Regioselective installation of fluorosulfate (-OSO2F) functionality into aromatic C(sp2)-H bonds for the construction of: Para-amino-arylfluorosulfates

Article abstract of DOI:10.1039/c9cc02659b

The construction of para-amino-arylfluorosulfates was achieved through installation of fluorosulfate (-OSO₂F) functionality into aromatic C(sp²)-H bonds by the reaction of N-arylhydroxylamine with sulfuryl fluoride (SO₂F

Full text of DOI:10.1039/c9cc02659b

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C9CC02659B
COMMUNICATION
Regioselective installation of fluorosulfate (-OSO2F) functionality
into aromatic C(sp2)–H bonds for the construction of para-amino-
arylfluorosulfates
Received 00th January 20xx,
Accepted 00th January 20xx
Wan-Yin Fang, Gao-Feng Zha, Chuang Zhao, and Hua-Li Qin*
DOI: 10.1039/x0xx00000x
Previous stepwise rearrangements of N-aryl hydroxylamines
(a)
The construction of para-amino-arylfluorosulfates was achieved
through installation of fluorosulfate (-OSO2F) functionality into
aromatic C(sp2)–H bonds from the reaction of N-
arylhydroxylamine with sulfuryl fluoride (SO2F2). This method
provides a mild process for the preparation of the broadly
applicable fluorosulfate moieties without requirement of phenols
or transition metals.
transition metal,
OR2
N
or heat / irradiation
or strong Brønsted acids
various
conditions
OH
N
H
H
N
R1
R1
R1
organic bases
OR2
ortho-position
R1 = Boc, Cbz, p-Ts, RC(O), ROC(O), RNHC(O), RSO2
R2
= Rf, Boc, RC(O), ROC(O), RNHC(O), RSO2
Rearrangement of N-phenoxyacetamide
(b)
OH
H
CH3
N
O
O
Rh (III)
NH
Sulfur (VI) fluoride exchange (SuFEx), a class of new click
reactions developed by Professor K. B. Sharpless and
coworkers,1 have emerged as one of the most powerful
scaffolds and been successfully applied in the fields of covalent
protein inhibitors and biological probes,2 19F radiolabeling
agents,3 heterocycles synthesis,4 and polymer synthesis and
modifications.5 Among all the SuFEx clickable moieties,
arylfluorosulfates (ArOSO2F) with their unique properties of
relatively unreactive toward hydrolysis, reduction, nucleophilic
substitution, thermolysis, whereas, exclusively reactive at the
sulfur center under appropriate conditions, have been
particularly recognized as a family of selectively addressable
protocols applied in a wide variety of targets in chemical
CH3
O
ortho-position
This work, para-exclusive one step rearrangement of N-aryl hydroxylamines
(c)
H
H
OH
N
R1
room temperature
O
transition metal free
N
F
R1
S
+
(SO2F2, balloon)
O
O
one single step
inorganic base (Na2CO3)
high para-selectivity
up to 94% isolated yield
27 examples
R1 = Boc, Cbz, Ac, Piv
Scheme 1. Representative rearrangement strategies for synthesis of
protected-anilines
The rearrangement of functionalized N-arylhydroxylamines
for the syntheses of functionalized phenols feathering aniline
derivatives has been extensively studied, which typically
requires elevated temperature, and/or strong Brønsted/Lewis
acids, transition metals or oxidants (Scheme 1a).9 In addition,
for this class of transformations, electron-deficient groups [CF3,
RSO2, RC(O), et al] are generally required to be preinstalled
onto both the hydroxyl (OH) groups and the amine (NH)
groups to activate the N-O bond for facilitating the rearrange-
ment process. The Rh(III)-catalyzed rearrangement of N-
phenoxyacetamide derivatives has also been successfully
conducted via migration of functionalized NH groups instead
of OH groups, which provides another valuable method for the
synthesis of functionalized phenols with aniline moieties
(Scheme 1b).10 However, most of the rearrangements of N-
arylhydroxylamines or N-phenoxyacetamide derivatives
proceeded through ortho C-H activation of aromatic rings with
the formation of ortho C-O bond or C-N bond, while the para
C-H activation type of rearrangement has gained limited
exploration. And SO2F2 (an inexpensive (about 1$/kg),
relatively inert gas (stable up to 400 ºC when dry) has been
served as one of the key reagents for SuFEx click chemistry
nowadays.11 Herein, we reported a SO2F2-mediated and
6
biology and drug discovery and as building blocks similar to
aryl triflates or aryl halides for various chemical
transformations.7 However, nowadays nearly all fluorosulfates
are derived from their phenolic compounds, which has
unfortunately limited the diversifying and accessing to new
fluorosulfates. On the other hand, anilines are prevalent in
pharmaceuticals and natural products and have been widely
utilized as versatile building blocks in peptides chemistry,
synthetic chemistry and fine chemicals.8 Therefore, the
development of efficient and novel methods for the
preparation of arylfluorosulfates (ArOSO2F) possessing aniline
moieties without the usage of phenols is of great importance
and highly desirable.
