Ni(II)/tBu-SMI-PHOX catalyzed enantioselective addition of arylboronic acids to cyclic N-sulfonyl aldimines

Article abstract of DOI:10.1016/j.tet.2020.131201

An efficient Ni(ClO₄)₂·6H₂O/SMI-PHOX catalyzed enantioselective addition of arylboronic acids to cyclic N-sulfonyl aldimines is envisioned to afford excellent enantioselectivities (up to 99% ee) in high yields (up to 98%). This protocol offers new opportunities for the synthesis of chiral benzosultams containing a stereogenic tertiary carbon center. The highlights of this method include mild reaction conditions, the use of cheap metal catalyst and a wide substrate scope.

Full text of DOI:10.1016/j.tet.2020.131201

Journal Pre-proof
Ni(II)/tBu-SMI-PHOX catalyzed enantioselective addition of arylboronic acids to cyclic
N-sulfonyl aldimines
Rui Sun, Zhongxuan Qiu, Guorui Cao, Dawei Teng
PII:
S0040-4020(20)30336-7
https://doi.org/10.1016/j.tet.2020.131201
TET 131201
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 February 2020
Revised Date: 7 April 2020
Accepted Date: 10 April 2020
Please cite this article as: Sun R, Qiu Z, Cao G, Teng D, Ni(II)/tBu-SMI-PHOX catalyzed
enantioselective addition of arylboronic acids to cyclic N-sulfonyl aldimines, Tetrahedron (2020), doi:
https://doi.org/10.1016/j.tet.2020.131201.
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition
of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of
record. This version will undergo additional copyediting, typesetting and review before it is published
in its final form, but we are providing this version to give early visibility of the article. Please note that,
during the production process, errors may be discovered which could affect the content, and all legal
disclaimers that apply to the journal pertain.
© 2020 Published by Elsevier Ltd.

Graphical Abstract
Ni(II)/tBu-SMI-PHOX catalyzed
enantioselective addition of arylboronic acids
to cyclic N-sulfonyl aldimines
Leave this area blank for abstract info.
Rui Sun, Zhongxuan Qiu, Guorui Cao*, Dawei Teng*
State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering, Qingdao
University of Science and Technology, Qingdao 266042, China.
An efficient Ni(ClO4)2•6H2O/SMI-PHOX catalyzed enantioselective addition of arylboronic acids to cyclic N-sulfonyl
aldimines is envisioned to afford excellent enantioselectivities (up to 99% ee) in high yields (up to 98%). This protocol
offers new opportunities for the synthesis of chiral benzosultams containing a stereogenic tertiary carbon center. The
highlights of this method include mild reaction conditions, the use of cheap metal catalyst and a wide substrate scope.

3

1
Tetrahedron
journal homepage: www.elsevier.com
Ni(II)/tBu-SMI-PHOX catalyzed enantioselective addition of arylboronic acids to
cyclic N-sulfonyl aldimines
Rui Sun, Zhongxuan Qiu, Guorui Cao*, Dawei Teng*
State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042,
China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient Ni(ClO4)2•6H2O/SMI-PHOX catalyzed enantioselective addition of arylboronic
acids to cyclic N-sulfonyl aldimines is envisioned to afford excellent enantioselectivities (up to
99% ee) in high yields (up to 98%). This protocol offers new opportunities for the synthesis of
chiral benzosultams containing a stereogenic tertiary carbon center. The highlights of this
method include mild reaction conditions, the use of cheap metal catalyst and a wide substrate
scope.
Available online
Keywords:
Chiral benzosultams
2014 Elsevier Ltd. All rights reserved
.
Spiro phosphine-oxazoline ligands
Asymmetric addition
Cyclic N-sulfonyl aldimines
1. Introduction
As an important structural motif, chiral benzosultams have
been reported to exhibit great medicinal potential in the
antibacterial and antiviral drugs including γ-secretase inhibitor1
and HIV-1 inhibitor2. Furthermore, these compounds can also be
used as chiral auxiliaries3 and fluorinating reagents4 in organic
synthesis reactions (Scheme 1). In light of the growing demand
for chiral benzosultams containing a stereogenic tertiary carbon
center, several groups have focused their efforts on the
development of efficient synthetic protocols, including
asymmetric hydrogenation of N-sulfonyl imines5, hydrogenolysis
of racemic N-sulfonyloxaziridines6 and intramolecular
asymmetric reductive amination7. However, these methods
commonly suffer from harsh reaction conditions and the use of
expensive metal catalysts (Scheme 2). Thus, developing a more
practical and general protocol for the synthesis of chiral
benzosultams is highly desirable.
Scheme 2. Representative synthetic approach to benzosultams containing a
stereogenic tertiary carbon center
T
he transition-metal-catalyzed addition of arylboron reagents
to cyclic N-sulfonyl ketimines was proved to be an excellent
approach for the enantioselective synthesis of benzosultams
containing a stereogenic quaternary carbon center. The success of
these methodologies depends largely on the rhodium8- and
palladium9-catalyst. The viability of other low-cost transition-
metal-catalysts to provide chiral benzosultams is still worth
Scheme 1. Chiral benzosultams
* Corresponding author, Tel.:+86-532-84022508; e-mail: caoguorui@qust.edu.cn; dteng@qust.edu.cn

2
Tetrahedron
exploring. As a group 10 metal, nickel is often viewed as a low-
initially investigated the asymmetric addition of phenylboronic
cost substitute for palladium and is commonly applied to cross-
coupling reaction10, C-H activation11, Heck reaction12 and
reduction coupling13. However, there are few reports concerning
the nickel-catalyzed addition of arylboronic acids to N-sulfonyl
imines14 (Ni/P,N-ligands, Scheme 2). Inspired by these
pioneering studies and as a continuation of our interest in the
application of spiro-monoindane-based PHOX ligand15 (SMI-
PHOX, Scheme 2), we report the nickel-catalyzed asymmetric
addition of arylboronic acids to cyclic N-sulfonyl aldimines to
afford high yields of benzosultams with good to exellent
enantioselectivities.
acid 2a to cyclic N-sulfonyl aldimines 1 in the presence of
Ni(ClO4)2•6H2O (5 mol%), ligand (7.5 mol%) and TFE at 60
.
