Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo Compounds with Pentafluorosulfanyl Chloride

Article abstract of DOI:10.1002/anie.202103606

Pentafluorosulfanyl chloride (SF₅Cl) is the most prevalent reagent for the incorporation of SF₅ group into organic compounds. However, the preparation of SF₅Cl often relies on hazardous reagents and specialized apparatus. Herein, we described a safe and practical synthesis of a bench-stable and easy-to-handle solution of SF₅Cl in n-hexane under gas-reagent-free conditions. The synthetic application of SF₅Cl was demonstrated through the unprecedented reaction with diazo compounds. The chemoselective hydro- and chloropentafluorosulfanylations of α-diazo carbonyl compounds were developed in the presence of K₃PO₄ or copper catalyst, respectively. These reactions provide a direct and efficient access to various α-pentafluorosulfanyl carbonyl compounds of high value for potential applications.

Full text of DOI:10.1002/anie.202103606

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Accepted Article
Title: Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo
Compounds with Pentafluorosulfanyl Chloride
Authors: Feng-Ling Qing, Jia-Yi Shou, and Xiu-Hua Xu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202103606
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Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo
Compounds with Pentafluorosulfanyl Chloride
Jia-Yi Shou, Xiu-Hua Xu, and Feng-Ling Qing*
[a]
J.-Y. Shou, Dr. X.-H. Xu, Prof. Dr. F.-L. Qing
Key Laboratory of Organofluorine Chemistry
Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of
Sciences
345 Lingling Lu, Shanghai 200032, China
E-mail: flq@mail.sioc.ac.cn
Supporting information for this article is given via a link at the end of the document.
Abstract: Pentafluorosulfanyl chloride (SF5Cl) is the most prevalent
reagent for the incorporation of SF5 group into organic compounds.
However, the preparation of SF5Cl often relied on hazardous reagents
and specialized apparatuses. Herein we described a safe and
practical synthesis of a bench-stable and easy-to-handle solution of
SF5Cl in n-hexane under gas-reagent-free conditions. The synthetic
application of SF5Cl was demonstrated through the unprecedented
reaction with diazo compounds. The chemoselective hydro- and
chloropentafluorosulfanylations of α-diazo carbonyl compounds were
developed in the presence of K3PO4 or copper catalyst respectively.
These reactions provide a direct and efficient access to various α-
pentafluorosulfanyl carbonyl compounds of high value for potential
applications.
reported in the patent literatures. Winter disclosed that the
reaction of dry KF, sulfur powder, and Cl2 in the presence of Br2
afforded SF5Cl in excellent yield.[13] Togni observed the formation
of SF5Cl from the mixture of sulfur powder, dry KF, and
trichloroisocyanuric acid (TCCA) in MeCN using trifluoroacetic
acid (TFA) as the catalyst.[14] Although Togni’s protocol is very
intriguing in terms of gas-reagent-free conditions, neither the yield
nor purification process of SF5Cl was provided. To develop a
synthetically useful method in common research laboratories, we
optimized Togni’s procedure (Scheme 1). It was found that the
catalytic amounts of TFA was not necessary for the formation of
SF5Cl,[6e] and the protection from light is crucial for this reaction.
The reaction of sulfur powder, dry KF, and TCCA in MeCN under
light only afforded the byproducts SO2F2 and SOF2, whereas
SF5Cl was formed in the absence of light along with SO2F2 and
SOF2. To our delight, SF5Cl was easily purified through simple
extraction with n-hexane. The resulting solution of SF5Cl in n-
hexane could be stored on the bench for months without
noticeable decomposition. Finally, the reaction was easily scaled
up in an average yield of 47% from 0.46 mmol[14] to 32 mmol.