State Key Laboratory of Silicate Materials for Architectures; and School of
Chemistry, Chemical Engineering and Life Science Wuhan University of
Technology, Wuhan 430070 (China). E-mail: qinhuali@whut.edu.cn.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See DOI:
10.1039/x0xx00000x
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COMMUNICATION
inorganic base
Journal Name
promoted
rearrangement
of
N- Interestingly, the substrates 3c and 3d possessing aliphatic
View Article Online
DOI: 10.1039/C9CC02659B
arylhydroxylamine, a para selective, mild and practical method ester groups provided higher yields of the corresponding
for the synthesis of arylfluorosulfates (ArOSO2F) possessing fluorosulfates (4c and 4d) comparing to their counterparty 3e
para-aniline moieties with broad functional group possessing aromatic ester. Furthermore, halide-containing
compatibility (Scheme 1c).
starting materials (4f-4i and 4m-4o) tolerated this SO2F2-
After screening a large variety of conditions (see Supporting mediated rearrangement system well. Besides, the position of
Information for details), we were delighted to find that the substituents on the aryl rings also exhibited an obvious
SO2F2-mediated rearrangement of N-aryl hydroxylamines for influence on the efficiency. The substituents on the ortho-
highly para-selective installation of -OSO2F into aromatic position to -OSO2F group possessing steric hindrance
C(sp2)–H bonds was accomplished in good yield using Na2CO3 accomplished less effectively than their meta-position
as promoter in a co-solvent of DMF-H2O (v/v = 3:1) at room counterparties, to generate their corresponding products in
temperature.
lower yields (e.g. 4g compared to 4n and 4h compared to 4o).
The acetal moiety in 3j remained intact during the
rearrangement to provide the desired product 4j in 94%
isolated yield. Pleasingly, ketone, a versatile building block in
synthesis, tolerated well without undergoing side reactions
(4k). This method was also applied to Cbz-protected N-
arylhydroxylamines functionalized with multi-substituents on
the aromatic rings (3p and 3q), to provide their corresponding
products (4p and 4q) in 73% and 71% yield, respectively.
Notably, extending reaction time to 5 hours seemed to be
crucial for complete consumption of 3q due to the steric-
hindrance effect of two methyl groups at the ortho-position.
Table 1. Scope of SO2F2-mediated Rearrangement of tert-
Butoxycarbonyl(Boc)-Protected N-Aryl hydroxylaminesa, b
SO2F2 (balloon)
FO2SO
R
Na2CO3 (3.0 eq.)
Boc
R
Boc
N
OH
DMF:H2O = 3:1 (v/v), r.t., 3 h
N
H
1
2
FO2SO
FO2SO
FO2SO
Cl
Boc
Boc
Boc
Boc
N
H
N
H
N
H
H3C
2a
2b
2c
, 62%
, 77%
, 80%
, 56%
Notably,
a
detectable trace amount of the ortho-
FO2SO
Br
FO2SO
F3C
FO2SO
F3CO
rearrangement products was also produced during this SO2F2-
mediated rearrangement process. Pleasingly, the scalability of
Boc
Boc
N
H
N
H
N
H
2d
2e
2f
, 61%
, 70%
this transformation was achieved through
a gram-scale
experiment of 3a (5 mmol, 1.22 g) resulting in 69% isolated
yield of the corresponding product 4a consuming about 2.25
equivalent of SO2F2. However, when the para-functionalized N-
aryl hydroxylamines were used, the rearrangement provided a
mess mixture of undesired products.
aReaction conditions: Boc-Protected N-aryl hydroxylamine (1, 1
mmol) and Na2CO3 (318 mg, 3 mmol, 3.0 eq.) were stirred in
the co-solvent (10 mL, 0.1 M, DMF:H2O =3:1 (v/v) ) with a
SO2F2 balloon at r.t. for 3 h. bIsolated yields.