We were pleased to find that all the ligands L1-L3 are proved to
be suitable for the reaction. When we chosed L3 as chiral ligand,
excellent enantioselectivity and yield were achieved (99% ee and
98% yield, Table 1, Entry 3). Different metal salts were tested
instead of Ni(ClO4)2•6H2O and resulted in low yield and low
enantioselectivity (Table 1, Entries 4-8). Among various solvents
screened, TFE was found to be the best one (Table 1, Entries 3 vs
9-12). The solvent had a remarkable impact on the reactivity and
efficiency of the reaction. Other solvents such as DCE, Toluene,
CHCl3, CH3CN gave small amounts of the product. Subsequent
optimization with respect to temperature indicated that the
optimal temperature was 60 (Table 1, Entries 3 vs 13-15).
2. Results and discussion
With the chiral SMI-PHOX ligands L1-L3 in hand15a, we
Table 1. The effects of reaction conditions on the asymmetric addition of phenylboronic acid to cyclic N-sulfonyl aldiminea
Entry
1
2
3
4
5
6
7
8
ligand
L1
L2
L3
L3
L3
L3
L3
L3
L3
L3
L3
L3
L3
L3
L3
Metal salt
solvent
TFE
TFE
TFE
TFE
TFE
TFE
TFE
TFE
DCE
Toluene
CHCl3
CH3CN
TFE
Temp(
60
)
Time(h)
24
24
24
24
24
24
24
24
24
24
24
24
48
48
12
Yieldb(%)
98
eec(%)
97
98
99
55
57
69
75
-
38
23
50
31
-
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
NiCl2•6H2O
Ni(OAc)2•4H2O
Ni(DPPE)Cl2
60
60
60
60
60
60
60
60
60
60
60
25
40
75
98
98
79
75
51
54
n.r
38
33
45
32
n.r
36
98
Ni(acac)2
Fe(ClO4)2•4H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
Ni(ClO4)2•6H2O
9
10
11
12
13
14
15
TFE
TFE
98
97
aReaction conditions: cyclic N-sulfonyl aldimine (1) (0.2 mmol), PhB(OH)2 (2a) (0.3 mmol), ligand (0.015 mmol), metal salt (0.01 mmol), TFE (2 mL), 60 , 24
h. bIsolated yield. cDetermined by chiral HPLC analysis. The absolute configuration was assigned as R by comparison with literature data5a.
Entry
1
2
3
4
5
6
7
8
Ar
C6H5
4-MeOC6H4
4-MeC6H4
4-tBuC6H4
4-FC6H4
4-ClC6H4
3-MeOC6H4
3-FC6H4
Product
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
Yieldb(%)
98
eec(%)
99
92
99
71
87
80
88
99
99
73
76
98
99
93
98
99
Under the optimized conditions, we next made a thorough
examination of Ni(ClO4)2•6H2O/L3 catalyzed enantioselective
addition of a variety of arylboronic acids 2 to cyclic N-sulfonyl
aldimine 1. As summarized in Table 2, a wide array of
arylboronic acids reacted smoothly with 1 affording the desired
benzosultams 3a-3p in high yields and good to excellent
enantioselectivities. Both arylboronic acids with electron-
donating substituents (Me, OMe) and those with electron-
withdrawing ones (F, Cl) led to corresponding products with
good yields and enantioselectivities (Table 2, Entries 2-4 vs 5-6).
The position of the substituent on the phenyl group had limited
effect on the results, and good yields and enantioselectivities
could be obtained in all case (Table 2, Entries 2-13). Notably,
ortho-substituted arylboronic acids showed outstanding
97
98
98
96
97
96
97
97
95
80
95
90
98
93
92
9
3-ClC6H4
10
11
12
13
14
15
16
3-CF3C6H4
2-MeC6H4
2-MeOC6H4
2-ClC6H4
3,5-diMeC6H3
2-F-4-MeOC6H3
2-Naphthyl
3m
3n
3o
3p
performance
in
good
yields
(80-95%)
and
high
aReaction conditions: cyclic N-sulfonyl aldimine (1) (0.2 mmol), ArB(OH)2
(2) (0.3 mmol), L3 (0.015 mmol), Ni(ClO4)2•6H2O (0.01 mmol), TFE (2 mL),
60 ℃, 24 h. bIsolated yield. cDetermined by chiral HPLC analysis. The
absolute configurations were assigned as R by comparison with literature
data5.
enantioselectivities (76% to 99% ee) (Table 2, Entries 11-13).
Arylboronic acid with a much bulkier group also gave 3d in 98%
yield and 71% ee. Fused-ring aryl and disubstituted arylboronic
acids could also afford their corresponding products with high
yields and excellent enantioselectivities (Table 2, Entries 14-16).
To further investigate the scope of this protocol, six-
membered cyclic N-sulfonyl aldimine 4 was used as reactant and
a series of chiral benzosulfamidates 5 were obtained under the
optimized reaction conditions (Table 3). Arylboronic acids with
both electron-withdrawing and electron-donating substituents
could give the corresponding products with excellent yields and
enantioselectivities (5b-5c vs 5f and 5h). Compared with
previous work14, better results were obtained when the
Table 2. Scope of the arylboronic acids in the Ni-catalyzed
enantioselective addition to cyclic N-sulfonyl aldimine 1a

3
substitution was at the ortho position of the benzene ring, leading
to benzosulfamidates (5b and 5d) in excellent yields (95-99%)
and enantioselectivities (92% to 99% ee). Furthermore,
disubstituted arylboronic acid could also give 5g in 98% yield
and 87% ee.
enantioselectivities (up to 99% ee) and high yields (up to 98%).
The highlights of this method include mild reaction conditions,
the use of cheap metal catalysts and a wide substrate scope.
Future work will be undertaken to transition-metal-catalyzed
enantioselective addition of arylboronic acids to macrocyclic
sulfonamides.
