CzIPN not only a
metal-free alternative to transition metal photocatalysts but also
an irreplaceable powerful photocatalyst in modern synthesis.

3. 4CzIPN/metal (Ni or Pd)

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dual-photoredox systems
3.1 4CzIPN in radical generation and metal catalyst
regeneration
The application of 4CzIPN as a photocatalyst for organic reactions
just started in 2016 by Zhang and co-workers.11 For the energetically
demanding photoredox/Ni dual catalytic decarboxylative arylation,
the suggested reaction mechanism (Scheme 2) revealed that a
photocatalyst with high oxidative potential (4+1.1 V) was necessary Scheme 3 4CzIPN/Ni catalyzed arylation of aryl halides with carboxylic
for the generation of reactive radical  R2 via a single electron compounds and alkyltrifluoroborates.
transfer (SET) from the precursors like carboxylic acids 2,
alkyltrifluoroborates 4, silicates 8, and glyoxylic acid monohydrate
14, etc.16 On the other hand, reduced photocatalyst [4CzIPN]  halides 1 and carboxylic compounds 2 (Scheme 3a) and cross-
underwent a SET to regenerate the Ni(0) catalyst species. coupling of alkyltrifluoroborates 4 with aryl halides (Scheme 3b)
Accordingly, reactions following this general mechanism will under light irradiation from a compact fluorescence lamp (CFL).
be summarized in this section. Subsequently in 2016, the group of Ollivier and Fensterbank17
Given that the reductive potential of photoexcited 4CzIPN found that the photooxidation of benzyl bis(catecholato)silicates 5
([4CzIPN]*) is +1.35 V (vs. SCE), while the oxidative potential of (E1/2(Ox/red) = +0.3 to B+0.9 V vs. SCE) with 4CzIPN (E1/2([4CzIPN]*/
amino acid N-tert-butoxycarbonyl-proline (N-Boc-pro) is +0.95 V [4CzIPN] ) = +1.35 V vs. SCE) was possible to generate benzyl
(vs. SCE), it should be feasible for [4CzIPN]* to obtain an electron radicals, which could be trapped by TEMPO 6 (2,2,6,6-tetramethyl-1-
from N-Boc-pro. After the evaluation of rationally designed piperidinyloxy) affording 7 under the irradiation of blue LED light
CDCB-based donor–acceptor (D–A) fluorophores, 4CzIPN was (Scheme 4a). Therefore, a 4CzIPN/Ni dual-catalytic system was
demonstrated to be a stable and active photoredox catalyst for applied for the reaction of various alkyl bis(catecholato)silicates 8
the photoredox/Ni dual catalytic decarboxylative arylation of aryl as radical precursors with radical acceptors 9 such as allylsulfones,
alkenyl halides, b-bromostyrene, etc. (Scheme 4b).
Having known that aryl–NiII complexes, formed from aromatic
halides and nickel catalysts (Scheme 2), are good radical acceptors
for the in situ generated radicals from carboxylic acids, alkyltri-
fluoroborates, and silicates, some other approaches were also
developed by using the 4CzIPN/Ni system for the construction of
C–C bonds. For instance, Molander’s group reported that the
4CzIPN/Ni dual-catalytic system could be utilized in the synthesis
of natural and unnatural flavanones 12 from trifluoroborato-
chromanones 11 with aryl and heteroaryl bromides 10 under

Scheme 2 The proposed mechanism of photoredox/Ni dual catalytic

decarboxylative arylation. Scheme 4 4CzIPN/Ni catalyzed arylation of aryl halides with silicates.