To investigate the reaction scope, further extension of other
substrates possessing representative functional groups was
conducted subsequently and the results were collected in
Table 1. Gratefully, tert-butoxycarbonyl(Boc)-protected N-aryl
hydroxylamines reacted under the optimized conditions
smoothly to afford their corresponding rearrangement-
products in moderate to good yields (56-80%) on a standard
1.0 mmol scale (2a-2f). It’s important to note that the
efficiency of this transformation was significantly influenced by
the electronic effect on the aryl rings, owing to the stability of
carbocation intermediates during the rearrangement process.
The starting materials functionalized with electron-donating
groups usually afforded higher yields of their corresponding
products comparing to those with electron-withdrawing
groups, for example, the yield of 2b (CH3, 80%) vs the yield of
2e (CF3, 56%).
To further study the reaction scope of this transformation,
we shifted the carbamate protecting group of the starting
material arylhydroxylamines to Cbz group. As shown in the
Table 2, a large variety of structurally and electronically diverse
Cbz-protectd N-arylhydroxylamines were smoothly converted
to their corresponding products in good to excellent yields
under the aforementioned optimal condition (57-94%). Both
the prevalent electron-donating and electron-withdrawing
substituents on the aromatic rings were well tolerated.
Table 2. Substrate Scope Study of Cbz-Protected N-Aryl
hydroxylaminesa, b
SO2F2 (balloon)
FO2SO
R
Na2CO3 (3.0 eq.)
Cbz
R
Cbz
N
DMF:H2O = 3:1 (v/v), r.t., 3 h
N
OH
H
3
4
FO2SO
FO2SO
H3C
FO2SO
EtO2C
FO2SO
AcO
Cbz
Cbz
Cbz
Cbz
N
N
N
N
H
H
H
H
,
78% (69%)c,d
4a
d
e
4b
, 64%
4c
4d
, 73%
, 91%
4'a
, ortho-OSO2F (< 3%)
FO2SO
FO2SO
FO2SO
FO2SO
Cbz
FO2SO
Cbz
Cbz
Cbz
Cbz
Cbz
MeO2C
N
F
N
H
Cl
N
Br
N
I
N
H
H
H
H
d
4f
4g
4h
4i
, 60%
, 58%
, 59%
FO2SO
, 64%
4e
, 64%
FO2SO
FO2SO
CH3
FO2SO
F
Cbz
Cbz
Cbz
O
O
N
N
N
H
N
H
H
H
O
4j
4k
4l
4m
, 94%
, 79%
, 79%
, 57%
CH3
FO2SO
CH3
Cbz
FO2SO
Cl
FO2SO
Br
FO2SO
CH3
Cbz
Cbz
N
N
H
N
H
Cbz
H
N
CH3
H
e
4n
4o
4p
4q
, 71%
, 68%
, 85%
, 73%
aReaction conditions: Cbz-Protected N-aryl hydroxylamine (3, 1
mmol) and Na2CO3 (318 mg, 3 mmol, 3.0 eq.) were stirred in the co-
solvent (10 mL, 0.1 M, DMF:H2O =3:1 (v/v)) with SO2F2 balloon at r.t.
b
c
for 3 h. Isolated yields. Gram-scale experiment (3a, 5 mmol, 1.22
g). dr.t., 4 h. er.t., 5 h.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
COMMUNICATION
FO2SO
FO2SO
FO2SO
OSO2
F
HO
SO2F2 (balloon)
Na2CO3 (3.0 eq.)
SO2F2 (balloon)
Na2CO3 (3.0 eq.)