Table 3. Scope of the Ni-catalyzed enantioselective addition of
arylboronic acids to six-membered cyclic N-sulfonyl aldimine 4a
4. Experimental section
4.1 General
All the reagents were purchased from TCI chemicals and local
suppliers and used without purification. All reactions were
monitored by TLC. Chromatography refers to open column
chromatography on silica gel (100-200 mesh).
1H NMR spectra were recorded on 500 MHz, 13C NMR
spectra were recorded on 125 MHz by using a Bruker Avance
500M spectrometer. Chemical shifts were reported in parts per
million (δ) relative to tetramethylsilane (TMS). Optical rotations
were measured on SGW-1 automatic polarimeter and reported as
follows : [α]TD (c g/100 mL, solvent). Chiral HPLC analysis was
performed using a Shimadzu LC-20 HPLC. Ligands L1-L3 were
prepared according to the reported procedure15. Cyclic N-sulfonyl
aldimines 117a and 417b were synthesized by the known
procedures.
4.2 General procedure for compounds 3 and 5
In the Ar atmosphere, ligand L3 (6.2 mg, 7.5 mol%) and
Ni(ClO4)2•6H2O (3.7 mg, 5 mol%) were dissolved in TFE (1.5
mL) in a dried Schlenk tube and stirred at room temperature for
30 min, N-sulfonyl aldimine (1 or 4, 0.2 mmol) and arylboronic
acid (0.3 mmol) were added into the tube. The wall of the tube
was rinsed with an additional of TFE (0.5 mL). The mixture was
stirred at 60 ℃for 24 h. After that, The mixture was diluted with
EtOAc and washed with saturated NH4Cl (aq) and the organic
layer was separated and dried with Na2SO4, evaporated to remove
solvent under reduced pressure. The residue was subjected to
column chromatography to give corresponding compounds 35 or
514.
aReaction conditions: cyclic N-sulfonyl aldimine (4) (0.2 mmol), ArB(OH)2
(2) (0.3 mmol), L3 (0.015 mmol), Ni(ClO4)2•6H2O (0.01 mmol), TFE (2 mL),
60 ℃, 24 h. bIsolated yield. cDetermined by chiral HPLC analysis. The
absolute configurations were assigned as S by comparison with literature
data9c.
Finally, the reaction stereochemical outcome can be explained
using a transition state model shown in Scheme 3. The spiro-
backbone-based PHOX ligands have shown remarkable success
in versatile asymmetric transformations owing to their stable and
rigid structure15-16. The nucleophilic aryl group bound to the Ni
center is cis to the diphenylphosphine group, and the imine is
trans to the the diphenylphosphine group of L3. To minimize
unfavorable steric interactions with the tertiary butyl group on
the oxazoline ring. The sulfonyl moiety of the imine substrate
oriented away from the tertiary butyl group attached to the
oxazoline ring, leads to the product 3a of R configuration which
was confirmed by comparison with literature data5a.
4.2.1 (R)-3-phenyl-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide
(3a) [CAS 296776-36-8 for S configuration, Ref.[5a] : 98% ee,
[α]25 = +93.6 (c = 1.00, CHCl3)]. 98% yield and 99% ee,
D
determined by chiral HPLC analysis (Daicel Chiralpak AD-H,
Hexanes : IPA = 80 : 20, 0.5 mL/min, λ = 224 nm), tR (major) =
31.779 min, tR (minor) = 27.888 min. [α]25 = -27.4 (c = 0.67,
D
CH2Cl2). 1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 6.8 Hz, 1H),
7.41-7.47 (m, 2H), 7.28 (s, 5H), 7.04 (d, J =7.1 Hz, 1H), 5.63 (d,
J = 3.8 Hz, 1H), 5.17 (d, J = 2.3 Hz, 1H). 13C NMR (125 MHz,
CDCl3) δ 139.8, 138.7, 134.8, 133.4, 129.5, 129.3, 129.1, 127.6,
125.4, 121.2, 61.4.
4.2.2 (R)-3-(4-methoxyphenyl)-2,3-dihydrobenzo[d]isothiazole
1,1-dioxide (3b) 97% yield and 92% ee, determined by chiral
HPLC analysis (Daicel Chiralpak OD-H, Hexanes : IPA = 80 :
20, 0.6 mL/min, λ = 224 nm), tR (major) = 43.200 min, tR (minor)
= 64.393 min. [α]2D5 = -22.8 (c = 0.72, CH2Cl2). H NMR (500
1
Scheme 3. The plausible reaction mechanism
MHz, CDCl3) δ 7.77 (d, J = 8.1 Hz, 1H), 7.46-7.51 (m, 2H),
7.19-7.21 (m, 2H), 7.06 (d, J = 7.0 Hz, 1H), 6.83 (d, J = 8.6 Hz,
2H), 5.61 (d, J = 4.0 Hz, 1H), 4.81 (d, J = 3.1 Hz, 1H), 3.74 (s,
3H); 13C NMR (125 MHz, CDCl3) δ 160.1, 140.3, 134.9, 133.3,
130.7, 129.4, 129.0, 125.4, 121.0, 114.6, 60.9, 55.4.
3. Conclusions
In summary, we have developed
a enantioselective
Ni(II)/tBu-SMI-PHOX catalytic system for the asymmetric
addition of arylboronic acids to cyclic N-sulfonyl aldimines. It is
a more general and practical protocol for the synthesis of chiral
4.2.3 (R)-3-(p-tolyl)-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide
(3c) 98% yield and 99% ee, determined by chiral HPLC analysis
(Daicel Chiralpak AD-H, Hexanes : IPA = 80 : 20, 0.6 mL/min, λ
benzosultams containing
a
tertiary carbon center. The
corresponding benzosultams were afforded in excellent

4
Tetrahedron
= 224 nm), tR (major) = 27.496 min, tR (minor) = 24.765 min.
analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 : 20, 0.6
[α]2D5 = -35.4 (c = 0.65, CH2Cl2). H NMR (500 MHz, CDCl3) δ
7.75-7.77 (m, 1H), 7.46-7.50 (m, 2H), 7.17-7.20 (m, 2H), 7.12 (d,
J = 8.0 Hz, 2H), 7.06-7.07 (m, 1H), 5.62 (d, J = 4.0 Hz, 1H), 4.82
(d, J = 2.7 Hz, 1H), 2.29 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
140.1, 139.0, 135.8, 133.3, 129.9, 129.4, 127.5, 125.4, 121.1,
61.2, 21.2.
mL/min, λ = 224 nm), tR (major) = 22.896 min, tR (minor) =
1
20.107 min. [α]2D5 = -40.2 (c = 0.87, CH2Cl2). H NMR (500
1
MHz, CDCl3) δ 7.82-7.85 (m, 1H), 7.55-7.60 (m, 2H), 7.25-7.38
(m, 4H), 7.15 (d, J = 6.8 Hz, 1H), 5.70 (d, J = 4.2 Hz, 1H), 5.17
(d, J = 3.5 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 140.8, 138.9,
135.1, 134.5, 133.5, 130.5, 129.8, 129.2, 127.6, 125.7, 125.3,
121.3, 60.6.