The pentafluorosulfanyl (SF5) group, an unique octahedral
geometry around sulfur atom and a square pyramidal array of
fluorine atoms, has attracted increasing attention due to its
intriguing physicochemical properties, such as strong electron-
withdrawing capability, substantial steric hindrance, significant
lipophilicity, and high chemical stability.[1] It has been intensively
used as a bioisosteric replacement of the CF3 group in a multitude
of drug candidates.[2] Furthermore, the SF5 group is frequently
exploited in the development of new materials, especially in the
area of optoelectronic materials.[3] Recently, the application of SF5
group in the design of molecular catalysts has been developed.[4]
Consequently, the considerable advances have been made in the
introduction of the SF5 group into organic molecules in the past
decade.[5] To date, most of these synthetic methods focused on
the improvement of the fluorination process for the preparation of
SF5-substituted aromatic compounds[6] and transformation of SF5-
containing building blocks.[7] The synthesis of aliphatic
Scheme 1. Preparation of a solution of SF5Cl in n-hexane.
The reactions of SF5Cl mainly involve the atom-transfer
radical addition (ATRA) with unsaturated compounds, such as
alkenes (Scheme 2a)[8,15] and alkynes (Scheme 2b)[7f,16]. The
resulting chloropentafluorosulfanylated products are important
precursors for the preparation of other SF5-containing compounds.
The transformation of SF5Cl adducts formed from vinyl esters or
ethers is the common approach to α-SF5 aldehydes, ketones,
carboxylic acids, and esters (Scheme 2c).[7a,c,17] Recently, Paquin
developed a multistep synthesis of α-SF5 ketones starting from
the addition of SF5Cl to alkynes (Scheme 2d).[7f] These α-SF5
carbonyl compounds are valuable building block for further
diversification.[7c,d,18] To the best of our knowledge, there was only
one example of the direct synthesis of α-SF5 carbonyl compounds
from the addition of SF5Cl to ketene (Scheme 2e).[19] Inspired by
recent advances in radical addition reactions of diazo
compounds,[20] which are easily available and versatile
intermediates in organic synthesis,[21] herein we disclose the
pentafluorsulfanylated
pentafluorosulfanylation reactions was less developed probably
due to lack of efficient and easily available
compounds
through
direct
a
pentafluorosulfanylating reagents.
Among the reported pentafluorosulfanylating reagents,
pentafluorosulfanyl chloride (SF5Cl) is most extensively used in
terms of the balance between reactivity and stability.[8] Especially,
it is more stable than pentafluorosulfanyl bromide (SF5Br)[9] and
more reactive than sulfur hexafluoride (SF6)[10]. However, SF5Cl is
hardly commercially available, and its synthesis is difficult to
execute in common organic chemistry laboratories. Normally,
SF5Cl was prepared from the toxic and corrosive sulfur
tetrafluoride (SF4) in an autoclave.[11,12] Recently, more
convenient synthetic methods without the use of SF4 were
1
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10.1002/anie.202103606
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unprecedented reaction of SF5Cl with diazo compounds. This
protocol enables the direct and facile access to α-SF5 ketones and
esters for the first time. Notably, the hydro- and
chloropentafluorosulfanylated products were chemoselectively
formed in the presence of base (Scheme 2f) or copper catalyst
(Scheme 2g), respectively.
was harmful to this reaction, probably due to the competing
electrophilic chlorination reaction.[24] Notably, terminal alkenyl-
and alkynyl-substituted substrates were not suitable for this
reaction. Sterically hindered (1j) and polysubstituted (1k)
substrates furinshed the desired products in moderate yields. α-
Diazoesters 1l and 1m were also compatible with the reaction
conditions. Dehydroepiandrosterone-derived substrate 1n
underwent the reaction smoothly, delivering 2n in 56% yield. The
reaction of 1a was scaled up to 1.25 mmol without erosion of the
yield.
Scheme 2. Preparation of α-SF5 carbonyl compounds with SF5Cl.