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(Scheme 7b), the reaction of radical 18 and the Ni(0) complex

produced diacetal-nickel(I) intermediate 19, followed by an oxidative
addition of 1 affording Ni(III) complexes 20. After the reductive
elimination, aryl diacetal 21 was obtained, which could then be
Scheme 5 4CzIPN/Ni catalyzed arylation of aryl bromides with trifluoro-
converted into aryl aldehyde 17 by acidic workup. This work
borates.
represents a cost-effective formylation strategy for the synthesis of
aromatic aldehydes starting from substantial aryl chlorides and
mild conditions (weak base, ambient temperature, and visible- avoiding the use of toxic CO and tin compounds under extremely
light) (Scheme 5).18 mild conditions.
In medicinal chemistry, the introduction of C-glycoside
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Moreover, glyoxylic acid monohydrate 14 was successfully

applied as a formyl radical precursor via photoinduced decarb- moieties into drug molecules has become an effective strategy
oxylation, which then coupled with aryl iodides/bromides 13 to for the development of novel pharmaceutical compounds,
synthesize various arene and heteroarene carbaldehydes 15 which may display unique activities as antitumor and antibiotic
under the dual catalysis of 4CzIPN/Pd (Scheme 6).19 A plausible agents.21 In particular, C-acyl-glycoside is one of the most
reaction mechanism was proposed, which is similar to the attractive compounds towards complex bioactive molecules.22
mechanism of the 4CzIPN/Ni system shown in Scheme 2. This However, the direct synthesis of C-acyl-glycoside using easily
procedure provides a practical method for the construction of available carboxylic acid as an acyl source is very challenging.23
aryl aldehydes under mild conditions. Recently, Molander and co-workers24 used high-throughput
In 2017, Mariano and Wang et al.20 demonstrated that experimentation techniques demonstrating that dimethyl
readily available 2,2-diethoxyacetic acid 16 has a low oxidative dicarbonate (DMDC) is a good activator for various carboxylic
potential (+0.95 V vs. SCE, Cs salt of 16 in CH3CN), which acids for the formylation reaction, in which glycosyl substituted
should be a promising radical precursor in the presence of 1,4-dihydropyridines 23 were employed as radical precursors25
photoexcited 4CzIPN ([4CzIPN]*). Furthermore, studies established under blue LED light with 4CzIPN/Ni dual catalysis (Scheme 8a).
a formylation of organic (pseudo)halides with 16 as a radical Notably, a free hydroxy group and steroidal moieties (24a and 24b)
precursor to generate  CH2(OEt)2 radical 18 by the catalysis of can be well tolerated in this elegant procedure. Subsequently, a
the 4CzIPN/Ni dual-catalytic system under the irradiation of blue similar strategy was applied to the arylation of highly functionalized
LED light (Scheme 7a). As shown in the proposed mechanism saccharides 26 from aryl bromide 25 and glycosyl substituted
1,4-dihydropyridines 23 with 4CzIPN/Ni dual catalysis under
visible-light irradiation (Scheme 8b).26
The construction of the C–S bond has been an important
issue in heteroatom chemistry, material science and medicinal
chemistry.27 Alkynyl sulphides could be obtained by using
umpolung-type strategies including sulfur umpolung and alkyne
umpolung.28 However, methods for the direct synthesis of alkynyl
Scheme 6 4CzIPN/Pd catalyzed formylation of aryl halides.
sulphides are rare, because the direct reaction of thiols and
terminal alkynes generally gives the thiol–yne click reaction
products.29 In 2017, Collins and co-workers realized the oxidative
coupling of bromoalkynes 27 and thiols 28 to synthesize thioalkynes

Scheme 7 4CzIPN/Ni catalyzed formylation of aryl halides and triflates. Scheme 8 4CzIPN/Ni catalyzed synthesis of acylated/arylated glycosides.