4.2.4 (R)-3-(4-(tert-butyl)phenyl)-2,3-dihydrobenzo[d]isothiazole
1,1-dioxide (3d) 98% yield and 71% ee, determined by chiral
HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 :
20, 0.6 mL/min, λ = 224 nm), tR (major) = 16.124 min, tR (minor)
4.2.10
(R)-3-(3-(trifluoromethyl)phenyl)-2,3-dihydrobenzo[d]
isothiazole 1,1-dioxide (3j) 95% yield and 73% ee, determined by
chiral HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA =
80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 15.732 min, tR
(minor) = 14.474 min. [α]2D5 = -34.5 (c = 0.56, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.85-7.86 (m, 1H), 7.63-7.67 (m, 2H), 7.56-
7.60 (m, 3H), 7.53 (t, J = 7.7 Hz, 1H), 7.13-7.15 (m, 1H), 5.80 (d,
J = 4.3 Hz, 1H), 5.20 (d, J = 3.0 Hz, 1H); 13C NMR (125 MHz,
CDCl3) δ 140.0, 138.8, 134.5, 133.6, 130.9, 129.9, 129.8, 125.9,
125.2, 124.3, 121.3, 60.6.
= 17.665 min. [α]2D5 = -30.2 (c = 0.74, CH2Cl2). H NMR (500
1
MHz, CDCl3) δ 7.75-7.77 (m, 1H), 7.46-7.49 (m, 2H), 7.33 (d, J
= 8.4 Hz, 2H), 7.19-7.22 (m, 2H), 7.09 (d, J = 6.9 Hz, 1H), 5.63
(d, J = 4.0 Hz, 1H), 4.86 (d, J = 3.5 Hz, 1H), 1.24 (s, 9H); 13C
NMR (125 MHz, CDCl3) δ 152.3, 140.1, 135.6, 135.0, 133.3,
129.4, 127.4, 126.2, 125.5, 121.1, 61.2, 34.7, 31.2.
4.2.5 (R)-3-(4-fluorophenyl)-2,3-dihydrobenzo[d]isothiazole 1,1-
dioxide (3e) 96% yield and 87% ee, determined by chiral HPLC
analysis (Daicel Chiralpak OD-H, Hexanes : IPA = 80 : 20, 0.6
mL/min, λ = 224 nm), tR (major) = 21.152 min, tR (minor) =
4.2.11 (R)-3-(o-tolyl)-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide
(3k) 80% yield and 76% ee, determined by chiral HPLC analysis
(Daicel Chiralpak AD-H, Hexanes : IPA = 80 : 20, 0.6 mL/min, λ
= 224 nm), tR (major) = 21.292 min, tR (minor) = 18.611 min.
35.546 min. [α]2D5 = -24.5 (c = 0.74, CH2Cl2). H NMR (500
1
[α]2D5 = -33.2 (c = 0.64, CH2Cl2). H NMR (500 MHz, CDCl3) δ
1
MHz, CDCl3) δ 7.81-7.84 (m, 1H), 7.54-7.59 (m, 2H), 7.33-7.37
(m, 2H), 7.12-7.13 (m, 1H), 7.05-7.10 (m, 2H), 5.72 (d, J = 4.2
Hz, 1H), 5.09 (d, J = 3.3 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ
139.6, 134.7, 134.6, 133.4, 129.6, 129.5, 129.4, 125.3, 121.2,
116.3, 116.1, 60.6.
7.73-7.75 (m, 1H), 7.46-7.49 (m, 2H), 7.14-7.18 (m, 2H), 7.06-
7.09 (m, 1H), 7.01-7.04 (m, 2H), 5.91 (d, J = 4.5 Hz, 1H), 4.94
(d, J = 4.0 Hz, 1H), 2.35 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
140.1, 136.7, 136.3, 135.6, 133.3, 131.2, 129.4, 129.0, 128.1,
127.0, 125.2, 121.3, 58.3.
4.2.6 (R)-3-(4-chlorophenyl)-2,3-dihydrobenzo[d]isothiazole 1,1-
dioxide (3f) 97% yield and 80% ee, determined by chiral HPLC
analysis (Daicel Chiralpak OD-H, Hexanes : IPA = 80 : 20, 0.6
mL/min, λ = 224 nm), tR (major) = 26.754 min, tR (minor) =
4.2.12 (R)-3-(2-methoxyphenyl)-2,3-dihydrobenzo[d]isothiazole
1,1-dioxide (3l) 95% yield and 98% ee, determined by chiral
HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 :
20, 0.6 mL/min, λ = 224 nm), tR (major) = 28.258 min, tR (minor)
43.172 min. [α]2D5 = -42.3 (c = 0.89, CH2Cl2). H NMR (500
1
= 23.731 min. [α]2D5 = -34.0 (c = 0.84, CH2Cl2). H NMR (500
1
MHz, CDCl3) δ 7.81-7.83 (m, 1H), 7.54-7.59 (m, 2H), 7.25-7.38
(m, 2H), 7.34 (dd, J = 8.5 Hz, J = 19.6 Hz, 4H), 7.12-7.13 (m,
1H), 5.71 (d, J = 4.2 Hz, 1H), 5.15 (d, J = 3.4 Hz, 1H); 13C NMR
(125 MHz, CDCl3) δ 139.2, 137.3, 135.1, 134.7, 133.5, 129.7,
129.5, 128.9, 125.3, 121.3, 60.6.