Initially, 2-diazo-1-phenylethanone (1a) was chosen as the
model substrate to react with SF5Cl under Et3B-catalyzed
conditions developed by Dolbier in 2002.[22] However, no SF5-
containing product was observed (Scheme 3a). Unexpectedly,
the reaction of 1a and SF5Cl in DCM without any additive afforded
the
hydropentafluorosulfanylated
product
α-
pentafluorosulfanylketone (2a), α-chloroketone (3a), and other
byproducts (Scheme 3b). The expected ATRA-type
chloropentafluorosulfanylated product was not formed.
Encouraged by this result, the reaction conditions were optimized
to improve the yield of 2a (see the Supporting Information).
Previous studies showed that the byproduct 3a was presumably
formed from the reaction of 1a and in situ generated HCl.[23]
Consequently, different bases were added to suppress the
formation of 3a. To our delight, the addition of K3PO4 afforded 2a
in 51% yield, and no 3a was detected (Scheme 3c).
Scheme 4. Substrate scope of hydropentafluorosulfanylation of diazo
compounds. Reaction conditions: 1 (0.1 mmol), SF5Cl (0.15 mmol), K3PO4 (0.15
mmol), DCM (2.0 mL), N2, rt, 3 h, isolated yields. [a] Reaction was performed
on a 1.25 mmol scale. [b] Reaction time 12 h. [c] 1 (0.15 mmol), SF5Cl (0.1
mmol).
To
gain
insight
into
the
reaction,
mechanism
several
of
control
the
hydropentafluorosulfanylation
experiments were performed. When ethynylbenzene was added
to the standard reaction of 1a, the hydropentafluorosulfanylated
product 2a was not formed, whereas ethynylbenzene-derived
chloropentafluorosulfanylated product 4 was obatined in low yield
(Scheme 5a). These results indicated that SF5 radical was
probably generated as the key intermediate and the reaction of
SF5 radical with alkynes should be faster than that with diazo
compounds. Furthermore, the deuteration experiments were
performed in DCM-d2 (Scheme 5b) or using a solution of SF5Cl in
n-hexane-d14 (Scheme 5c), respectively. The deuterated product
[D]2a was observed in the presence of n-hexane-d14,
demonstrating that n-hexane acts as a hydrogen atom donor.
Notably, a chlorination product from n-hexane was also detected
in the reaction mixture, which supports the formation of hexyl
radical. On the basis of the above results and previous reports,[5,20]
a plausible reaction mechanism for hydropentafluorosulfanylation
of diazo compounds was proposed in Scheme 5d. Initially, SF5
radical is generated from SF5Cl by the reaction with diazo
compounds 1[25] or photo-irradiation. Then, the addition of SF5
Scheme 3. Reaction of 1a and SF5Cl.
Then, the substrate scope of hydropentafluorosulfanylation of
diazo compounds with SF5Cl was examined (Scheme 4). α-
Diazoketones 1b-i bearing electron-withdrawing groups reacted
efficiently to afford the corresponding products in moderate to
excellent yields. The substituents including ester (1b), nitrile (1c),
halogen (1d-h), and trifluoromethyl (1i) at different positions of the
aromatic ring were all well tolerated. The presence of electron-
donating groups, such as alkoxyl and amino, on the phenyl ring
2
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radical to diazo compounds 1 gives radical intermediate A, which
releases of one molecule of N2 to afford radical intermediate B.
The presence of adjacent electron-withdrawing SF5 and carbonyl
groups makes radical B highly electrophilic. Thus, the abstraction
of electrophilic Cl atom from SF5Cl by electrophilic radical B is
unfavorable. Instead, radical B abstracts hydrogen atom from n-
hexane to furnish the hydropentafluorosulfanylated products 2.
On the other hand, hexyl radical is formed, and then reacts with
SF5Cl to give chlorohexane and SF5 radical.
several transition metal catalysts including FeCl2, CoCl2, NiCl2,
and CuCl2 were added to the reaction mixture (Table 1, entries 1-
4). Only the reaction in the presence of CuCl2 afforded the desired
chloropentafluorosulfanylated product 5a in low yield, along with
the hydropentafluorosulfanylated product 2a (entry 4). Further
screening of different copper catalysts demonstrated that
Cu(MeCN)4PF6 led to the selective formation of 5a (entries 5-8).