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3.2 4CzIPN in photocatalytic metal catalyst regeneration

The transformation of carbon dioxide (CO2) into valuable
products under mild conditions has drawn huge attention in
the past few decades.32 Selective hydrocarboxylation of styrenes
with CO2 is one of the most challenging reactions.33 Recently,
König and co-workers reported a ligand-controlled selective
Markovnikov and anti-Markovnikov hydrocarboxylation of styrenes
with CO2 under mild conditions. As shown in Scheme 11a, the
hydrocarboxylation products could be tuned by using different
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ligands.34 For example, when 1,4-bis-(diphenylphosphino)butane

(dppb, L1) as a ligand gave anti-Markovnikov product 42 (linear/
branched Z 97 : 3), neocuproine (L2) as a ligand afforded
Scheme 9 4CzIPN/Ni catalyzed synthesis of thioalkynes.
Markovnikov product 43 (branched/linear = 100 : 0) by 4CzIPN/
Ni dual catalysis.
29 using continuous flow techniques involving 4CzIPN/Ni dual In the mechanistic studies, it was found that radical inhibitors
photocatalysis.30 It is believed that the thiyl radical is generated could not inhibit the reaction, suggesting that radical intermediates
from thiols 28 under the catalysis of 4CzIPN under LED light. The are not essential. On this basis, a possible mechanism with two
procedure was highly efficient (30 min, 50–96% yields) and showed pathways was proposed as shown in Scheme 11b. For the anti-
high reproducibility (gram scale). In particular, 19-membered Markovnikov reaction, the Ni(0) species might first coordinate with
macrocyclic alkynyl sulphide 29a could be synthesized, albeit in CO2 generating Aresta’s complex 44,35 which was followed by alkene
28% yield under flow conditions, via an intramolecular coupling by insertion affording 5-membered nickelalactone 45. After a SET step,
using this dual photocatalytic system (Scheme 9). nickel carboxylate 46 was produced, and then anti-Markovnikov
In 2018, direct C–H oxidation of 2-arylpyridines and 2-aryl- product 42 was released via a subsequent reduction (nickel catalytic
benzothiazoles 30 towards phenols 31 with the metallaphoto- cycle I). On the other hand, H2 was detected in the reaction
redox system under visible-light with O2 as a green oxidant was indicating that a nickel hydride intermediate (H–NiII) was plausible.
reported by Singh’s group (Scheme 10).31 In this protocol, For the Markovnikov reaction, the reaction pathway (nickel catalytic
BrCCl3 and toluene (or cyclohexane) were found to be significant cycle II) involving nickel hydride intermediate 47 was also
for this transformation. It was proposed that  CCl3 radical 35 was reasonable.
first produced from BrCCl3 catalyzed by 4CzIPN, which then
induced benzyl radical 36 (or cyclohexyl radical 37) from toluene
(or cyclohexane). Subsequently, radical 36 (or 37) was trapped by
O2 to produce intermediate peroxo radical 38 (or 39), which then
released hydroxyl radical 40 (HO ).

Scheme 10 4CzIPN/Pd catalyzed hydroxylation. Scheme 11 4CzIPN/Ni catalyzed hydrocarboxylation of styrene with CO2.

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4. Metal-free catalytic system

Compared with the classic photocatalysts with strong excited
state reduction potential (i.e. Ru/Ir complexes), 4CzIPN has
prominent features such as low cost and easy preparation.9a,11
Therefore, 4CzIPN was applied as an excellent organophotocatalyst
for various transformations under the irradiation of visible-light.
With the catalysis of 4CzIPN, radical precursors could be converted
into reactive radicals, which could be trapped by organic
substrates, such as unsaturated CQC or CQN bonds, rendering
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metal-free photocatalytic approaches. Therefore, reactions employing

4CzIPN as the sole metal-free photocatalyst are summarized in
this section.

