A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for aerobic oxidation of alcohols

Article abstract of DOI:10.1039/d0cc05799a

A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for the aerobic oxidation of alcohols has been developed for the first time, and the photoredox aerobic oxidation of secondary and primary alcohols provided the corresponding ketones and carboxylic acids, respectively, in high to excellent yields.

Full text of DOI:10.1039/d0cc05799a

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DOI: 10.1039/D0CC05799A
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A sodium trifluoromethanesulfinate-mediated photocatalytic
strategy for aerobic oxidation of alcohols
Xianjin Zhu, Can Liu, Yong Liu, Haijun Yang and Hua Fu*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
7
A
sodium trifluoromethanesulfinate-mediated photocatalytic alternatives to the conventional catalytic strategies, and some
strategy for the aerobic oxidation of alcohols has been developed photocatalytic aerobic oxidations of alcohols to carbonyl
8
for the first time, and the photoredox aerobic oxidation of compounds have been developed (Scheme 1c). However, most
secondary and primary alcohols provided the corresponding organic compounds do not absorb light in the visible light region
ketones and carboxylic acids, respectively, in high to excellent (400-800 nm), so use of photocatalysts is necessary to realize
9
yields.
the organic reactions. The common photocatalysts are the
7
b,7c,10-12
expensive and toxic transition metal complexes
and
which restricts photochemical
widespread applications for high cost.
The functions of organic compounds are highly dependent on
their functional groups, so the transformation of functional
groups is one of the most important chemical processes in
organic chemistry. Alcohols are ubiquitous in nature and
chemical field, and ketones and carboxylic acids are key
chemicals and intermediates in the synthesis of diverse organic
13-16
elaborate organic dyes,
OH
O
(a)
traditional oxidants
R1
R2
R1
R2
(b)
OH
R2
O
transition-metal catalysts
air or O2
R1
R2
R1
O
R1
1
compounds. Therefore, the selective oxidation of alcohols
represents one of the most addressed problems in organic
synthesis. However, the traditional methods for oxidation of
alcohols often use stoichiometric amount of environmentally
unfriendly oxidants (Scheme 1a) such as metal oxides, methyl
hypervalent iodine,2 sulfoxides, and peroxides.
contrast, molecular oxygen including oxygen and air is
economic and environmentally benign oxidant. However,
molecular oxygen in the ground state is inactive to organic
transition-metal photocatalysts
or organic photocatalysts
(
c)
O
OH
R1
R2
R2
hv, air or O2
2
2a
(d)
b,2c
2d
2e,2f
OH
In sharp
O
S
R1
R2
R1
R2
F3C
ONa
or
or
R1 COOH
O2 or air, LED, rt
R1
OH
this work
substrates, so it should previously be activated to transform Scheme 1 Oxidation of alcohols to carbonyl compounds.
into reactive oxygen species such as singlet oxygen, superoxide
anion radical, hydrogen peroxide, and hydroxy radical.
Although many catalytic aerobic oxidations of alcohols to the
Very recently, we have developed a light and oxygen-enabled
3
sodium trifluoromethanesulfinate-mediated selective oxidation
1
7
of C-H bonds. Inspired by the results above, we had speculated
that the sodium trifluoromethanesulfinate photocatalytic
system could promote aerobic oxidation of alcohols to carbonyl
compounds (Scheme 1d). A detailed description of our
suggested mechanistic photocatalytic cycle is shown in Figure 1.