Subsequently, a variety of N,N-bidentate ligands including 2,2'-
bipyridine (L1), 1,10-phenanthrolines (L2-8) were employed
(entries 9-16). Pleasingly, all of them promoted the desired
chloropentafluorosulfanylation reaction. Among them, ligand L7
was optimal to give 5a in 84% yield (entry 15).
Table 1. Optimization of the reaction conditions[a]
Entry
Catalyst
Ligand
Yield (2a/5a, %)[b]
1
FeCl2
―
―
―
―
―
―
―
―
L1
L2
L3
L4
L5
L6
L7
L8
5/0
2
CoCl2
0/0
3
NiCl2
3/0
4
CuCl2
11/2
17/trace
17/0
10/trace
0/5
5
Cu(OAc)2
Scheme 5. Investigations of hydropentafluorosulfanylation reaction.
6
Cu(acac)2
7
CuCl
8
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
Cu(MeCN)4PF6
9
0/42
0/45
0/74
0/44
0/78
0/31
0/84
0/60
10
11
12
13
14
15
16
[a] Reaction conditions: 1a (0.2 mmol), SF5Cl (0.1 mmol), catalyst (0.01 mmol),
ligand (0.012 mmol), DCM (2.0 mL), N2, rt, 3 h. [b] Yields determined by 19F
NMR spectroscopy using trifluoromethylbenzene as an internal standard.
Scheme 6. Transition-metal-catalyzed polarity reversal strategy for
chloropentafluorosulfanylation reaction.
The
substrate
scope
of
copper-catalyzed
chloropentafluorosulfanylation of diazo compounds was also
investigated. As shown in Scheme 7, a range of diazo compounds
1 were converted to the chloropentafluorosulfanylated products 5
in moderate to excellent yields. In general, the yields are higher
than those of hydropentafluorosulfanylation reactions. The mild
conditions allow the tolerance of both of electron-withdrawing and
electron-donating group. Heteroaryl (1p,q) and alky (1r) ketone
derivatives were also suitable substrates. Furthermore, α-
diazosulfone 1s underwent the reaction smoothly to give 5s in 54%
yield. However, other diazo compounds, such as diaryl
To
overcome
the
challenges
for
the
chloropentafluorosulfanylation of diazo compounds and inspired
by recent progress in transition-metal-catalyzed ATRA
reactions,[26,27] a transition-metal-catalytic strategy for the reaction
of SF5Cl with diazo compound was proposed in Scheme 6. We
reasoned that the single electron transfer (SET) reaction of SF5Cl
and MXLn would afford SF5 radical and ClMXLn. In this process,
the polarity of Cl atom is reversed, thus enabling the transfer of Cl
atom from ClMXLn to electrophilic radical B for the formation of
chloropentafluorosulfanylated products 5. To test our hypothesis,
3
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diazomethanes, failed to yield the desired products. The structure
of 5f was confirmed by X-ray crystallographic analysis.
This work represents the rare examples of 1,1-difunctionalized
pentafluorosulfanylation reactions and affords the direct synthetic
route to the valuable α-pentafluorosulfanyl carbonyl compounds.
Acknowledgements
National Natural Science Foundation of China (21421002,
21991211) and the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDB20000000) are greatly
acknowledged for funding this work.
Conflict of interest
The authors declare no conflict of interest.
Keywords: pentafluorosulfanylation • diazo compounds •
pentafluorosulfanyl chloride • copper • radical reactions
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Scheme 7. Substrate scope of chloropentafluorosulfanylation of diazo
compounds. Reaction conditions:
1 (0.2 mmol), SF5Cl (0.1 mmol),
[5]
[6]
Cu(MeCN)4PF6 (0.01 mmol), L7 (0.012 mmol), DCM (2.0 mL), N2, rt, 3 h,
isolated yields. [a] Reaction was performed on a 1.25 mmol scale.
Finally, the transformation of previously unknown α-chloro-α-
pentafluorosulfanyl carbonyl compounds
5 was launched.
Reduction of α-pentafluorosulfanylketone 5a with LiAlH4 afforded
the corresponding alcohol 6 in 57% yield (Scheme 8a). Treatment
of α-pentafluorosulfanylester 5l with Cy2BCl/Et3N, followed by
chlorination
with
N-chlorophthalimide
(NCP)
gave
pentafluorosulfanyldichloroacetate 7 in 54% yield (Scheme 8b).
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initiation of the reaction with SF5Cl, see: a) J. R. Case, N. H. Ray, H. L.
Roberts, J. Chem. Soc. 1961, 2066; b) M. V. Ponomarenko, Y. A.
Serguchev, G.-V. Röschenthaler, J. Fluorine Chem. 2010, 131, 270.
[26] For selected examples of Cu-catalyzed ATRA reactions, see: a) X.-J.
Tang, W. R. Dolbier, Jr., Angew. Chem. Int. Ed. 2015, 54, 4246; Angew.
Chem. 2015, 127, 4320; b) D. B. Bagal, G. Kachkovskyi, M. Knorn, T.
Rawner, B. M. Bhanage, O. Reiser, Angew. Chem. Int. Ed. 2015, 54,
6999; Angew. Chem. 2015, 127, 7105; c) Z. Liu, H. Chen, Y. Lv, X. Tan,
H. Shen, H.-Z. Yu, C. Li, J. Am. Chem. Soc. 2018, 140, 6169.
[16] For recent examples, see: a) W. R. Dolbier, Jr., Z. Zheng, J. Org. Chem.
2009, 74, 5626; b) M. V. Ponomarenko, N. Kalinovich, Y. A. Serguchev,
M. Bremer, G.-V. Röschenthaler, J. Fluorine Chem. 2012, 135, 68; c) A.
Gilbert, M. Birepinte, J.-F. Paquin, J. Fluorine Chem. 2021, 243, 109734.
[17] a) W. R. Dolbier, Jr., S. Aït-Mohand, T. D. Schertz, T. A. Sergeeva, J. A.
Cradlebaugh, A. Mitani, G. L. Gard, R. W. Winter, J. S. Thrasher, J.
Fluorine Chem. 2006, 127, 1302; b) H. Martinez, Z. Zheng, W. R. Dolbier,
Jr., J. Fluorine Chem. 2012, 143, 112.
[18] For selected examples, see: a) S. C. Ngo, J.-H. Lin, P. R. Savoie, E. M.
Hines, K. M. Pugliese, J. T. Welch, Eur. J. Org. Chem. 2012, 4902; b) A.
L. Dreier, A. V. Matsnev, J. S. Thrasher, G. Haufe, J. Fluorine Chem.
2014, 167, 84; c) P. Dudziński, A. V. Matsnev, J. S. Thrasher, G. Haufe,
J. Org. Chem. 2016, 81, 4454; d) M. V. Ponomarenko, S. Grabowsky, R.
Pal, G.-V. Röschenthaler, A. A. Fokin, J. Org. Chem. 2016, 81, 6783; e)
[27] For selected examples of other transition metal-catalyzed ATRA
reactions, see: a) T. Xu, C. W. Cheung, X. Hu, Angew. Chem. Int. Ed.
2014, 53, 4910; Angew. Chem. 2014, 126, 5010; b) B. Chen, C. Fang, P.
Liu, J. M. Ready, Angew. Chem. Int. Ed. 2017, 56, 8780; Angew. Chem.
2017, 129, 8906; c) G. Wu, A. J. von Wangelin, Chem. Sci. 2018, 9, 1795.
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10.1002/anie.202103606
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A practical synthesis of SF5Cl from sulfur powder, dry KF, and trichloroisocyanuric acid (TCCA) in MeCN is described. The new
synthetic utility of SF5Cl is well demonstrated by the chemoselective hydro(chloro)pentafluorosulfanylation of diazo compounds.
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