4.1 Reactions involving CQ

QC bonds
After demonstrating that 2,2-diethoxyacetic acid 16 as a radical
precursor could generate  CH2(OEt)2 radical 18 by 4CzIPN
catalysis under the irradiation of blue LED light (Scheme 7a),20
the research group of Mariano and Wang36 subsequently developed Scheme 13 4CzIPN catalyzed defluorinative alkylation.
a regioselective hydroformylation reaction of aryl olefins with
diethoxyacetic acid 16 as the formylation reagent using a
continuous flow system (Scheme 12). In their proposed mechanism, developed a radical cyclopropanation reaction of alkenes 59 via a
relatively stable benzylic radical 52 was produced via the anti- single-electron photocatalysis approach with 4CzIPN catalysis
Markovnikov addition of radical 18 to the CQC bond, which under visible-light (Scheme 14). In this work, triethylammonium
then underwent a SET process affording anion 53. Anion 53 was bis(catecholato)iodomethylsilicate 60 was applied as a cyclo-
easily converted into the desired aldehyde 51 by protonation propanating reagent, which generated a halomethyl radical in
and acid catalyzed hydrolysis. the reaction. The mechanistic studies revealed that the addition
Almost at the same time, Molander’s group disclosed a mild of this halomethyl radical to 59 was followed by a SET process
and efficient method for the construction of gem-difluoroalkenes using 4CzIPN, which converted the resulting radical adduct 62
56 from trifluoromethyl-substituted alkenes 55 which underwent to an anion 63 that undergoes anionic 3-exo-tet cyclization
radical defluorinative alkylation with the photocatalysis of producing the product 61.
4CzIPN (Scheme 13).37 Various radical precursors including alkyl Subsequently, the 4CzIPN photocatalytic system was further
bis(catecholato)silicates, organotrifluoroborate, and a-silylamine applied to the cyclopropanation reaction of homoallylic tosylate
were investigated in this procedure. Key intermediate 58 was formed 64 and radical precursors 65 under blue light (Scheme 15).39
via the radical addition and the SET process, followed by an E1cB- This method is a more general cyclopropanation strategy because
type fluoride elimination delivering gem-difluoroalkenes 56. various radicals are applicable for the radical addition with the
Considering the importance of cyclopropyl in pharmaceutical CQC bond of 64.
active molecules, direct cyclopropanation from easily available Due to the similar bond dissociation energies (BDEs) of Si–H
compounds is highly valuable. Consequently, Molander’s group38 and C–H bonds, the selective activation of Si–H bonds is
challenging.40 Recently, Wu and co-workers41 demonstrated
that the combination of photocatalyst 4CzIPN and hydrogen
atom transfer (HAT) catalysts 72 and 73 was an efficient
catalytic system for the hydrosilylation of alkenes through
Si–H activation (Scheme 16). As Si is more electropositive than C,

Scheme 12 4CzIPN catalyzed hydroformylation reaction of aryl olefins. Scheme 14 4CzIPN catalyzed cyclopropanation of alkenes.

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Scheme 15 4CzIPN catalyzed radical/polar annulation reactions of homo-

allylic tosylate.

