Synthesis of chiral quaternary fluorinated cyclic sulfamidates via palladium-catalyzed arylation with arylboronic acids

Article abstract of DOI:10.1016/j.tetlet.2019.151280

An enantioselective palladium-catalyzed arylation of fluorinated cyclic N-sulfonyl ketimines with arylboronic acids is described. This methodology provides an efficient and convenient route to chiral quaternary fluorinated cyclic sulfamidates in high yields with up to 99% ee.

Full text of DOI:10.1016/j.tetlet.2019.151280

Journal Pre-proofs
Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladium-
catalyzed Arylation with Arylboronic Acids
Mu-Wang Chen, Xuechun Mao, Yue Ji, Jianjun Yuan, Zhihong Deng, Yiyuan
Peng
PII:
S0040-4039(19)31060-3
DOI:
https://doi.org/10.1016/j.tetlet.2019.151280
TETL 151280
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
30 August 2019
10 October 2019
12 October 2019
Please cite this article as: Chen, M-W., Mao, X., Ji, Y., Yuan, J., Deng, Z., Peng, Y., Synthesis of Chiral Quaternary
Fluorinated Cyclic Sulfamidates via Palladium-catalyzed Arylation with Arylboronic Acids, Tetrahedron Letters
(2019), doi: https://doi.org/10.1016/j.tetlet.2019.151280
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Synthesis of Chiral Quaternary Fluorinated Cyclic
Sulfamidates via Palladium-catalyzed Arylation
with Arylboronic Acids
Mu-Wang Chena, Xuechun Maoa, Yue Jib, Jianjun Yuana, Zhihong Denga, Yiyuan Peng*a
O
O
O
O
O
Pd(OCOCF3)2/(S)-tBu-Phox
TFE, 40 o
tBu
S
N
S
O
O
NH
Ar'
ArB(OH)2
Ar'
+
N
C
PPh2
Rf
Rf Ar
(S)-tBu-Phox
1
2
3
up to 99% ee

1
Tetrahedron Letters
journal homepage: www.elsevier.com
Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladium-
catalyzed Arylation with Arylboronic Acids
Mu-Wang Chena, Xuechun Maoa, Yue Jib, Jianjun Yuana, Zhihong Denga, Yiyuan Peng*a
aKey Laboratory of Functional Small Organic Molecules, Ministry of Education, Jiangxi Province’s Key Laboratory of Green Chemistry, and Jiangxi Normal
University, Nanchang 330022, China
b College of Chemistry & Chemical Engineering, Xian Shiyou University, Xian 710065, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An enantioselective palladium-catalyzed arylation of fluorinated cyclic N-sulfonyl ketimines
with arylboronic acids is described. This methodology provides an efficient and convenient
route to chiral quaternary fluorinated cyclic sulfamidates in high yields with up to 99% ee.
2015 Elsevier Ltd. All rights reserved.
Available online
Keywords:
asymmetric-addition
quaternary fluorinated cyclic sulfamidate
palladium catalyst
arylboronic acid
Chiral cyclic sulfamidates are valuable and prevalent building
blocks in biologically active natural products, agrochemicals,
pharmacophores and functional materials (Figure 1).1 Therefore,
their catalytic enantioselective syntheses have attracted a great
deal of interests in the past decades. One of the most
straightforward and atom-efficient approaches for the synthesis
of chiral sulfamidates was asymmetric hydrogenation of cyclic
sulfamidate ketimines.2-3 Another effect method to construction
of chiral cyclic sulfamidates was through enzymes catalyzed
intramolecular C-H amination.4 Furthermore, metal-catalyzed
enantioselective addition of carbon nucleophiles (the
organoboron reagents) to cyclic N-sulfonyl ketimines was proved
to be a powerful strategy for synthesis of chiral cyclic
sulfamidates (Scheme 1).5-13 Since the pioneering researches
reported by Hayashi,6 Lam,7 Xu8 and Zhang9 et al10 the rhodium
or palladium-catalyzed asymmetric addition of organoboron
reagents to cyclic sulfamidates have been extensively studied. In
addition, other transition-metal (Ni,11 Co,12 Ag13)-catalyzed
asymmetric addition of nucleophiles to cyclic N-sulfonyl
ketimines for the synthesis of chiral cyclic sulfamidates was also
successively developed. In contrast, only a few methods8a,9a,10a
have been applied to synthesis of chiral sulfamidates bearing a
trifluoromethyl group on the quaternary carbon stereogenic
center. Especially, the introduction of fluorine into organic
molecules can greatly modify the lipophilicity, metabolic
stability and biological activity of fluorinated compounds.14 In
2013, Xu and co-workers reported a Rh-catalyzed asymmetric
addition of arylboronic acids to trifluoromethyl cyclic N-sulfonyl
ketimines, giving the trifluoromethylated sulfamidates with
excellent enantioselectivity.8a Subsequently, a new approach
based on palladium-catalyzed enantioselective addition of
arylboronic acids to cyclic ketimines was described by Zhang’s
group, which includes only one example of chiral
trifluoromethylated sulfamidates with 95% ee and 71% yield
under 10 mol% catalyst loading.9a Therefore, it is still necessary
to develop efficient methods for the asymmetric synthesis of
fluorinated cyclic sulfamidates in organic chemistry.
Previous work
: Metal-catalyzed asymmetric arylation of cyclic sulfamidate imines
O
O
O
O
S
S
[M]/L* catalyst
NH

N
+
ArB(OH)2
R
R
M = Rh, Pd, Ni, Co, Ag
Ar
R = H, alkyl, aryl, CO2R', CF3
This work
: Pd-catalyzed asymmetric arylation of fluorinated cyclic sulfamidate imines
O
O
O
O
S
S
[Pd]/L* catalyst
O
O
ArB(OH)2
+
N
NH
Ar
Rf
Rf
14 examples, up to 99% ee
Scheme 1. Catalytic asymmetric addition of arylboron reagents
to cyclic sulfamidate imines.
In the past decades, chiral palladium catalyst has been
successfully applied in organic synthesis.2a,15 Especially, the
pioneering work of the Pd-catalyzed asymmetric addition of
arylboronic acids to aldimines was reported by Lu and co-
workers.16 In 2013, an elegant work about the palladium-
catalyzed addition of arylboron acids to ketimines was first
reported by Zhang.9 Subsequently, Lu/Hayashi 6e,17 and Zhou18 et
al groups have also reported the related studies. Although great
O
S
O
O
S
O
N
O
O
Et
N
O
H
Me
N
*
H
Ph
F3C
O
Ph
Inhibitor of HIV-1
Inhibitor of Calpain 1
Figure 1 Some bioactive molecules containing the chiral
sulfamidates moiety

2
Tetrahedron Letters
progress has been made in this area, achieving stereocontrol
investigated the different electronic properties of substituent on
the aromatic ring. The electronic properties of substrates had a
little effect on reactivity and enantioselectivity (3d-3f). In
addition, 1g can proceed smoothly with excellent yield and
enantioselectivity by increasing the catalyst loading to 8%. In
addition, a variety of arylboronic acids were examined for
addition to different fluorinated cyclic N-sulfonyl ketimines (1h-
1n). The electronic properties of the arylboronic acids had a
certain influence on reactivity (3j-3l). For examples, electron-rich
arylboronic acids (2j & 2k) both gave excellent yields, but
arylboronic acids bearing electron-withdrawing group such as Cl
gave moderate yield (3l, 61%). Notably, 3,5-dimethylboronic
acid (2n) also gave excellent yield and enantioselectivity.
Unfortunately, only <5 % conversion was observed for the
reaction using o-tolylboronic acid under optimized conditions.
and no product was observed for the reaction using
alkenylboronic or alkylboronic acid.
with a broad substrate scope is still highly desirable. Herein, we
report a catalytic asymmetric arylation of fluorinated cyclic N-
sulfonyl ketimines by chiral palladium complex, giving the chiral
quaternary fluorinated cyclic sulfamidates in high yields with up
to 99% ee..
We began our investigation on the addition of phenyl-boronic
acid to 4-(trifluoromethyl)benzo[e][1,2,3]oxathiazine 2,2-dioxide
1a using Pd(OCOCF3)2/(R)-tBu-Phox as catalyst in
trifluoroethanol (TFE) at 40 oC. Gratifyingly, the reaction
proceeded smoothly and furnished 3a in 73% conversion and 99%
ee (Table 1, entry 1). Subsequently, different solvents were
examined, and solvent effect played a crucial role in both
reactivity and enantioselectivity. The reaction shut down in
dichloromethane, methanol or toluene (entries 2–4). Next, we
further screened several commercially available chiral phosphine
ligands (entries 5-7), L2 gave the desired product with excellent
ee value and moderate yield. The planarly chiral ferrocene N-P
ligand (L3) and axiallly chiral ligand Quinap (L4) afforded the
desired product in excellent ee value but only moderate reactivity.
Considering that 1a could not be completely converted into 3a
and the formation of boronic acid self-coupling products, we
tried to add phenylboronic acid step by step. To our delight, the
conversion was further improved, and enantioselectivity was also
retained with another 1.5 equivalent 2a was added after 24 hours.
Therefore, the optimal conditions were established:
Pd(OCOCF3)2/(S)-tBu-Phox as the catalyst, TFE as solvent under
40 oC and stage addition of arylboronic acid.
Scheme 2. Palladium-catalyzed asymmetric addition of arylboronic acids 2 to
fluorinated cyclic sulfonyl ketimines 1a
O
O
O
O
Pd(OCOCF3)2/(S)-tBu-Phox
S
N
S
O
O
NH
Ar'
ArB(OH)2
Ar'
+
TFE, 40 o
C
Rf
Rf Ar
1
2
3
O
O
O
O
O
O
O
S
S
S
O
O
NH
NH
Ph
NH
Ph
HF2C
3b
F3CF2C
3c
F3C Ph
3a
>99% ee, 81% yield
>99% ee, 98% yield
>99% ee, 86% yield
Table 1 Optimization of reaction parametersa
O
O
O
MeO
O
Cl
O
Me
O
O
S
S
O
S
O
O
O
NH
O
NH
O
S
N
S
NH
L
O
Pd(OCOCF3)2/ *
O
NH
PhB(OH)2
+
Ph
Ph
Ph
F3C
3e
F3C
Solvent, 40 o
C
F3C

3d
3f
CF3
F3C
3a
Ph
>99% ee, 99% yield
>99% ee, 93% yield
>99% ee, 78% yield
1a
2a
O
O
O
NH
O
O
O
NH
O
O
O
NH
S
S
S
Entry
Solvent
L
L1
L1
L1
L1
L2
L3
L4
L1
Conv. (%)b
Ee (%)c
99
Me
F3C
F3C
F3C
TFE
CH2Cl2
MeOH
Toluene
TFE
73
NR
NR
NR
55
1
2
Me
3h
>99% ee, 77% yield
OMe
3i
>99% ee, 71% yield
3gb,c
NA
NA
NA
99
>99% ee, 92% yield
O
O
O
Me
O
Me
O
Me
O
S
S
S
3
O
O
NH
O
NH
NH
4
F3C
F3C
F3C
5
Cl
OMe
Me
3kb
3lb
3j
>99% ee, 92% yield
>99% ee, 95% yield
>99% ee, 61% yield
TFE
35
99
6
O
O
O
NH
Me
O
O
O
NH
TFE
20
98
S
7
Me
O
O
S
S
O
8d
TFE
>95
99
NH
F3C
Me
F3C
Me
F3C
R
O
tBu
N
O
N
O
Me
tBu
tBu
N
3mb,c
3nb
F3C
R = alkenyl, alkyl
NR
PPh2
N
>99% ee, 88% yield
>99% ee, 99% yield
PPh2
Fe
PPh2
PPh2
L2
a Reaction conditions: Pd(OCOCF3)2 (4.0 mol%), (S)-tBu-Phox (6.0
mol%), 1 (0.20 mmol), 2 (0.60 mmol)(stage addition: first addition
1.5 equivalent 2 and then another 1.5 equivalent 2 was added after
24 hours ), TFE (3.0 mL), 40 oC, 72 h, the ee values determined by
L1
L3
L4
a Reaction conditions: Pd(OCOCF3)2 (4.0 mol%), L (6.0 mol%), 1a (0.10
mmol), 2a (0.15 mmol), Solvent (2.0 mL), 40 oC, 72 h. b Determined by
1H NMR. c Determined by HPLC. d 1.5 equivalent 2a was added after 24
hours. NR: no reaction, NA: no analysis.
b
o
c
HPLC. 80 C. Pd(OCOCF3)2 (8.0 mol%), (S)-tBu-Phox (12.0
mol%). NR = no reaction.
With the optimized conditions in hand, we next explored the
substrate scope of the addition reaction (Scheme 2). Various
substrates performed very well under the standard reaction
conditions with excellent enantioselectivities (99%) and high
yields (61–99%). For different fluoroalkyl-substituted cyclic N-
sulfonyl ketimines 1b and 1c, both of them provided the desired
products with >99% ee and good yields. Subsequently, we
Based on the above results, the stereochemistry of this
reaction could be explained by the stereochemical models in
Figure 2. The fluorinated cyclic N-sulfonyl imine bound to Pd
center is in trans to the ligand’s diphenylphosphine group, and
aryl group from the boronic acid is in cis to diphenylphosphine
group.9b There are two possible orientations in the transition state,

3
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but due to the steric interaction between the sulfonyl moiety of
the ketimine substrate and the bulky tertiary butyl group of ligand,
one leads to the disfavored configuration, and the other
orientation does not suffer from such interactions, leading to the
R product, which is the major enantiomer obtained in experiment.
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O
O
H
O
N
O t
H
tBu
O
Bu
Ph2P
N
O
S
Ph2P
Ar
Pd
N
F3C
Ar
Pd
N
S
O
CF3
O
B: Favored
A: Disfavored
O
O
O
O
S
S
O
O
NH
NH
Ar
Major
F3C Ar
F3C
Minor
enantiomer
enantiomer
Figure 2. Stereochemical model
In summary, we have developed a highly enantioselective
palladium-catalyzed arylation of fluorinated cyclic N-sulfonyl
ketimines with arylboronic acids. This methodology provides an
efficient and facile route to chiral quaternary fluorinated cyclic
sulfamidates in high yields with up to 99% ee. Further
investigations on asymmetric addition of nucleophile to
fluorinated cyclic N-sulfonyl ketimines are currently on going in
our laboratory.
Acknowledgments
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Chem. Int. Ed. 2015, 54, 13696; (b) Huang, Y.; Huang, R.-Z.; Zhao,
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G.; Zhang, W. Chem. Eur. J. 2018, 24, 1241.
13. Osborne, C. A.; Endean, T. B. D.; Jarvo, E. R. Org. Lett. 2015, 17,
5340.
We are grateful for financial support from the National
Natural Science Foundation of China (21502188, 21801204
21362014 and 21762020), the Science and Technology Program
of Xian, China (201805038YD16CG22(4)).
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4
Tetrahedron Letters
Dear Editor Prof. Lin,
Enclosed please find our manuscript
entitled “Synthesis of Chiral Quaternary
Fluorinated Cyclic Sulfamidates via
Palladium-catalyzed Arylation with
Arylboronic Acids”
Following is the highlights for
publication as an article in Tetrahedron
Letters.
(1) Arylation
of
fluorinated
cyclic
ketimines with arylboronic acids was
reported.
(2) The substrate scope is good and the
catalyst loading is relatively low.
(3) Chiral fluorinated cyclic sulfamidates
was synthesized with up to 99% ee.
19.