MHz, CDCl3) δ 7.75 (d, J = 6.8 Hz, 1H), 7.44-7.49 (m, 2H),
7.26-7.29 (m, 1H), 7.15-7.21 (m, 2H), 6.87-6.90 (m, 2H), 6.08 (d,
J = 5.0 Hz, 1H), 5.02 (d, J = 4.4 Hz, 1H), 3.76 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 157.0, 140.5, 135.3, 133.2, 130.2, 129.2,
128.7, 126.5, 125.3, 121.3, 121.1, 111.2, 56.3, 55.6.
4.2.7 (R)-3-(3-methoxyphenyl)-2,3-dihydrobenzo[d]isothiazole
1,1-dioxide (3g) 96% yield and 88% ee, determined by chiral
HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 :
20, 0.6 mL/min, λ = 224 nm), tR (major) = 36.618 min, tR (minor)
4.2.13
(S)-3-(2-chlorophenyl)-2,3-dihydrobenzo[d]isothiazole
1,1-dioxide (3m) 90% yield and 99% ee, determined by chiral
HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 :
20, 0.6 mL/min, λ = 224 nm), tR (major) = 23.034 min, tR (minor)
= 26.011 min. [α]2D5 = -12.4 (c = 0.79, CH2Cl2). H NMR (500
1
= 17.754 min. [α]2D5 = -36.2 (c = 0.87, CH2Cl2). H NMR (500
1
MHz, CDCl3) δ 7.74 (d, J = 8.4 Hz, 1H), 7.44-7.50 (m, 2H),
7.20-7.24 (m, 1H), 7.10 (d, J = 7.0 Hz, 1H), 6.88 (d, J = 7.7 Hz,
1H), 6.80-6.84 (m, 2H), 5.61 (d, J = 4.0 Hz, 1H), 5.10 (d, J = 3.6
Hz, 1H), 3.70 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 160.2,
140.4, 139.7, 134.6, 133.3, 130.3, 129.5, 125.4, 121.1, 119.7,
114.5, 112.9, 61.2, 55.3.
MHz, CDCl3) δ 7.74 (d, J = 7.2 Hz, 1H), 7.45-7.50 (m, 2H), 7.36
(d, J = 7.8 Hz, 1H), 7.26-7.31 (m, 1H), 7.14-7.23 (m, 3H), 6.28
(d, J = 4.0 Hz, 1H), 5.25 (d, J = 2.6 Hz, 1H); 13C NMR (125
MHz, CDCl3) δ 138.8, 136.7, 134.8, 133.5, 133.1, 130.0, 129.9,
129.7, 129.1, 127.9, 125.3, 121.3, 57.4.
4.2.8 (R)-3-(3-fluorophenyl)-2,3-dihydrobenzo[d]isothiazole 1,1-
dioxide (3h) 97% yield and 99% ee, determined by chiral HPLC
analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 : 20, 0.6
mL/min, λ = 224 nm), tR (major) = 27.474 min, tR (minor) =
4.2.14
(R)-3-(3,5-dimethylphenyl)-2,3-dihydrobenzo[d]
isothiazole 1,1-dioxide (3n) 98% yield and 93% ee, determined
by chiral HPLC analysis (Daicel Chiralpak AD-H, Hexane : IPA
= 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 16.108 min, tR
(minor) = 14.436 min. [α]2D5 = -22.5 (c = 0.67, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.82-7.84 (m, 1H), 7.52-7.57 (m, 2H), 7.14-
7.15 (m, 1H), 7.00 (s, 1H), 6.95 (s, 2H), 5.63 (d, J = 4.0 Hz, 1H),
4.9 (d, J = 2.9 Hz, 1H), 2.30 (s, 6H); 13C NMR (125 MHz,
CDCl3) δ 140.1, 139.0, 138.5, 134.8, 133.3, 130.8, 129.4, 125.4,
125.3, 121.1, 61.4, 21.3.
21.443 min. [α]2D5 = -33.5 (c = 0.62, CH2Cl2). H NMR (500
1
MHz, CDCl3) δ 7.76-7.78 (m, 1H), 7.48-7.53 (m, 2H), 7.28-7.33
(m, 1H), 7.09-7.14 (m, 2H), 6.98-7.04 (m, 2H), 5.56 (d, J = 4.1
Hz, 1H), 5.03 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 139.0,
133.5, 130.9, 130.8, 129.7, 125.3, 123.2, 121.2, 116.1, 115.9,
114.6, 114.4, 60.6.
4.2.9 (R)-3-(3-chlorophenyl)-2,3-dihydrobenzo[d]isothiazole 1,1-
4.2.15
(R)-3-(2-fluoro-4-methoxyphenyl)-2,3-dihydrobenzo[d]
dioxide (3i) 97% yield and 99% ee, determined by chiral HPLC
isothiazole 1,1-dioxide (3o) 93% yield and 98% ee, determined

5
by chiral HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA
= 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 36.528 min, tR
(minor) = 31.378 min. [α]2D5 = -23.4 (c = 0.74, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.74 (d, J = 7.5 Hz, 1H), 7.45-7.51 (m, 2H),
7.11-7.18 (m, 2H), 6.59 (d, J = 10.1 Hz, 2H), 5.99 (d, J = 4.5 Hz,
1H), 4.92 (d, J = 3.5 Hz, 1H), 3.71 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 139.5, 135.0, 133.4, 129.5, 125.2, 121.2, 111.0, 101.9,
101.7, 55.7, 54.2, 29.7.
oxathiazine 2,2-dioxide (5e) 97% yield and 98% ee, determined
by chiral HPLC analysis (Daicel Chiralpak OD-H, Hexanes : IPA
= 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 27.182 min, tR
(minor) = 33.632 min. [α]2D5 = -18.6 (c = 0.86, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.26-7.35 (m, 4H), 7.17 (d, J = 9.2 Hz, 1H),
7.01-7.06 (m, 2H), 6.75 (d, J = 7.8 Hz, 1H), 5.80 (d, J = 8.5 Hz,
1H), 4.66 (d, J = 8.4 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ
151.6, 139.8, 135.4, 130.9, 130.1, 129.9, 129.1, 128.5, 127.2,
125.6, 121.4, 119.1, 61.5.