We imagined that initial light-irradiation of pentacoordinate
sulfide intermediate 4 would yield the photoexcited state 4*,
corresponding carbonyl compounds have been developed, the
expensive and toxic transition metal catalysts, such as
4
5
6a,b
6c
ruthenium, palladium copper
and cobalt complexes are
usually required (Scheme 1b). Over the past decades, the
photocatalytic organic reactions have attracted great attention
because they are atom-economic and environmentally friendly
and energy transfer (ET) bettwen 4* and molecular oxygen
1
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology
would regenerate 4 releasing singlet oxygen O
(5). Single-
2
(Ministry of Education), Department of Chemistry, Tsinghua University, Beijing
electron transfer (SET) of 4* to oxygen would produce radical 6
and superoxide anion radical 7. Abstraction of the hydrogen
atom at the same carbon of hydroxyl in 1 by 6 would lead to an
1
00084, P. R. China. E-mail: fuhua@mail.tsinghua.edu.cn
1
7
†
Electronic Supplementary Information (ESI) available: Synthetic procedures,
mechanism investigations, characterization data and NMR spectra of the
synthesized compounds. See DOI: 10.1039/x0xx00000x
8
α-hydroxyl radical 8 releasing 9, and exchange of the proton in
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COMMUNICATION
Journal Name
+
9
7
with Na would regenerate photocatalyst 4. Reaction of 8 with this transformation. Subsequently, the secondary alcohols
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in the presence of a proton would give an α-hydroxy peroxyl containing two aryl groups were investigaDtOedI:,1a0n.1d03t9h/eDy0CaCff0o5r7d9e9dA
radical 10, and desorption of hydroperoxide from 10 would excellent yields under the standard conditions (see 2y-2al, 86-
provide the target product (2). Meanwhile, treatment of 8 with 100% conversion yields). However, the substrates containing
O or 5 would afford radical 10', and then reaction of 10' with 1 methyl on the aryl rings gave slightly low yields because of
2
would form intermediates 8 and 10 mentioned above.
oxidation of small amounts of methyl to carboxyl (see 2z and
aa, 88% and 86% conversion yields, respectively). Next, the
2
*
F
O
F
photocatalytic aerobic oxidations of aliphatic secondary
alcohols including acyclic and cyclic alcohols were surveyed, and
they were also suitable substrates giving the corresponding
products (see 2am-2as) in excellent conversion yields (92-99%).
Gratifyingly, the present reaction could tolerate various
ONa
S
F
O
O
hv
4*
O2
O2
7
1O2
detected by EPR
5
detected by EPR
O2
F
O
S
F
O
O
O
O
S
O O
6
F
O2
F
functional groups including ether, CF and nitro groups, C-F, C-
ONa
F
F
Na
R1
R2
3
S
F
hv
NaO
F
2
O
O
F
Cl and C-Br bonds and N- and O-heterocycles.
4
3a
-
H2O2
OH
CF3SO2Na (3a, 5 mol%)
OH
R2
O
HO OOH
R1 R2
Na+
R1
R2
O2 or air (1 atm.)
+
1
R1
R1
R2
H+
-
F
10
LED (400-405 nm)
CH CN, rt, 12 h
3
O
2
F
8
1
OH
S
F
O
O
O2
+ H+
Synthesis of arylalkyl ketones
O
1
9
O
a, 100% (87%)
H3CO
O
O
O
O
OH
HO OO
R1
R1
R2
R2
8
H3C
2b , 96% (85%)
tBu
H3CO
H3CO
OCH3
10'
OCH3
1O2 or O2
2
a
2c, 95% (83%)
2d , 93% (85%) 2e , 93% (84%)
b
b
2fb, 81% (75%)
O
O
O
O
O
O
Figure 1 Proposed mechanistic pathway of photocatalytic aerobic
oxidation of alcohols (1) to carbonyl compounds (2).
F
F
Cl
OCH3
F
Cl
gb, 72% (65%)
2h, 100% (89%) 2i, 100% (90%)
2j, 100% (89%)
2k, 98% (86%)
2l, 99% (88%)
2
To verify our hypothesis in Figure 1, aerobic oxidation of 1-(4-
fluorophenyl)ethanol (1h) to 1-(4-fluorophenyl)ethanone (2h)
was used as the model to optimize conditions, and the results
showed that optimal conditions for the photoredox aerobic
