Accepted Article

Accepted Article
Title: Organophotocatalytic Remote Thiocyanation Reaction via Ring-
Opening Functionalization of Cycloalkanols

Authors: Ruirui Hua, Qing Wang, Hongquan Yin, and Fu-Xue Chen

This manuscript has been accepted after peer review and appears as an
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Article as a result of editing. Readers should obtain the VoR from the
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To be cited as: Chem. Eur. J. 2024, e202400453

Link to VoR: https://doi.org/10.1002/chem.202400453

01/2020
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RESEARCH ARTICLE
Organophotocatalytic Remote Thiocyanation Reaction via Ring-
Opening Functionalization of Cycloalkanols
Ruirui Hua,[a] Qing Wang,[a] Hongquan Yin,[a,b] and Fu-Xue Chen*[a,b]
[a] Ruirui Hua, Qing Wang, Dr. Hongquan Yin, Prof. Dr. Fu-Xue Chen
School of Chemistry & Chemical Engineering
Beijing Institute of Technology (Liangxiang Campus)
No. 8 Liangxiang East Road, Fangshan District, Beijing 102488, China
E-mail: fuxue.chen@bit.edu.cn
[b] Key Laboratory of Medical Molecule Science and Pharmaceutics Engineering, Ministry of Industry and Information Technology, Beijing Institute of
Technology, No. 8 Liangxiang East Road, Fangshan District, Beijing 102488, China

Accepted Manuscript
Abstract: The remote C(sp3)-SCN bond formation via ring-opening
functionalization of cycloalkanols with N-thiocyanatosaccharin as the
precursor of SCN radicals and pyrylium salt as the organic
photocatalyst under visible light has been developed. Thus, various
terminal keto thiocyanates were prepared without transition metals
and oxidants in moderate to good yields. The simplicity, wide
substrate scope and mild conditions feature its synthetic application
capability.

Introduction

Alkyl thiocyanates are widely present in bioactive molecules and

natural products, such as 4-phenoxyphenoxyethyl thiocyanate
and psammaplin B (Figure 1).[1] Moreover, these thiocyanated
intermediates serve as essential building blocks that can be
readily converted into a variety of sulphur-containing compounds,
adding to their significance in various chemical processes and
applications.[2] Currently, there are two mainstream methods for
the synthesis of alkyl thiocyanates. One is the cyanation reaction
of sulphur-containing compounds (Scheme 1A).[3] The other is the
thiocyanation reaction4a of alkyl substrates containing specific
functional groups, such as alkyl halides,[4b,c] alkyl alcohols,[4d]
alkylboronic acids,[4e] thiols,[4f] and the direct C-H thiocyanation[5]
(Scheme 1B). In recent years, electrophilic C-H thiocyanation
reactions have been developing rapidly due to its mild reaction
conditions, inexpensive non-toxic reagents, and high efficiency.
However, the synthesis of alkyl thiocyanates through electrophilic
reactions is currently limited to substitution reactions of -keto
esters,[6a] oxoindole,[6b] and bifunctionalization reactions of Scheme 1. Synthesis of alkyl thiocyanates.
unsaturated hydrocarbons as well.[6c-h] It is particularly challenging
to achieve simple and efficient synthesis of terminal alkyl alkoxypyridinium salts under dual photoredox/copper catalysis. In
thiocyanates.[7,8] 2020, Zhang's[9a] and Liu’s[9b] group independently disclosed an
Recently, the development of radical thiocyanation reactions intermolecular C(sp3)−H site-selective thiocyanation of aliphatic
has greatly enriched the synthesis methodology of remote alkyl sulfonamides catalysed by Cu(I) complexes. Photocatalytic
thiocyanates (Scheme 1C). In 2019, Zhu and co-workers[9c] decarboxylative functionalization of carboxylic acids and their
developed a remote C(sp3)−H thiocyanation by N- esters has been emerging as a powerful tool for the synthesis of
target molecules.[10] In 2023, Aggarwal’s group had accomplished
visible-light photoredoxcatalysed protocols for the
decarboxylative thiocyanation of N-hydroxyphthalimide esters.[10a]
The ring-opening functionalization of cyclic alcohols is an
effective strategy for the synthesis of distally functionalized
Figure 1. Selected examples of SCN-containing bioactive compounds. carbonyl compounds[11] especially from strained rings, such as