4.2.16 (R)-3-(naphthalen-2-yl)-2,3-dihydrobenzo[d]isothiazole
1,1-dioxide (3p) 92% yield and 99% ee, determined by chiral
HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA = 80 :
20, 0.6 mL/min, λ = 224 nm), tR (major) = 43.947 min, tR (minor)
4.2.22
(S)-4-(4-chlorophenyl)-3,4-dihydrobenzo[e][1,2,3]
oxathiazine 2,2-dioxide (5f) 97% yield and 92% ee, determined
by chiral HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA
= 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 13.371 min, tR
(minor) = 14.419 min. [α]2D5 = -20.4 (c = 0.86, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.42 (d, J = 8.4 Hz, 2H), 7.35 (t, J = 7.8 Hz,
1H), 7.29 (d, J = 8.4 Hz, 2H), 7.12-7.07 (m, 2H), 6.81 (d, J = 7.8
Hz, 1H), 5.89 (d, J = 8.6 Hz, 1H), 4.70 (d, J = 8.0 Hz, 1H); 13C
NMR (125 MHz, CDCl3 ) δ 151.4, 136.2, 135.5, 130.2, 129.9,
129.6, 128.4, 125.3, 121.4, 118.9, 61.2.
= 36.322 min. [α]2D5 = -38.0 (c = 0.76, CH2Cl2). H NMR (500
1
MHz, CDCl3) δ 7.76-7.82 (m, 5H), 7.44-7.50 (m, 4H), 7.30 (dd, J
= 1.6 Hz, J = 8.6 Hz, 1H), 7.06-7.08 (m, 1H), 5.81 (d, J = 4.0 Hz,
1H), 5.02 (d, J = 3.3 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ
139.7, 135.9, 134.8, 133.5, 133.4, 133.1, 129.6, 128.0, 127.8,
127.2, 126.9, 126.8, 125.5, 124.4, 121.2, 61.6.
4.2.17 (S)-4-phenyl-3,4-dihydrobenzo[e][1,2,3]oxathiazine
2,2-dioxide (5a) [CAS 1025505-92-3 for S configuration, Ref.[9c]
97% ee, [α]2D5 = -18.0 (c = 1.01, CHCl3)]. 95% yield and 93% ee,
determined by chiral HPLC analysis (Daicel Chiralpak AD-H,
Hexanes : IPA = 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) =
:
4.2.23
(R)-4-(2-fluoro-4-methoxyphenyl)-3,4-dihydrobenzo[e]
[1,2,3]oxathiazine 2,2-dioxide (5g) 98% yield and 87% ee,
determined by chiral HPLC analysis (Daicel Chiralpak AD-H,
Hexanes : IPA = 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) =
15.227 min, tR (minor) = 14.326 min. [α]25 = -22.4 (c = 0.89,
18.900 min, tR (minor) = 20.448 min. [α]25 = -10.4 (c = 0.68,
D
D
CH2Cl2). 1H NMR (500 MHz, CDCl3) δ 7.42-7.44 (m, 3H), 7.31-
7.34 (m, 3H), 7.06-7.10 (m, 2H), 6.82 (d, J = 7.7 Hz, 1H), 5.90
(d, J = 8.7 Hz, 1H), 4.71 (d, J = 8.5 Hz, 1H); 13C NMR (125
MHz, CDCl3) δ 151.5, 137.9, 129.7, 129.6, 129.5, 128.8, 128.6,
125.3, 122.0, 118.8, 62.0.
CH2Cl2). H NMR (500 MHz, CDCl3) δ 7.32 (t, J = 7.7Hz, 1H),
1
7.21 (t, J = 8.6Hz, 1H), 7.09 (t, J = 7.6 Hz, 1H), 7.05 (d, J = 8.3
Hz, 1H), 6.80 (d, J = 7.8 Hz, 1H), 6.74-6.76 (m, 1H), 6.68-6.71
(m, 1H), 6.05 (d, J = 9.5 Hz, 1H), 5.01 (d, J = 9.2 Hz, 1H), 3.83
(s, 3H); 13C NMR (125 MHz, CDCl3) δ 151.2, 131.2, 129.7,
127.6, 125.3, 121.7, 118.8, 116.4, 116.3, 110.7, 102.6, 102.4,
56.6, 55.8.
4.2.18
(S)-4-(2-methoxyphenyl)-3,4-dihydrobenzo[e][1,2,3]
oxathiazine 2,2-dioxide (5b) 99% yield and 92% ee, determined
by chiral HPLC analysis (Daicel Chiralpak AD-H, Hexanes : IPA
= 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 28.988 min, tR
(minor) = 32.829 min. [α]2D5 = -20.8 (c = 0.65, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.33-7.37 (m, 1H), 7.26-7.28 (m, 1H), 7.18-
7.21 (m, 1H), 6.87-6.96 (m, 4H), 6.60 (d, J = 7.8 Hz, 1H), 5.83
(d, J = 10.3 Hz, 1H), 5.61 (d, J = 10.2 Hz, 1H), 3.60 (s, 3H); 13C
NMR (125 MHz, CDCl3) δ 157.2, 151.1, 131.3, 131.0, 129.2,
126.8, 124.9, 124.5, 122.8, 121.3, 118.3, 112.1, 60.3, 55.7.
4.2.24
(S)-4-(3-(trifluoromethyl)phenyl)-3,4-dihydrobenzo[e]
[1,2,3]oxathiazine 2,2-dioxide (5h) 95% yield and 75% ee,
determined by chiral HPLC analysis (Daicel Chiralpak AD-H,
Hexanes : IPA = 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) =
9.174 min, tR (minor) = 9.722 min. [α]2D5 = -15.2 (c = 0.71,
CH2Cl2). 1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 7.4 Hz, 1H),
7.63 (s, 1H), 7.55-7.60 (m, 2H), 7.38 (t, J = 7.8 Hz, 1H), 7.13
(dd, J = 7.6 Hz, J = 14.7 Hz, 2H), 6.81 (d, J = 7.8 Hz, 1H), 5.98
(d, J = 8.5 Hz, 1H), 4.81 (d, J = 8.4 Hz, 1H); 13C NMR (125
MHz, CDCl3) δ 151.5, 138.8, 132.3, 130.2, 130.1, 128.3, 126.5,
125.8, 125.5, 121.0, 119.2, 61.4.