Si–H bonds are generally more hydridic than C–H bonds. Therefore,
it is feasible to generate silyl radicals via selective Si–H activation by
using a highly electrophilic HAT catalyst.42 In this work, the
hydrosilylation of both electron-deficient 69 and electron-rich
alkenes 70 toward the corresponding products 74 and 75 was
achieved by using different HAT catalysts 72 or 73 incorporated
with 4CzIPN under mild blue light irradiation.
CO2 is an abundant, renewable C1 feedstock, and an important
electrophile for organic synthesis. Transformations of CO2 under
mild conditions have drawn considerable attention in the past few
decades.43 In the proposed reaction pathway of combined photo-
redox system (4CzIPN/HAT) catalyzed hydrosilylation of olefins
(Scheme 16b), silyl radical addition adduct 76 underwent a
single-electron reduction giving the corresponding nucleophilic
anion 77. Inspired by this key step, Wu’s group44 realized the
silacarboxylation of alkenes 84 with silane and CO2 under
similar photocatalytic conditions (Scheme 17). Significantly, Scheme 16 4CzIPN/HAT catalyzed hydrosilylation of alkenes.
the unprefunctionalized C(sp3)–H alkanes also proceeded smoothly
to react with alkene and CO2 under identical conditions delivering
the important g-amino acid motifs as products.
Cascade radical reactions have emerged as a powerful method
for the rapid construction of complex scaffolds in the past few
decades.45 In particular, photocatalysis methods are powerful and
Scheme 17 4CzIPN/HAT catalyzed silacarboxylation of alkenes with silane
sustainable synthetic protocols to initiate the radical cascade and CO2.
reactions.46 Very recently, the research group of Cai reported a
series of visible-light promoted radical cascade reactions using
4CzIPN as a metal-free photocatalyst (Scheme 18). For example,
the trifluoromethylation/aryl migration reaction of a,a-diaryl
allylic alcohols 86 and CF3SO2Na (Langlois reagents) 87 with
4CzIPN photocatalysis produced b-trifluoromethyl-a-aryl ketones 88
as products (Scheme 18a).47 This method avoids the use of transi-
tion metal catalysts, expensive trifluoromethyl sources and strong
oxidants.48 Similarly, the same catalytic system could also be applied
to the reaction of N-arylacrylamides 89 and Langlois reagent 87,
affording CF3-containing oxindoles (Scheme 18b).49 In addition,
using dimethyl sulfoxide 91 as a radical precursor, a-aryl-g-
methylsulfinyl ketones 92 were constructed from a,a-diaryl Scheme 18 4CzIPN catalyzed radical cascade reactions.
allylic alcohols 86 by 4CzIPN photocatalysis. In this work,
phenyliodonium bis(trifluoroacetate) (PhI(OCOCF3)2, PIFA) and
1,3,5-trimethoxybenzene were added to form the hypervalent isotope effect demonstrated that C–H bond cleavage might be
iodine(III) compound intermediate as an oxidant. The kinetic the rate-determining step (Scheme 18c).50

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Scheme 19 4CzIPN catalyzed 1,2-amidoalkynylation of unactivated alkenes.

Very recently, Studer’s group reported the 1,2-amidoalkynylation

of unactivated alkenes 93 with 4CzIPN photocatalysis.51 Troc-
protected a-aminoxy acids 94 (Troc = 2,2,2-trichloroethoxy-
carbonyl) were used as precursors for the formation of amidyl
radicals 99. The nucleophilic addition of N-radicals 99 with
alkenes 93 afforded the adduct radicals 100, which were then
trapped by hypervalent iodine(III) compounds to eventually
provide amidoalkynylation products 96 (Scheme 19). Notably,
various mono-, di- and trisubstituted unactivated alkenes are Scheme 21 Two possible reaction pathways.

employed as substrates for the construction of diverse b-alkynylated

Troc-amides under mild conditions. radical 106. In the two possible pathways, although the reduction
of imine 103 to the corresponding a-amino radical anion 108 was
4.2 Reactions involving CQ
QN bonds unfavourable, pathway b could not be excluded in this process.
In 2018, the group of Weng and Lu53 disclosed 4CzIPN-
Besides the above-mentioned unsaturated CQC bonds, the
catalyzed decarboxylative benzylation of imines 109 under the
CQN bonds were also reported as radical acceptors for novel
irradiation of visible-light (Scheme 22). A variety of primary,
transformations under 4CzIPN photocatalysis. On the other
secondary, and tertiary arylacetic acids 110 were successfully
hand, it is also possible to generate a-amino radical anions
applied as precursors of benzyl radicals, enabling the facile
from CQN bonds via a SET process, rendering a possible
benzylation of a variety of imines affording diverse b-aryl-
radical–radical coupling reaction. For instance, Molander’s
ethylamines 111. In the mechanistic studies, some imine
group reported a C–C bond formation reaction from imines
reduction and imine dimer by-products were observed, thus
103 and ammonium alkyl bis(catecholato)silicates 104 using
ruling out the radical-addition pathway.
4CzIPN as the sole photocatalyst in DMSO without any additives
In 2018, Yu’s group developed the 4CzIPN-catalyzed hydro-
(Scheme 20).52
carboxylation of imines (or enamides) 112 with a CO2 atmosphere to
In this procedure, the single-electron oxidation of silicates
synthesize a,a-disubstituted a-amino acids 113 under irradiation of
104 produced C-centered radicals 106. Subsequently, two reaction
visible-light (Scheme 23).54 The traditional umpolung hydrocarb-
pathways should be possible (Scheme 21): (a) The addition of
oxylation of imines with CO2 is very challenging;55 however, it is
radical 106 to imine 103, followed by a single-electron reduction of
hypothesized that a-amino carbanions 114 could be generated by
the resulting N-centered radical 107; or (b) a ‘‘persistent radical’’,
the visible-light-driven reduction of imines 112, followed by the
i.e., a-amino radical anion 108 was produced by the single-electron
nucleophilic addition of CO2 to give carboxylates 115.
reduction of 103, followed by a radical–radical coupling with

Scheme 20 4CzIPN catalyzed alkylation of imines. Scheme 22 4CzIPN catalyzed decarboxylative benzylation of imines.

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Scheme 26 4CzIPN catalyzed direct C–H functionalization.

Scheme 23 4CzIPN catalyzed hydrocarboxylation of imines.

In Molander’s recent report, 4CzIPN was also found to be an
efficient photocatalyst for the direct C–H functionalization of
heteroarene 129 with tert-butyltrifluoroborate 130 affording
product 131 in the presence of K2S2O8 and trifluoracetic acid
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(TFA) (Scheme 26).58 However, when primary alkyltrifluorobo-

rate was employed as a substrate, the yield was very poor,
probably due to the extremely high oxidation potential of primary
alkyltrifluoroborates.

4.3 Miscellaneous reactions

In 2018, the group of Cramail and Landais described a 4CzIPN
photocatalyzed oxidative decarboxylation of oxamic acids 132
with alcohol 133 or amine 136 to synthesize urethanes 135 and
Scheme 24 4CzIPN catalyzed one-pot synthesis of a,a-difluoroketone ureas 137 (Scheme 27).59 In this strategy, a hypervalent iodine
hydrazones.
reagent (BI-OAc, 134) was employed as an oxidant. Adduct 138,
resulting from 132 and 134, underwent a free-radical decarboxyla-
The research group of Zhou and Wang56 used the one-pot tion under visible-light, generating carbamoyl radical 140, followed
approach to realize the synthesis of a,a-difluoroketone hydrazones by oxidation which furnished the key isocyanate intermediate 141.
119 from aldehydes 116, hydrazines 117, and bromodifluorinated Finally, the addition of alcohol 133 or amine 136 to 141 delivered
reagents 118 via visible-light photoredox catalysis (Scheme 24). The the corresponding products urethanes 135 and ureas 137.
condensation of aldehydes 116 and hydrazines 117 produced Due to the importance of deuterium- and tritium-labelled
the corresponding hydrazones 120, followed by a single-electron pharmaceutical compounds for drug discovery, in 2017 MacMillan
oxidation to generate radical 121 or 122. On the other hand, the and co-workers60 reported an efficient dual photo-/HAT-catalysis
single-electron reduction of BrCF2R4 118 under photoredox system for the installation of deuterium (D) and tritium (T) at the
conditions afforded radical 123. The radical addition of 122 a-amino C(sp3)–H of 18 drug molecules in a single step using
and 123 furnished intermediate 124, which then converted into isotopically labelled water (D2O or T2O) as the source of the
the desired product 119 by deprotonation. hydrogen isotope (Scheme 28). For example, commercially
Sherwood et al. reported an improved, one-pot Minisci available antidepressant drug clomipramine 142 was deuterated
reaction using carboxylic acids and N-containing heterocycles to give the corresponding product 143 in 76% yield using
including quinoline, pyridine, quinaldine, isoquinoline, quinazoli- 4CzIPN as a photocatalyst and thiol 73 as a HAT catalyst.
none, purine, phthalazine, quinoxaline, 7-azaindoles, benzimidazole,
benzothiazole, caffeine, nebularine, etc. with the 4CzIPN photo-
catalysis system (Scheme 25).57 Carboxylic acids 126 first
undergo N-(acyloxy)phthalimides (NAPs) 128 formation in the
presence of N-hydroxyphthalimide (NHPI) and N,N 0 -diisopropyl-
carbodiimide (DIC) and DMAP. Subsequently, the NAPs generate
the alkyl radical releasing CO2 and phthalimide under photo-
catalytic conditions, followed by radical addition with hetero-
cycles 125 giving the C–C bond formation product 127.

Scheme 25 4CzIPN catalyzed one-pot Minisci reaction. Scheme 27 4CzIPN catalyzed oxidative decarboxylation coupling.

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fragmentation giving amidyl radical 153, followed by enthalpy-

favorable 1,5-HAT resulting in the key radical 154. Then, the SH2
reaction between 154 and SOMOphiles 151 furnished the
targeted products 152. This procedure provides an efficient
method for the incorporation of F, Cl, SPh, CN, and alkyne
functionalities into amides and amines via a cascade process of
Scheme 28 Dual photo-/HAT-catalysis system for C(sp3)–H deuteration
(gram scale). 1,5-HAT and SH2-functionalization.

5. Conclusions
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Visible-light promoted organic synthesis with metal complexes

(Ru and Ir, etc.) as photocatalysts has gained huge attention in
the past few decades. To a great extent, 1,2,3,5-tetrakis(carbazol-
9-yl)-4,6-dicyanobenzene (4CzIPN) is an excellent and inexpensive
metal-free alternative for those noble photocatalysts. In this
review, the recent advances of the application of 4CzIPN as a
photoredox catalyst for the generation of various radicals in
organic reactions were summarized. For instance, benzyl radicals,
Scheme 29 Trifluoromethylthiolation of tertiary ethers. formyl radicals,  CH2(OEt)2 radical,  CCl3 radical, silyl radicals,
amidyl radicals, alkyl radicals, carbamoyl radicals, thiyl radicals,
Recently, the research group of Xie and Zhu disclosed an etc. from many different precursors could be achieved via 4CzIPN
elegant synergistic photo-/HAT-catalysis system to realize the photocatalysis. However, 4CzIPN photocatalysis offers far more
transition-metal-free, site-specific trifluoromethylthiolation of than a metal-free alternative to the classic noble complexes. As a
tertiary ethers 144 with 4CzIPN as a photocatalyst and BINOL- typical donor–acceptor molecule, 4CzIPN has shown an excellent
based phosphorothiol 146 as a HAT catalyst (Scheme 29).61 redox window, good chemical stability and broad applicability. It is
Based on the calculation of singly occupied molecular orbital convenient for researchers to modify the charge transfer char-
(SOMO) energies of several kinds of thiyl radicals, compound 146 acteristics of 4CzIPN analogues with specific redox potentials by
with significantly high electrophilic reactivity was proved to be a changing the donors and acceptors.10 Overall, 4CzIPN has been
potential HAT catalyst. Under photocatalysis, 146 was converted used as a photocatalyst for organic transformation just since
into a thiyl radical to abstract the most hydridic C–H bond of the 2016. The application of simple and economical 4CzIPN as a
ether providing radical 148. Radical 148 underwent a homolytic metal-free photocatalyst will open new avenues for the exploration
cleavage of the C–O bond forming tertiary alkyl radical 149, which of novel visible-light-promoted transformations.
then reacted with 145 resulting in product 147 via the radical–
radical pathway or the radical-addition pathway. Conflicts of interest
Leonori and co-workers62 described a 4CzIPN-involved photo-
catalysis approach for the remote C(sp3)–H functionalization of There are no conflicts to declare.
amides and amines 150 with polarized SOMOphiles (X–Y) 151
(Scheme 30). Substrate 150 suffered from a SET oxidation and Acknowledgements
We gratefully acknowledge the National Natural Science Foundation
of China (No. 21501010) and the Hunan Provincial Natural Science
Foundation of China (No. 2019JJ20008) for the financial support.

Notes and references

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