oxidation of secondary alcohols to ketones were as follows: 5-
O
O
O
O
O
O
Br
Br
2n, 100% (91%) 2o, 98% (89%)
F
Br
F3C
2q, 99% (90%)
Br
2m, 91% (80%)
2p, 95% (83%)
2rc, 93% (84%)
O
O
O
O
O
O
2
5 mol% of sodium trifluoromethanesulfinate (3a) as the
precursor of photocatalyst, MeCN or DMF as the solvent, LED
400-405 nm) as the light source under oxygen or air
N
H3CO
2ub, 100% (93%)
O
2sc,d, 98% (93%) 2t, 100% (89%)
2v, 100% (94%)
2wc, 87% (79%) 2xc, 87% (82%)
(
Synthesis of diaryl ketones
O
O
O
O
atmosphere (1 atm.) at room temperature for 12 h (see Tables
S1-S7 in ESI for details). Subsequently, substrate scope for the
sodium trifluoromethanesulfinate-mediated photocatalytic
aerobic oxidation of secondary alcohols was investigated. As
shown in Scheme 2, a myriad of secondary alcohols containing
an aryl and an alkyl were first investigated. In general, all the
substrates could smoothly perform this aerobic oxidation under
the standard conditions giving the corresponding ketones in
high to excellent yields (see 2a-2x, 72-100% conversion yields)
with good functional group tolerance. The substrates containing
methoxyl groups on aryl rings needed 25 mol% sodium
trifluoromethanesulfinate (3a) as the precursor of
photocatalyst and DMF as the solvent (see 2d-2g and 2u, 72-
CH3
CH3
H3C
CH3
H3CO
2
y, 100% (93%)
2z, 88% (85%)
2aa, 86% (81%)
2ab, 98% (91%)
O
O
O
O
O
H3CO
OCH3
F
F
F
F
Cl
2ac, 98% (92%)
2ad, 100% (92%)
2ae, 99% (90%)
2af, 98% (88%)
2ag, 100% (91%)
O
O
O
O
O
Cl
Cl
Cl O N
2
O
2
ah, 96% (88%)
2ai, 94% (86%)
2ajc, 100% (94%)
2ak, 100% (91%)
2al, 100% (95%)
Synthesis of dialkyl ketones
O
O
O
O
O
c
2an, 97% (71%)
2ao, 95% (73%)
2ap, 98% (68%)
2aq, 99% (77%)
2
am , 99% (75%)
O
O
1
00% conversion yields), and those containing two methoxyl
groups on aryl rings provided lower yields (see 2f and 2g, 75 and
2% conversion yield, respectively). Notably, aerobic oxidation
2
ar, 99% (81%)
2as, 92% (86%)
Scheme 2 Substrate scope for the photocatalytic aerobic oxidation of
7
secondary alcohols (1) to ketones (2). Reaction conditions: under O
2
or
of 1-(p-tolyl)ethanol (1b) in MeCN gave small amount of 4-
acetylbenzoic acid (about 30% conversion yield), while the
reaction in DMF afforded 1-(p-tolyl)ethanone (2b) in 96%
conversion yield without 4-acetylbenzoic acid appearing.
Moreover, the substrate containing a pyridyl that was subjected
to the reaction under LED (400-405 nm) irradiation exhibited
lower reactivity, and a 98% conversion yield was provided under
irradiation of LED (380-385 nm) (see 2s). It should be noted that
no obvious steric effect and electronic effect were observed for
air atmosphere (1 atm.), secondary alcohol (1) (0.1 mmol), CF
3
SO
2
Na
o
(
3a) (5 mol%), MeCN (1.0 mL), room temperature (~25 C), time (12 h)
in a sealed tube under irradiation of 3 W LED (400-405 nm). The
conversion yields were determined by GC-MS using dodecane as the
a
internal standard (isolated yields in the parentheses). Using DMF (1.0
b
mL) as the solvent. Using DMF (1.0 mL) as the solvent in the presence
c
of 25 mol% CF
dUsing 3 W LED (380-385 nm) as the light source.
3
SO
2
Na (3a). In the presence of 10 mol% CF
3
SO
2
Na (3a).
2
| J. Name., 2012, 00, 1-3
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COMMUNICATION
(A) Aerobic oxidation of the natural products
O
4
Ba), which indicated that oxygen plays an important role in this
OH
View Article Online
DOI: 10.1039/D0CC05799A
O
H
transformation; (b) After irradiation of 3a in acetonitrile with 3
W LED (400-405 nm) for 8 h under oxygen atmosphere, FNMR
H
H
H
H
19
H
H
H
H
O
HO
O
H
17
H
H
3a (10 mol%)
O2 (1 atm.)