FO2SO
View Article Online
Cbz
(a)
(b)
(c)
+
+
Cbz
Cbz
Cbz
N
N
H
N
DOI: 10NH.1039/C9CC02659B
Piv
DMF:H2O = 3:1 (v/v), r.t., 3 h
OH
H
Piv
N
DMF:H2O = 3:1 (v/v), r.t., 3 h
standard condition
4aa,
5%
N
3a,
3a,
4a,
4a,
4'a,
< 3%
1 mmol
78%
55%
OH
H
6
, 60%
5
SO2F2 (balloon)
Na2CO3 (3.0 eq.)
Cbz
SO2F2 (balloon)
Na2CO3 (3.0 eq.)
Cbz
N
FO2SO
N
H
dry DMF, r.t., 3 h
OH
1 mmol
R
Ac
R
Ac
N
DMF:H2O = 3:1 (v/v), r.t., 3-4 h
N
FO2S18
O
OH
H
SO2F2 (balloon)
Na2CO3 (3.0 eq.)
7
8
Cbz
Cbz
Cbz
N
OH
+
N
H
N
7a
7b
7c
dry DMF:H218O = 3:1 (v/v)
r.t., 3 h
, R = H
8a
8b
8c,
, 72% (3 h)
, 70% (4 h)
54% (3 h)
H
3a,
4a,
4''a,
minor
0.2 mmol
major
, R = 2-Br
, R = 2-Cl-5-CF3
Scheme 4. Mechanism investigation
Scheme
2.
Examination
of
Carbonyl-Protected
N-
Arylhydroxylamines
OSO2F
FO2SO
H
SO2F2 (balloon)
proton transfer
proton transfer
To further demonstrate the wide scope of our developed
method in synthesis, carbonyl (Piv and Ac group) protected N-
arylhydroxylamines (Scheme 2), were also subjected to the
SO2F2 mediated rearrangement to afford their corresponding
arylfluorosulfates in acceptable yields (54-72%). Not
surprisingly, somewhat lower yield was also observed for the
electron-deficient substrate 7c.
PG
PG
N
N
Base
N
H
OH
2
PG
E
1
Base
SO2F2
OH
HO
H
HF
Base
SO2F2
PG
N
N
H
OSO2F
H2O
PG
G
F
N-OSO2F
bond cleavage
PG
N
N
N
N
OSO2F
PG
PG
PG
FO2SO
OSO2F
B
C
D
A
Boc
N
H
Scheme 5. Proposed mechanism of the SO2F2 mediated para-
2a
selective rearrangement.
TFA
DCM
r.t., 12 h
96%
OSO2
F
As illustrated in Scheme 5, a plausible mechanism for the
base-promoted, SO2F2 mediated para-selective rearrangement
was proposed. The hydroxy group of N-arylhydroxylamine
proceeded a SuFEx type of substitution with SO2F2 to afford
the fluorosulfates A. Subsequent cleavage of N-OSO2F bond
generates nitrogen cationic intermediate B, which have two
OSO2
F
Ibuprofen
SO2F2, DIPEA
N-Boc-proline
SO2F2, DIPEA
O
FO2SO
(a)
O
N
NH
MeCN, r.t., 5 h
MeCN, r.t., 5 h
H
NH2
N
9
Boc
Ibuprofen amide
N-Boc-proline amide
10
11
, 89%
, 80%
FO2SO
O
DBU (20 mol%)
DMF, r.t., 5 h
O
S
O
Boc
(b)
+
O
O
O
OTBS
N
H
Boc
N
2a
12
13,
93%
H
other resonance contributors
nucleophilic addition of OSO2F anion and H2O to the most
C and D. The following
Scheme 3. Diversifications of Rearrangement Product 2a.
Subsequently, some extended work focusing on the applications
of this novel class of arylfluorosulfates (ArOSO2F) in organic
transformations was conducted using the rearrangement product
2a as the starting material. Primary aniline 9 was isolated with
nearly quantitatively yield and high purity after hydrolysis of 2a
with trifluoroacetic acid in DCM, and the subsequent coupling with
Ibuprofen (a nonsteroidal anti-inflammatory drug) and N-Boc-
proline (a prevalent amino acid) provided their corresponding
amides 10 and 11 in 80% and 89% yields, respectively (Scheme 3a).