4.2.19 (S)-4-(p-tolyl)-3,4-dihydrobenzo[e][1,2,3]oxathiazine 2,2-
dioxide (5c) 97% yield and 84% ee, determined by chiral HPLC
analysis (Daicel Chiralpak OD-H, Hexanes : IPA = 80 : 20, 0.6
mL/min, λ = 224 nm), tR (major) = 12.464 min, tR (minor) =
Appendix A. Supplementary date
15.649 min. [α]2D5 = -21.5 (c = 0.83, CH2Cl2). H NMR (500
1
Supplementary date to this article can be found online at
https://doi.org/
MHz, CDCl3) δ 7.24 (t, J = 7.9 Hz, 1H), 7.12-7.18 (m, 4H), 7.00
(t, J = 8.5 Hz, 2H), 6.74 (d, J = 7.8 Hz, 1H), 5.79 (d, J = 8.7 Hz,
1H), 4.57 (d, J = 8.5 Hz, 1H), 2.31 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 151.5, 139.6, 134.9, 130.1, 129.6, 128.7, 128.6, 125.2,
122.3, 118.8, 61.7, 21.2.
References
1
2
3
J. Vicente, R. T. Hendricks and D. B. Smith, Bioorg. Med. Chem.
Lett., 2009, 19, 5652.
G. J. Wells, M. Tao, K. A. Josef and R. Bihovsky, J. Med. Chem.,
2001, 44, 3488.
(a) M. Penso, D. Albanese, D. Landini, V. Lupi and A. Tagliabue, J.
Org. Chem., 2008, 73, 6686. (b) A. W. M. Lee, W. H. Chan, S. J.
Zhang and H. K. Zhang, Curr. Org. Chem., 2007, 11, 213.
4.2.20
(R)-4-(2-chlorophenyl)-3,4-dihydrobenzo[e][1,2,3]
oxathiazine 2,2-dioxide (5d) 95% yield and 99% ee, determined
by chiral HPLC analysis (Daicel Chiralpak OD-H, Hexanes : IPA
= 80 : 20, 0.6 mL/min, λ = 224 nm), tR (major) = 12.313 min, tR
(minor) = 17.148 min. [α]2D5 = -32.2 (c = 0.74, CH2Cl2). 1H NMR
(500 MHz, CDCl3) δ 7.41 (d, J = 7.9 Hz, 1H), 7.23-7.33 (m, 4H),
7.03 (t, J = 7.6 Hz, 1H), 6.99 (d, J = 8.3 Hz, 1H), 6.71 (d, J = 7.8
Hz, 1H), 6.24 (d, J = 6.2 Hz, 1H), 5.12 (d, J = 5.5 Hz, 1H); 13C
NMR (125 MHz, CDCl3) δ 151.5, 135.0, 134.1, 131.2, 130.9,
130.7, 129.8, 127.8, 127.7, 125.4, 121.2, 118.9, 59.4.
4
E. Differding, G. M. Rüegg and R. W. Lang, Tetrahedron Lett., 1991,
32, 1779.
5
(a) C. -B. Yu, D. -W. Wang and Y. -G. Zhou, J. Org. Chem., 2009, 74,
5633. (b) Y. Gao, F. Yang, D. Pu, R. D. Laishram, R. Fan, G. Shen, X.
Zhang, J. Chen and B. Fan, Eur. J. Org. Chem., 2018, 45, 6274. (c) Y.
Li, M. Lei, W. Yuan, E. Meggers and L. Gong, Chem. Commun.,
2017, 53, 8089. (d) F. Chen, Z. Li, Y. He and Q. Fan, Chinese J.
4.2.21
(S)-4-(3-chlorophenyl)-3,4-dihydrobenzo[e][1,2,3]

6
Tetrahedron
Chem., 2010, 28, 1529. (e) H. Xu, P. Yang, P. Chuanprasit, H. Hirao
12 (a) T. M. Gøgsig, J. Am. Chem. Soc., 2012, 134, 443. (b) R.
Matsubara, A. C. Gutierrez and T. F. Jamison, J. Am. Chem. Soc.,
2011, 133, 19020. (c) S. Z. Tasker, A. C. Gutierrez and T. F. Jamison,
Angew. Chem. Int. Ed., 2014, 53, 1858. (d) J. K. Vandavasi, X. Y.
Hua, H. H. Ben and S. G. Newman, Angew. Chem. Int. Ed., 2017, 56,
15441.
and J. Zhou, Angew. Chem. Int. Ed., 2015, 54, 5112. (f) F. Yang, J.
Chen, G. Shen, X. Zhang and B. Fan, Chem. Commun., 2018, 54,
4963. (g) X. Zhang, J. Chen, Y. Gao, K. Li, Y. Zhou, W. Sun and B.
Fan, Org. Chem. Front., 2019, 6, 2410.
B. Song, C. -B. Yu, W. -X. Huang, M. -W. Chen and Y. -G. Zhou, Org.
Lett., 2015, 17, 190.
B. Song, C. -B. Yu, Y. Ji, M. -W. Chen and Y. -G. Zhou, Chem.
Commun., 2017, 53, 1704.
(a) T. Jiang, Z. Wang and M. -H. Xu, Org. Lett., 2015, 17, 528. (b) T.
Nishimura, A. Noishiki, G. C. Tsui and T. Hayashi, J. Am. Chem.
Soc., 2012, 134, 5056. (c) H. Wang, T. Jiang and M. -H. Xu, J. Am.
Chem. Soc., 2013, 135, 971.
6
7
8
13 (a) M. G. Beaver and T. F. Jamison, Org. Lett., 2011, 13, 4140. (b) R.
M. Moslin and T. F. Jamison, Org. Lett., 2006, 8, 455. (c) H. A.
Malik, G. J. Sormunen and J. Montgomery, J. Am. Chem. Soc., 2010
132, 6304. (d) P. Liu, J. Montgomery and K. N. Houk, J. Am. Chem.