2at (87% from 11a)
(85% from 11b)
79% from 11c)
spectrum showed 3a was converted into 4, then 1h was added
to the system, and a continued irradiation under the same
condition for 8 h provided 2h in a quantitative conversion yield
(Scheme 4Bb). The result indicated that 4 could be the actual
photocatalyst for this transformation; (c) As shown in Scheme
Epiandrosterone (11a)
Stanolone (11b)
(
3
W LED
400-405 nm)
CH3CN, rt, 12 h
OH
OH
O
(
H
H
H
H
H
H
H
H
H
HO
Dihydro-androsterone (11c)
O
O
H
Testosterone (11d)
2au (82% from 11d)
4
Bc, the reaction did not work in the presence of 2,2,6,6-
(
B) Synthesis of drug Fenofibrate
O
tetramethyl-1-piperidinyloxy (TEMPO) as the radical scavenger,
which showed that a radical pathway can be involved in the
transformation in Scheme 2. (C) To further understand the role
of O for the reaction, isotopic labelling experiment was carried
2
out (Scheme 4C). When O
OH
Cl
OH
Cl
11e
OH
2ba, 76%
O
Br
O
CF3SO2Na (10 mol%)
O2 (1 atm)
18
16
12
2
replaced O
2
as the oxygen source,
KHCO3, iPrOH
LED (400-405 nm)
CH3CN, rt, 12 h
16
refluxing for 48 h
2h containing O-carbonyl was a dominated product, which
indicated that oxygen of carbonyl in 2h was from hydroxyl of 1h
9
0%
83% yield
OH
O
2
rather than O . Based on the experiments above, we
rationalized that the proposed mechanism in Figure 1 is
reasonable.
O
O
Cl
O
Cl
O
11f
O
Fenofibrate (2bb)
O
Scheme 3 Applications of our method in late-stage modifications of
natural products and synthesis of fenofibrate (2bb).
(
A) Determination of reactive oxygen species by EPR
(
a) EPR experiments for singlet oxygen
(b) EPR experiments for superoxide radical anion
dark
light for 10 min
light for 22 min
light for 30 min
light for 35 min
light for 40 min
light for 44 min
To further demonstrate the utility of this protocol, we
performed the late-stage modifications of four natural products
dark
light for 2 min
light for 4 min
light for 6 min
(
Scheme 3A). To our delight, the biologically relevant natural
1
8
products (epiandrosterone (11a), stanolone (11b), dihydro-
androsterone (11c) and testosterone (11d)) underwent the
selective aerobic oxidation giving the corresponding ketones
(
2at and 2au) in high yields (79-87%). Finally, we prepared an
1
9
effective marketed hypolipidemic drug, fenofibrate (2bb) by
320
322
324
326
319 320 321 322 323 324 325 326
Megnetic Field (mT)
Megnetic filed (mT)
using the present method (Scheme 3B). Aerobic oxidation of
1
1
1e provided ketone 2ba in 76% yield, and coupling of 2ba with
2 in the presence of base gave fenofibrate (2bb) in 90% yield.
(
B) Control experiments
(a)
OH
O
CF3SO2Na (25 mol%)
CF3SO2Na (25 mol%)
The other route is aerobic oxidation of 11f leading to 2bb in 83%
yield.
Ar (1 atm.)
O2 (1 atm.)
no reaction
LED (400-405 nm)
CH3CN, rt, 12 h
1h
LED (400-405 nm)
CH3CN, rt, 12 h
F
2h
F
0
.2 mmol
100%
OH
To explore reaction mechanism on the sodium
trifluoromethanesulfinate-mediated photocatalytic aerobic
oxidation of secondary alcohols (1) to ketones (2), some
experiments were carried out as follows: (A) To confirm the
species of active oxygen involved in the aerobic oxidation, we
performed the electron paramagnetic resonance (EPR)
O
(
b)
O2 (1 atm.)
CH3CN (2 mL), rt, 8 h
1h
O
S
O
F
F3C
S
ONa
O
0.2 mmol
F3C
ONa
LED (400-405 nm)
F
2h
3a
O
O2 (1 atm.), rt, 12 h
LED (400-405 nm)
1
00%
0
.05 mol
4
OH
O
(c)
F
CF3SO2Na (25 mol%)
O2 (1 atm.)
1h
TEMPO (3.0 eq.)
LED (400-405 nm)
CH3CN, rt, 12 h
F
2h
0%
0
.2 mmol
experiments.
trifluoromethanesulfinate
tetramethylpiperidin-4-one (TMPD) as the trapping agent of O
When
a
solution
(3a)
of
sodium
(d)
OH
O
and
2,2,6,6-
CF SO Na (50 mol%)
3
3
O2 (1 atm.)
1
2
1h
LED (400-405 nm)
CH3CN, rt, 12 h
F
2h
F
0.2 mmol
0%
in acetonitrile was irradiated with full wavelength light (400-700
(C) 18O labelling experiment
OH
nm) under oxygen atmosphere, we found that the characteristic
16O
18O
1
signal of O
2
adduct with TMPD gradually became strong with
CF SO Na (25 mol%)
3
2
18O2 (1 atm.)
+
extension of irradiation time (Scheme 4Aa); When solution of
F
F
LED (400-405 nm)
CH3CN, rt, 12 h
F
1h
2h
total yield: 100%
h/2h' = 88:12
2h'
0
.2 mmol
3
a and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as the
2
•-
trapping agent of O
2
in acetonitrile was irradiated with the full
Scheme 4 Investigations on mechanism for the photocatalytic aerobic
oxidation of secondary alcohols (1) to ketones (2).
wavelength light under oxygen atmosphere, we also observed a
•-
characteristic signal of O
2
adduct with DMPO (Scheme 4Ab).
Inspired by the excellent results above, we next investigated
photocatalytic aerobic oxidation of primary alcohols to
carboxylic acids. As shown in Scheme 5, arylmethanols were
first attempted as the substrates, and the corresponding aryl
formic acids were obtained in high to excellent yields with good
functional group tolerance (see 13a-13j, 81-96% yields). Three
(
B) Several control experiments were conducted as follows: (a)
No reaction occurred when 1-(4-fluorophenyl)ethanol (1h) was
treated under argon atmosphere instead of oxygen
atmosphere, and the subsequent reaction under oxygen
atmosphere gave 2h in a quantitative conversion yield (Scheme
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Page 4 of 4
COMMUNICATION
Journal Name
The authors would like to thank the National NaVtieuwraAlrtiSccleieOnnlcinee
heteroarylmethanols,
pyridin-4-ylmethanol,
pyridin-2-
ylmethanol and thiophen-2-ylmethanol, were attempted as the Foundation of China (Grant No. 217721D0O8I): 1a0n.1d039N/aDt0iCoCn0a5l7K9e9Ay
substrates, and the first two substrates provided excellent R&D Program of China (2016YFD0201207) for financial support.
yields (see 13k and 13l, 90% and 98% yields, respectively).
However, thiophen-2-ylmethanol only gave 56% yield because
of presence of sulfur atom (see 13m). Subsequently, two
Conflicts of interest
aliphatic primary alcohols were used in the photocatalytic
aerobic oxidation, and they also provided the satisfactory
results (see 13n and 13o, 62% and 72% yields, respectively).
There are no conflicts to declare.
Therefore, our sodium trifluoromethanesulfinate-mediated Notes and references
photocatalytic strategy is very useful method for the aerobic
oxidation of primary alcohols to carboxylic acids.
1
2
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O2 or air (1 atm.)
R
OH
R
COOH
12
LED (400-405 nm)
CH3CN, rt, 12 h
13
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MeO
COOH
COOH
COOH
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F
Cl
Br
1
3a, 96%
13b, 92%
COOH
Br
13c, 95%
COOH
O N
13d, 93%
COOH
13e, 95%
COOH
COOH
5
6
F3C
2
Br
1
13h, 91%
13g, 91%
13i, 92%
13j, 81%
3f, 89%
COOH
COOH
COOH
COOH
a
N
N
13n , 62%
S
1
3k, 90%
13l, 98%
13m, 56%
COOH
a
1
3o , 72%
7
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Scheme 5 Substrate scope for the photocatalytic aerobic oxidation of
primary alcohols (12) to carboxylic acids (13). Reaction conditions:
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Xiao, Angew. Chem., Int. Ed., 2012, 51, 6828–6838; (g) Y. Chen, L.-Q. Lu,
D.-G. Yu, C.-J. Zhu and W.-J. Xiao, Sci. China Chem., 2019, 62, 24–57; (h)
J. Wang, B. Li, L.-C. Liu, C. Jiang, T. He and W. He, Sci. China Chem., 2018,
under O
CF SO
2
or air atmosphere (1 atm.), primary alcohol (12) (0.1 mmol),
o
3
2
Na (3a) (10 mol%), MeCN (1.0 mL), room temperature (~25 C),
time (12 h) in a sealed tube under irradiation of LED (400-405 nm).
a
Isolated yields. Time (48 h).