Besides, as depicted in Scheme 3b, the SuFEx click reaction of 2a
with TBS-protected phenol derivate 12 generated sulfate 13 with
excellent yield, leaving an intact terminal alkyne moiety for further
transformations.
favorable and stable carbocation intermediate D occurred
predominately to provide
a mixture of corresponding
precursor E and F respectively, which further went through a
proton transfer process to generate their product fluorosulfate
2 and aminophenol G, respectively. After reacting with
another equivalent of SO2F2, the aminophenol G was also
converted to the corresponding fluorosulfate 2.
In conclusion, we have developed an efficient method for
the synthesis of arylfluorosulfates (ArOSO2F) possessing para-
aniline moieties through a SO2F2-mediated rearrangement of
N-arylhydroxylamine process without any metal catalyst. The
starting material substrates were readily prepared from the
abundant nitroarenes. The transition-metal-free protocol
proceeded with high regioselectivity, wide scope, and
functional group compatibility without strict requirement of
the exclusion of moisture and air to afford the extremely
useful para-amino-arylfluorosulfates.
As described in the Scheme 4, some investigations were
performed to figure out the mechanism of this SO2F2-mediated
rearrangement process. The reaction of 3a conducted under the
standard reaction condition resulted in a mixture of desired product
4a, by-product aminophenol 4aa and the ortho-OSO2F product 4’a
in 78%, 5% and <3% yields respectively (Scheme 4a). Interestingly,
when the reaction was operated in dry DMF, 55% yield of 4a was
obtained (Scheme 4b). Furthermore, the resulted mixture of 4a
(majority) and 4’’a (minority) in the 18O labeled experiment
(Scheme 4c) revealed that both the OSO2F anion and H2O have
served as nucleophiles during this transformation, while the later
one (H2O) provided the aminophenol intermediate 4aa initially
before the subsequent conversion to the corresponding
fluorosulfate 4a.
We are grateful to the National Natural Science Foundation
of China (Grant No. 21772150), the Wuhan applied
fundamental research plan of Wuhan Science and Technology
Bureau (grant NO. 2017060201010216), the 111 Project (grant
No. B18038) and Wuhan University of Technology for the
financial support.
Conflicts of interest
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Journal Name
57, 6858; (g) C. Ma, C.-Q. Zhao, X.-T. Xu, Z.-M. Li, X.-Y. Wang,
There are no conflicts to declare.
View Article Online
K. Zhang and T.-S. Mei, Org. Lett., 2019, 21, 2464.
DOI: 10.1039/C9CC02659B
8
9
(a) G. Guillena, D. J. Ramón and M. Yus, Chem. Rev., 2010,
110, 1611; (b) P. Ruiz-Castillo and S. L. Buchwald, Chem. Rev.,
2016, 116, 12564.
Notes and references
For review of N-arylhydroxylamines rearrangement, see: (a)
A. A. Tabolin, and S. L. Ioffe, Chem. Rev., 2014, 114, 5426; For
examples of N-arylhydroxylamines rearrangement, see: (b) S.
Shaaban, V. Tona, B. Peng and N. Maulide, Angew. Chem., Int.
Ed., 2017, 56, 10938; (c) I. Nakamura, T. Jo, Y. Ishida, H.
Tashiro and M. Terada, Org. Lett., 2017, 19, 3059; (d) J. W.
Lee, D. N.; Spiegowski and M.-Y. Ngai, Chem. Sci., 2017, 8,
6066; (e) P. Feng, K. N. Lee, J. W. Lee, C. Zhan and M.-Y. Nga,
Chem. Sci., 2016, 7, 424; (f) K. N. Hojczyk, P. Feng, C. Zhan
and M.-Y. Ngai, Angew. Chem., Int. Ed., 2014, 53, 14559; (g)
A. Porzelle, M. D. Woodrow and N. C. O. Tomkinson, Org.
Lett., 2010, 12, 1492; (h) A. Porzelle, M. D. Woodrow and N.
C. O. Tomkinson, Org. Lett., 2009, 11, 233; (i) M. Novak, K. S.
Rangappa and R. K. Manitsas, J. Org. Chem., 1993, 58, 7813.
(j) P. G. Gassman and J. E. Granrud, J. Am. Chem. Soc., 1984,
106, 1498; (k) P. G.; Gassman and J. E. Granrud, J. Am. Chem.
Soc., 1984, 106, 2448; (l) M. Pelecanou and M. Novak, J. Am.
Chem. Soc., 1985, 107, 4499.
1
For review of SuFEx click chemistry, see: (a) J. Dong, L.
Krasnova, M. G. Finn and K. B. Sharpless, Angew. Chem., Int.
Ed., 2014, 53, 9430. For examples of synthesis of SuFEx
clickable Sulfur (VI) fluorides, see: (b) Q. Zheng, J.; Dong and
K. B. Sharpless, J. Org. Chem., 2016, 81, 11360; (c) H.-L. Qin,
Q. Zheng, G. A. L. Bare, P. Wu and K. B. Sharpless, Angew.
Chem., Int. Ed., 2016, 55, 14155; (d) G.-F. Zha, Q. Zheng, J.
Leng, P. Wu, H.-L. Qin and K. B. Sharpless, Angew. Chem., Int.
Ed., 2017, 56, 4849; (e) G.-F. Zha, G. A. L. Bare, J. Leng, Z.-P.
Shang, Z. Luo and H.-L. Qin, Adv. Synth. Catal., 2017, 359,
3237; (f) S. Li, P. Wu, J. E. Moses and K. B. Sharpless, Angew.
Chem., Int. Ed., 2017, 56, 2903; (g) T. Guo, G. Meng, X. Zhan,
Q. Yang, T. Ma, L. Xu, K. B. Sharpless and J. Dong, Angew.
Chem., Int. Ed., 2018, 57, 2605.
(a) E. C. Hett, H. Xu, K. F. Geoghegan, A. Gopalsamy, R. E.
Kyne Jr, C. A. Menard, A. Narayanan, M. D. Parikh, S. Liu, L.
Roberts, R. P. Robinson, M. A. Tones and L. H. Jones, ACS
Chem. Biol., 2015, 10, 1094; (b) N. P. Grimster, S. Connelly, A.
Baranczak, J. Dong, L. B. Krasnova, K. B. Sharpless, E. T.
Powers, I. A. Wilson and J. W. Kelly, J. Am. Chem. Soc., 2013,
135, 5656; (c) Q. Zhao, X. Ouyang, X. Wan, K. S. Gajiwala, J. C.
Kath, L. H. Jones, A. L.; Burlingame and J. Taunton, J. Am.
Chem. Soc., 2017, 139, 680.
2
10 X. Wang, T. Gensch, A. Lerchen, C. G. Daniliuc and F. Glorius,
J. Am. Chem. Soc., 2017, 139, 6506.
11 Sulfuryl fluoride (SO2F2) has been produced annually at
more than 3 million kilograms per year since 2000, with a
price as low as $1/kg. see: (a) M. P. Sulbaek Andersen, D. R.
Blake, F. S. Rowland, M. D. Hurley and T. J. Wallington,
Environ. Sci. Technol., 2009, 43, 1067; For reviews of SO2F2
utilization, see: (b) L. Revathi, L. Ravindar, J. Leng, K. P.
Rakesh and H.-L. Qin, Asian J. Org. Chem., 2018, 7, 662; For
some selected examples, see: (c) M. Epifanov, P. J. Foth, F.
Gu. C. Barrillon, S. S. Kanani, C. S. Higman, J. E. Hein and G. M.
Sammis, J. Am. Chem. Soc., 2018, 140, 16464; (d) G.-F. Zha,
W.-Y. Fang, Y.-G. Li, J. Leng, X. Chen and H.-L. Qin, J. Am.
Chem. Soc., 2018, 140, 17666; (e) X. Zhang, K. P. Rakesh and
H.-L. Qin, Chem. Commun., 2019, 55, 2845; (f) J. Gurjar, J.
Bater and V. V. Fokin, Chem. Eur. J., 2019, 25, 1906; (g) G.-F.
Zha, W.-Y. Fang, J. Leng and H.-L. Qin, Adv. Synth. Catal.,
2019, DOI: 10.1002/adsc.201900104; (h) W.-Y. Fang and H.-L.