1
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RESEARCH ARTICLE
cyclopropanols and cyclobutanols, where alkoxyl radicals are Table 1. Optimization of reaction conditions.[a]
highly susceptible to -scission driven by the release of ring-strain
energy.[12] However, the ring-opening functionalization of non-
strained rings is more challenging and typically requires harsh
conditions, such as stoichiometric oxidants and expensive
transition metals.[13] Based on our previous work[6f] and
literatures[14], RO-SCN active specie could be generated by
deprotonation of alcohols, thereby avoiding the equivalent
oxidants and bases. In 2023, our group[10d] reported the
photocatalytic decarboxylative selenocyanation of 2-aryloxy and
2-aryl carboxylic acids with N-selenocyanatophthalimide,
affording terminal aryloxyl and aryl selenocyanates but
unsuccessful for long-chain derivatives. In the same year, Besset

Accepted Manuscript
and co-workers developed a divergent selective synthesis of
thiocyanates and isothiocyanates using similar photocatalytic
Entry Photocatalyst [SCN] Solvent Yield[b] (%)
system.[10e] Herein, we report the synthesis of terminal alkyl
1 PC1 2a DCE 86
thiocyanates via ring-opening functionalization of cycloalkanols
under visible light with N-thiocyanatosaccharin as the precursor 2 PC1 2b DCE 70
of SCN radicals and pyrylium salt as the photocatalyst. 3 PC1 2c DCE 33
4 PC1 2d DCE 26
5 PC2 2a DCE 16
Results and Discussion
6 PC3 2a DCE 42

At the beginning, 1a was chosen as the standard substrate to 7 PC4 2a DCE 84

optimize the reaction conditions. First, different thiocyanating 8 PC5 2a DCE 13
reagents 2a−2d (2.0 equiv.) were screened and yielded the 9 PC6 2a DCE Trace
desired product 3a in 26-86% yields in the presence of pyrylium
10 fac-Ir(ppy)3 2a DCE 0
salt PC1 (2 mol%) for 12 h at room temperature under the
11 4CzIPN 2a DCE 0
illumination of a blue LED at 435-445 nm (Table 1, entries 1−4).
2a was identified as the suitable thiocyanating reagent (entry 1). 12 PC1 2a CH2Cl2 81

Second, a series of photocatalysts were evaluated. Structurally 13 PC1 2a CH3CN 35