6
1, 1594–1599.
Finally, we surveyed the photocatalytic aerobic oxidation of
alcohol 14 containing two different kinds of hydroxyls (Scheme
), and product 15 containing a carbonyl and a carboxyl was
obtained in 87% isolated yield. The result showed that our
method was very practical for synthesis of multi-functional
compounds.
8
For selected two reviews, see: (a) X. Lang, W. Ma, C. Chen, H. Ji and J.
Zhao, Acc. Chem. Res., 2014, 47, 355−363; (b) X. Cheng, X. Hu and Z. Lu,
Chin. J. Org. Chem., 2017, 37, 251–266; For representative examples of
photoinduced alcohol oxidation, see: (c) Y. Chen, Z. U. Wang, H. Wang, J.
Lu, S. Yu and H. Jiang, J. Am. Chem. Soc., 2017, 139, 2035−2044; (d) Q.
Wang, M. Zhang, C. Chen, W. Ma and J. Zhao, Angew. Chem., Int. Ed.,
6
2
010, 49, 7976-7979; (e) F. Su, S. C. Mathew, G. Lipner, X. Fu, M.
Antonietti, S. Blechert and X. Wang, J. Am. Chem. Soc., 2010, 132, 16299-
6301; (f) N. F. Nikitas, D. I. Tzaras, I. Triandafillidi and C. G. Kokotos,
CF3SO2Na (3a, 10 mol%)
OH
COOH
1
O2 (1 atm.)
HO
O
Green Chem., 2020, 22, 471–477; (g) A. H. Tolba, F. Vávra, J. Chudoba and
R. Cibulka, J. Org. Chem., 2020, 85, 1579–1585.
LED (400-405 nm)
CH3CN, rt, 12 h
1
4
0
.2 mmol
15, 87%
9
(a) D. A. Nicewicz and D. W. C. MacMillan, Science, 2008, 322, 77–80; (b)
M. A. Ischay, M. E. Anzovino, J. Du and T. P. Yoon, J. Am. Chem. Soc., 2008,
130, 12886–12887; (c) J. M. R. Narayanam, J. W. Tucker and C. R.
Stephenson, J. Am. Chem. Soc., 2009, 131, 8756–8757.
Scheme 6 Photocatalytic aerobic oxidation of alcohol containing two
different kinds of hydroxyls.
In summary, we have developed a highly efficient sodium
trifluoromethanesulfinate-mediated photocatalytic aerobic
oxidation of alcohols for the first time and found that the in-situ
formed pentacoordinate sulfide derived from sodium
trifluoromethanesulfinate and oxygen acted as the 13 N. A. Romero and D. A. Nicewicz, Chem. Rev., 2016, 116, 10075–10166.
photocatalyst. The photoredox aerobic oxidation of secondary 14 D. Ravelli, M. Fagnoni and A. Albini, Chem. Soc. Rev., 2013, 42, 97–113.
and primary alcohols provides the corresponding ketones and
carboxylic acids, respectively, in high to excellent yields. We
believe that the efficient and practical method will be widely 17 X. Zhu, Y. Liu, C. Liu, H. Yang and H. Fu, Green Chem., 2020, 2, 4357-4363.
1
1
1
0
1
2
S. Poplata, A. Tröster, Y.-Q. Zou and T. Bach, Chem. Rev., 2016, 116, 9748–
9815.
K. L. Skubi, T. R. Blum and T. P. Yoon, Chem. Rev., 2016, 116, 10035–
1
0074.
R. N. Perutz and B. Procacci, Chem. Rev., 2016, 116, 8506–8544.
1
1
5
6
D. A. Nicewicz and T. M. Nguyen, ACS Catal., 2014, 4, 355–360.
E. Arceo, E. Montroni and P. Melchiorre, Angew. Chem., Int. Ed., 2014,
5
3, 12064–12068.
1
8
F. G. Cirujano, I. Luz, M. Soukri, C. Van Goethem, I. F. J. Vankelecom, M.
Lail and D. E. De Vos, Angew. Chem., Int. Ed., 2017, 56, 13302–13306.
K. McKeage and G. M. Keating, Drugs, 2011, 71, 1917−1946.
used in organic synthesis.
1
9
4
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