Qin, J. Org. Chem., 2019, DOI: 10.1021/acs.joc.8b03164; (i)
S.-M. Wang, C. Zhao, X. Zhang and H.-L. Qin, Org. Biomol.
Chem., 2019, 17, 4087.
3
4
5
(a) J. A. H. Inkster, K. Liu, S. Ait-Mohand, P. Schaffer, B.
Guérin, T. J. Ruth and T. Storr, Chem. Eur. J., 2012, 18, 11079;
(b) L. Matesic, N. A. Wyatt, B. H. Fraser, M. P. Roberts, T. Q.
Pham and I. Greguric, J. Org. Chem., 2013, 78, 11262.
(a) X. Chen, G.-F. Zha, G. A. L. Bare, J. Leng, S.-M. Wang and H.-
L. Qin, Adv. Synth. Catal., 2017, 359, 3254; (b) X. Chen, G.-F.
Zha, W.-Y. Fang, K. P. Rakesh and H.-L. Qin, Chem. Commun.,
2018, 54, 9011.
(a) J. Yatvin, K. Brooks and J. Locklin, Angew. Chem., Int. Ed.,
2015, 54, 13370; (b) J. Dong, K. B. Sharpless, L. Kwisnek, J. S.
Oakdale and V. V. Fokin, Angew. Chem., Int. Ed., 2014, 53,
9466; (c) B. Gao, L. Zhang, Q. Zheng, F. Zhou, L. M. Klivansky,
J. Lu, Y. Liu, J. Dong, P. Wu and K. B. Sharpless, Nature Chem.,
2017, 9, 1083; (d) C. Yang, J. P. Flynn and J. Niu, Angew.
Chem., Int. Ed., 2018, 57, 16194.
(a) A. Baranczak, Y. Liu, S. Connelly, W.-G. H. Du, E. R. Greiner,
J. C. Genereux, R. L. Wiseman, Y. S. Eisele, N. C. Bradbury, J.
Dong, L. Noodleman, K. B. Sharpless, I. A. Wilson, S. E.
Encalada and J. W. Kelly, J. Am. Chem. Soc., 2015, 137, 7404;
(b) W. Chen, J. Dong, L. Plate, D. E. Mortenson, G. J. Brighty,
S. Li, Y. Liu, A. Galmozzi, P. S. Lee, J. J. Hulce, B. F. Cravatt, E.
Saez, E. T. Powers, I. A. Wilson, K. B. Sharpless and J. W. Kelly,
J. Am. Chem. Soc., 2016, 138, 7353; (c) Z. Liu, J. Li, S. Li, G. Li,
K. B. Sharpless and P. Wu, J. Am. Chem. Soc., 2018, 140, 2919;
(d) D. E. Mortenson, G. J. Brighty, L. Plate, G. Bare, W. Chen,
S. Li, H. Wang, B. F. Cravatt, S. Forli, E. T. Powers, K. B.;
Sharpless, I. A. Wilson and J. W. Kelly, J. Am. Chem. Soc.,
2018, 140, 200.
(a) P. S. Hanley, M. S. Ober, A. L. Krasovskiy, G. T. Whiteker
and W. J. Kruper, ACS Catal., 2015, 5, 5041; (b) Q. Liang, P.
Xing, Z. Huang, J. Dong, K. B.; Sharpless, X. Li and B. Jiang,
Org. Lett., 2015, 17, 1942.; (c) E. Zhang, J. Tang, S. Li, P. Wu, J.
E. Moses and K. B. Sharpless, Chem. Eur. J., 2016, 22, 5692;
(d) S. D. Schimler, M. A. Cismesia, P. S. Hanley, R. D. J. Froese,
M. J. Jansma, D. C. Bland and M. S. Sanford, J. Am. Chem.
Soc., 2017, 139, 1452; (e) W.-Y. Fang, J. Leng, and H.-L. Qin,
Chem. Asian J., 2017, 12, 2323; (f) K. Domino, C. Veryser, B. A.
Wahlqvist, C. Gaardbo, K. T. Neumann, K. Daasbjerg, W. M. D.
Borggraeve and T. Skrydstrup, Angew. Chem., Int. Ed., 2018,
6
7
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