modified pyrylium salts PC2−PC4 gave reduced yields (entries 14 PC1 2a THF Trace
5−7). When acridine salts PC5−PC6 were used low yields of 3a 15 PC1 2a Dioxane Trace
were obtained (entries 8 and 9). However, no product was formed
16 PC1 2a DMSO Trace
in the presence of fac-Ir(ppy)3 and 4CzIPN (entries 10 and 11).
17 PC1 2a Acetone 12
Next, solvent effect on the yield was investigated. Other polar
solvents gave poor yields of 3a (entries 13−18), except 18 PC1 2a HFIP 0
dichloromethane comparable yield with 1,2-dichloroethane (entry 19[c] PC1 2a DCE 70
12 vs 1). Subsequently, other reaction parameters such as 20[d] PC1 2a DCE 56
wavelength of the light and the reaction concentration were [e]
21 PC1 2a DCE 80
studied offering no improvement (entries 19−21). In addition,
22[f] PC1 2a DCE 77
stoichiometric amount of base eroded the yield (for optimization
of bases, see Supporting Information). Strong base other than [a] Reaction conditions: 1a (0.1 mmol), 2 (0.2 mmol), photocatalyst (0.002
sodium carbonate were observed to deteriorate the reagent 2a mmol, 2 mol%), Na2CO3 (0.02 mmol, 20 mol%), solvent (1.0 mL), rt, Ar, 12
quickly while a small amount of soft base is beneficial to yield h, a blue LED (435-445 nm, 5 W). [b] Isolated yield. [c] Purple LED (400-
(entry 22 vs 1). Therefore, the optimal reaction conditions are 2a 410 nm, 5 W). [d] Blue LED (465-475 nm, 5 W). [e] 0.15 M. [f] Na2CO3 (0.1
(2.0 equiv.), PC1 (2 mol%), Na2CO3 (20 mol%), in 1,2- mmol, 1.0 equiv.). DCE= 1,2-dichloroethane. DMSO = dimethyl sulfoxide.
dichloroethane (DCE) at room temperature under 435–445 nm HFIP = hexafluoroisopropanol.
blue LED irradiation.
After obtaining the optimal reaction conditions, we investigated worth noting that substrates with methyl on the benzene ring
the substrate scope. A diverse range of 1-aryl cyclohexanol underwent benzylic C-H thiocyanation as a side reaction.[10e]
derivatives were examined. Cyclohexanols bearing electron- Moreover, the title reaction can effectively take place in both
withdrawing groups at the para position, such as fluoro (1b), meta- and ortho-substituted substrates, regardless electron-
chloro (1c), and bromo (1d) groups, were well tolerated, giving withdrawing or electron-donating groups (3h−3k, 30−56%).
the corresponding products in good yields (3b−3d, 62−93%) while Comparing 3b, 3h, and 3j, it was found the closer the substituent
strong electron-withdrawing substituents such as CN and CF3 to the hydroxyl group is, the more pronounced effect on the yield.
exhibited low conversion. Substrates with electron-donating Besides, the presence of a strong electron-donating group (-OMe)
substituents at the para position of the benzene ring produced the on the ortho position led to a chaotic reaction. Next, various cyclic
desired products with moderate yields (3e−3f, 32−68%). It is
2

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RESEARCH ARTICLE
Table 2. Substrate scope.[a] 55% yields. Additionaly, under the optimal reaction conditions,
utilizing N-selenocyanatosaccharin (2e) as the selenocyanato
reagent successfully yielded the desired product of ring-opening
remote selenocyanate (3u, 54%). Further investigation was
conducted with chiral tertiary alcohol (1v) derived from L-menthol,
and the corresponding product 3v was obtained in 55% yield and
a diastereoselectivity ratio of 7:3.
To demonstrate the applicability of this protocol, we conducted
gram-scale experiments and 3c was obtained in 75% yield
(Scheme 2a). Further, the thiocyanato group in product 3c could
undergo a straightforward substitution reaction with TMSCF3,
affording product 4 in 70% yield (Scheme 2b).

Accepted Manuscript
Scheme 3. Control experiments.
[a] Reaction conditions: 1a (0.1 mmol), 2a (0.2 mmol), photocatalyst (0.002
mmol, 2 mol%), Na2CO3 (0.02 mmol, 20 mol%), 1,2-dichloroethane (1.0 To shed light on the mechanism, a series of control experiments
mL), rt, Ar, overnight, a blue LED (435-445 nm, 5W); [b] Isolated yield, the were performed (Scheme 3). In the absence of PC1 or visible light
diastereomeric ratio was determined by 1H NMR; [c] photocatalyst (0.005 3a was not detected (Scheme 3a and 3b). However, in the
mmol, 5 mol%); [d] N-Selenocyanatosaccharin (2e, 0.20 mmol, 2.0 equiv.) absence of PC1, treatment of 1a with 2a in dark at 100°C
instead of 2a; [e] 6h; [f] [α]20 D = -11.84 (c = 1 g/100 mL, CH2Cl2). produced 3a in 14% isolated yield (Scheme 3c), suggesting active
RO-SCN species involved in this reaction.[6f,14] Radical trapping
structures were examined. The tetrahydropyranol derivatives experiments with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)
were transformed into the desired products 3l with 59% yield. and 2,6-di-tert-butyl-4-methylphenol (BHT) turned out to be no
Substrates containing alkyl or aromatic substituents on the product formed (Scheme 3d and 3e, also see the ESI†). These
cyclohexanol framework also afforded the desired product in
moderate to good yields (3m−3o, 46−78%). In the case of
asymmetric substrates, product 3m and 3n was obtained through
regioselective -scission reaction by generating more stable alkyl
radicals. Moreover, substrates of different ring size were studied,
and 5-, 7-, 8-, 12-, and 15-membered rings (1p−1t) were
converted into corresponding products 3p−3t ranging in 34% to

Scheme 2. Gram-scale reaction and synthetic applications. Figure 2. Quenching of PC1 fluorescence emission with 1a.

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RESEARCH ARTICLE
Figure 3. Stern−Volmer plot. I0 is the inherent fluorescence intensity of PC1. I
is the fluorescence intensity of PC1 in the presence of 1a.
experimental results indicate that both alkyl and thiocyanato
radicals are involved in the catalytic cycle.
To elucidate the interactions between pyrylium salt PC1 and
substrates, the fluorescence quenching experiments of PC1 with
1-phenylethanol 1a and 2a were investigated, respectively. The
fluorescence emission intensity decreases regularly with
increasing concentration of 1a (Figure 2). This tendency was also
obvious in the corresponding Stern-Volmer plots[13a], indicating a
reduction quenching pathway (Figure 3).
Scheme 4. Proposed mechanism.
Based on these observations and literatures, we proposed a
possible mechanism for the ring-opening thiocyanation reaction
of cyclohexanol derivatives (Scheme 4). Under visible light
irradiation, the pyrylium salt absorbs a photon and becomes an
excited state photocatalyst. Then alcohol 1a is oxidized by the
excited photocatalyst via single-electron transfer (SET)[10d,e] and
forms a transient radical I (Path a). On the other hand, in situ
generated active species Int-SCN could not be excluded as a
secondary pathway (Path b).[6f,14] The homolysis of Int-SCN
species alternatively lead to the formation of the radical I.[13i]
Subsequently, the C-C bond undergoes cleavage, forming a distal
alkyl radical II. Finally, the product 3a was produced through
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radical thiocyanation with 2a. The resulting saccharin radical III is
subsequently reduced to the saccharin anion IV by PC•− and then
protonated by acid. This process simultaneously regenerates the
pyrylium photocatalyst and completes the photocatalytic cycle.
Conclusion
In summary, we have successfully achieved the photocatalytic
remote alkyl thiocyanation via ring-opening functionalization of
cycloalkanols without the transition metals and oxidants. Starting
with readily available cyclic alcohols, a series of ketones with
Accepted Manuscript
remote thiocyanato substituent have been efficiently synthesized
without the need for pre-installed leaving groups. This protocol
provides possibility for the synthesis of some naturally occurring
compounds with remote thiocyanate groups.
Experimental Section
General procedure for the synthesis of 3: To a 25 mL Schlenk
tube containing 1 (0.1 mmol, 1.0 equiv) was added PC1 (0.002
mmol, 2 mol%), Na2CO3 (0.02 mmol, 20 mol%) and dry 1,2-
dichloroethane (1.0 mL) under an argon atmosphere. Then, 2a
(0.2 mmol, 2.0 equiv) was added. The reaction was irradiated with
blue LED (435‒445 nm, 5 W) for overnight at room temperature.
When the reaction was completed, the product was purified by
column chromatography on silica gel with petroleum ether
(PE)/ethyl acetate to afford the product 3.
Acknowledgements
The authors are grateful for financial support provided by the
National Natural Science Foundation of China (21971013).
Keywords: photocatalysis • alkyl thiocyanation • ring-opening
functionalization • terminal thiocyanatoketone • synthetic
methodology
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10.1002/chem.202400453

A visible-light-induced remote alkyl thiocyanation via ring-opening functionalization of cycloalkanols with the electrophilic N-

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6
Entry for the Table of Contents

thiocyanatosaccharin has been developed.

RESEARCH ARTICLE
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