Soc., 2011, 133, 6956. (e) O. Yan, P. Yu and W. Li, Tetrahedron, 2019
75, 4486. (f) J. Liu and H. Gong, Org. Lett., 2018, 20, 7991. (g) S. -Z.
Sun, M. Borjesson, R. Martin-Montero and R. Martin, J. Am. Chem.
Soc., 2018, 140, 12765. (h) S. Ni, W. Zhang, H. Mei, J. Han and Y.
Pan, Org. Lett., 2017, 19, 2536.
,
,
9
(a) Y. Álvarez-Casao, D. Monge, E. Álvarez, R. Fernandez ́and J. M.
Lassaletta, Org. Lett., 2015, 17, 5104. (b) Z. Yan, B. Wu, X. Gao and
Y. -G. Zhou, Chem. Commun., 2016, 52, 10882. (c) B. Zhou, K. Li,
C. Jiang, Y. Lu and T. Hayashi, Adv. Synth. Catal., 2017, 359, 1969.
(d) G. Yang and W. Zhang, Angew. Chem. Int. Ed., 2013, 52, 7540.
14 (a) M. Quan, L. Tang, J. Q. Shen, G. Q. Yang and W. B. Zhang, Chem.
Commun., 2017, 53, 609. (b) W. Y. Sun, H. R. Gu and X. F. Lin, J.
Org. Chem., 2018, 83, 4034.
10 (a) T. Mesganaw and N. K. Garg, Org. Process Res. Dev., 2013, 17,
29. (b) M. Tobisu, T. Xu, T. Shimasaki, and N. Chatani, J. Am. Chem.
Soc., 2011, 133, 19505. (c) S. Ge, and J. F. Hartwig, Angew. Chem.
Int. Ed., 2012, 51, 12837. (d) M. A. Greene, I. M. Yonova, F. J.
Williams and E. R. Jarvo, Org. Lett., 2012, 14, 4293. (e) Q. Zhou, H.
15 (a) Z. Qiu, R. Sun and D. Teng, Org. Biomol. Chem., 2018, 16, 7717.
(b) Y. Gao, Z. Qiu, R. Sun, N. Gao, G. Cao and D. Teng, Tetrahedron
Lett., 2018, 59, 3938. (c) Z. Qiu, R. Sun, K. Yang and D. Teng,
Molecules., 2019, 24, 1575.
16 (a) S. Li, S. F. Zhu, C. M. Zhang, S. Song and Q. L. Zhou, J. Am.
Chem. Soc., 2008, 130, 8584. (b) S. Li, S. F. Zhu, J. H. Xie, S. Song,
C. M. Zhang and Q. L. Zhou, J. Am. Chem. Soc., 2010, 132, 1172. (c)
S. Song, S. F. Zhu, S. Yang, S. Li and Q. L. Zhou, Angew. Chem. Int.
Ed., 2012, 51, 2708. (d) S. Song, S. F. Zhu, L. Y. Pu and Q. L. Zhou,
Angew. Chem. Int. Ed., 2013, 52, 6072. (e) S. Song, S. F. Zhu, Y. B.
Yu and Q. L. Zhou, Angew. Chem. Int. Ed., 2013, 52, 1556. (f) J.
Shang, Z. B. Han, Y. Li, Z. Wang annd K. L. Ding, Chem. Commun.,
2012, 48, 5172. (g) X. M. Wang, Z. B. Han, Z. Wang and K. L. Ding,
Angew. Chem. Int. Ed., 2012, 51, 936. (h) S. -F. Zhu, J. -B. Xie, Y. -
Z. Zhang, S. Li and Q. -L. Zhou, J. Am. Chem. Soc., 2006, 128,
12886. (i) Z. Han, Z. Wang, X. Zhang and K. Ding, Angew. Chem.
Int. Ed., 2009, 48, 5345. (j) Y. Zhang, Z. Han, F. Li, K. Ding and A.
Zhang, Chem. Commun., 2010, 46, 156.
D. Srinivas, S. Dasgupta and M. P. Watson, J. Am. Chem. Soc., 2013
,
135, 3307. (f) E. Javier, G. Malcolm, H. Adrian, A. L. David, T. M.
Vanesa and J. Daniel, Chem. Sci., 2019, 10, 7269. (g) X. Ye, Z. Yuan,
Y. Zhou, Q. Yang, Y. Xie, Z. Deng and Y. Peng, J. Heterocyclic
Chem., 2016, 53, 1956. (h) S. -B. Mohammad and A. Zeinab,
Heteroatom Chem., 2015, 26, 355.
11 (a) K. Muto, J. Yamaguchi and K. Itami, J. Am. Chem. Soc., 2012
,
134, 169. (b) K. Amaike, K. Muto, J. Yamaguchi and K. Itami, J. Am.
Chem. Soc., 2012, 134, 13573. (c) H. Shiota, Y. Ano, Y. Aihara, Y.
Fukumoto and N. Chatani, J. Am. Chem. Soc., 2011, 133, 14952. (d)
Y. Aihara and N. Chatani, J. Am. Chem. Soc., 2013, 135, 5308. (e) Y.
Aihara and N. Chatani, J. Am. Chem. Soc., 2014, 136, 898. (f) X. -J.
Liu, Y. -Y. Tian, H. -Q. Cui and H. -J. Fan, Chem. Commun., 2018
,
54, 7912. (g) A. C. Kruegel, S. Rakshit, X. Li and D. Sames, J. Org.
Chem., 2015, 80, 2062.
17 (a) J. Sun, C. Mou, Z. Wang, F. He, J. Wu, Y. R. Chi, Org. Lett., 2018
20, 5969. (b) H. Wang, M. H. Xu, Synthesis, 2013, 45, 2125.
,

A new method was reported for the synthesis of chiral tertiary benzosultams.
A Ni(II)/SMI-PHOX catalyzed asymmetric addition of arylboronic acids was detected.
Milder reaction conditions and wider substrate scope were achieved.

Declaration of interests
The authors declare that they have no known competing financial interests or personal relationships
√
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: