Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic imines

Article abstract of DOI:10.1039/C6CC08759K

A Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic aldimines and ketimines is reported. Our tropos phosphine-oxazoline biphenyl ligand is crucial for the high catalytic activity, which coordinates to Ni(ii) to form a complex with a single axial configuration. The desired chiral amine products could be prepared with excellent yields (up to 99%) and enantioselectivities (up to 99.8%) under mild reaction conditions.

Full text of DOI:10.1039/C6CC08759K

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: M. Quan, L. Tang,
J. Shen, G. Yang and W. Zhang, Chem. Commun., 2016, DOI: 10.1039/C6CC08759K.
This is an Accepted Manuscript, which has been through the
Volume 52 Number
1 4 January 2016 Pages 1–216
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Accepted Manuscripts are published online shortly after
Chemical Communications
www.rsc.org/chemcomm
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
=
3
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 4
ChemComm
View Article Online
DOI: 10.1039/C6CC08759K
Journal Name
COMMUNICATION
Ni(II)-Catalyzed Asymmetric Addition of Arylboronic Acids to
Cyclic Imines
Mao Quan,a Liang Tang,a Jiaqi Shen,a Guoqiang Yang*a and Wanbin Zhang*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A Ni(II)-catalyzed asymmetric addition of arylboronic acids to cyclic hard organometallic reagents to cyclic α,β-enones was
aldimines and ketimines is reported. Our tropos phosphine- accomplished several years ago.7 However, these catalytic
oxazoline biphenyl ligand is crucial for the high catalytic activity, methods suffer from sensitivity to both air and moisture. The
which coordinates to Ni(II) to form a complex with a single axial use of arylboronic acids for Ni(II)-catalysis may overcome these
configuration. The desired chiral amine products could be prepared drawbacks. Indeed, several reports concerning the Ni(II)-
with excellent yields (up to 99%) and enantioselectivities (up to catalyzed addition of arylboronic acids to carbonyl compounds
99.8%) under mild reaction conditions.
and the conjugate addition of arylboronic acids to α,β-
unsaturated carbonyl compounds have recently been
developed.8,9,10 However, the Ni(II)-catalyzed addition of
arylboronic acids to imines [Ni(II) throughout the catalytic cycle,
see ESI] and its enantioselective variant have yet to be reported
and remain challenging. This may be due to the low nucleophilic
ability of the aryl-Ni(II) species and its tendency to undergo
homocoupling. In continuation of our efforts to develop
transition-metal-catalyzed asymmetric additions of arylboronic
acids,3h,3k,3m,11 we herein report the first Ni(II)-catalyzed
asymmetric addition of arylboronic acids to cyclic imines.
Interestingly, our tropos phosphine-oxazoline biphenyl ligand12
is crucial for obtaining the desired products in excellent yields
and with good enantioselectivities.
The transition-metal-catalyzed asymmetric addition of
organometallic reagents to imines is an excellent method for
the preparation of α-substituted chiral amines. The addition of
hard organometallic reagents to imines has been extensively
studied, with such procedures usually employing inexpensive
copper salts as metal catalysts.1 Owing to their good functional
group tolerance and ease of use, organoboron reagents have
attracted much attention for application in transition-metal-
catalyzed addition reactions.2,3 Rh-catalyzed asymmetric
additions of organoboron reagents to imines have been well
studied by the groups of Hayashi, Lin, Xu and Lam, etc.2 and Pd-
catalyzed asymmetric additions of organoboron reagents to
imines have been reported recently.3 However, despite the
success achieved through the rhodium- or palladium-catalyzed
asymmetric addition of organoboron reagents to imines, the
viability of transition metal catalysts in this reaction is still worth
exploring.
Table 1 Reaction optimizationa
Nickel is an abundant metal and much cheaper than
rhodium and palladium. Nickel catalysis is commonly used for
enantioselective cross-coupling reactions.4 Several groups have
developed Ni(0)-catalyzed addition reactions which proceed
through a Ni(0)-Ni(II)-Ni(0) catalytic cycle (see ESI).5,6 Using this
mechanism, Ni(0)-catalyzed additions of organoboron reagents
to electron-deficient olefins, aldehydes and ketones have been
realized.6 The Ni(II)-catalyzed asymmetric conjugate addition of
Entry
Ligand Ni Source
Yield (%)b ee (%)c
Ni(ClO4)2·6H2O NR --
1
2
3
4
5
6
7
8
--
L1a
L1b
L2a
L2b
L3a
L3b
L4
Ni(ClO4)2·6H2O 96
95
98
99
96
97
97
--
Ni(ClO4)2·6H2O 83
Ni(ClO4)2·6H2O 37
Ni(ClO4)2·6H2O 17
Ni(ClO4)2·6H2O 69
Ni(ClO4)2·6H2O 66
Ni(ClO4)2·6H2O trace
Ni(ClO4)2·6H2O trace
Ni(ClO4)2·6H2O 94
a.School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University,
800 Dongchuan Road, Shanghai 200240, China. Email: gqyang@sjtu.edu.cn;
wanbin@sjtu.edu.cn
9
10d
L5
L1a
--
96
†
Electronic Supplementary Information (ESI) available. See DOI:
10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 4
COMMUNICATION
Journal Name
11d
L1a
L1a
L1a
L1a
L1a
L1a
L1a
NiCl2·6H2O
Ni(OAc)2·4H2O 74
NiBr2 72
Ni(ClO4)2·6H2O trace
90
94
96
96
--
--
--
that the COD almost had no effect on the Ni(II)-catalyzed
addition (entry 17 vs 16).
View Article Online
DOI: 10.1039/C6CC08759K
12d
13d
14d,e
15d
16d,f
17d,f,g
Table 2 Scope of arylboronic acidsa
--
NR
NR
Ni(COD)2
Ni(ClO4)2·6H2O 90
94
a Reactions were carried out on a 0.20 mmol scale (1a) using
PhB(OH)2 (0.30 mmol), 5 mol% nickel salt, 7.5 mol% ligand in
unpurified solvent (2.0 mL) in a test tube for 48 h which was
opened to air at reflux. b Yield of isolated product. c Ees were
determined by HPLC using a chiral Daicel column. 60 C.
MeOH, EtOH, DCE or toluene instead of TFE were used as
Entry
1
2
3
4
5
6
7
8
Ar
Yield (%)b
94
99
98
96
87
95
89
89
99
93
87
90
98
91
99
82
ee (%)c
96
89
95
96
96
95
94
95
97
95
82
95
96
96
96
95
94
88
87
93
89
C6H5
2-MeOC6H4
3-MeOC6H4
4-MeOC6H4
3-MeC6H4
4-MeC6H4
4-tBuC6H4
4-PhC6H4
2-FC6H4
4-FC6H4
2-ClC6H4
3-ClC6H4
4-ClC6H4
d
o
e
f
f
solvent. N2 atmosphere in a sealed tube. COD was added
(10 mol%). TFE = trifluoroethanol, DCE = 1,2-dichloroethane,
NR = no reaction.
9
10
11
12
13
14
15
16
17
18
19
20
The use of cyclic aldimine benzoxathiazine-2,2-dioxdie 1a
for Rh(II)-catalyzed addition was studied by Lam group firstly.2m
Our study began with the reaction of 1a with phenylboronic acid
3-BrC6H4
4-BrC6H4
3-CF3C6H4
3-thienyl
2-naphthyl
3,4-(OCH2O)C6H3
3,5-diMeC6H3
2-F-4-MeOC6H3
(
2a) (Table 1). If the reaction was conducted in the absence of
77
82
85
92
L1a, no product was obtained and the starting materials were
recovered intact (entry 1). After screening various reaction
conditions, we found that excellent yield and good
enantioselectivity could be obtained by carrying out the
reaction with 5.0 mol% of Ni(ClO4)2·6H2O, 7.5 mol% ligand L1a
in TFE at reflux for 48 h, under air (Table 1, entry 2). The type of
ligand greatly influences this catalytic reaction (entries 2-8). If
L1b is used instead of L1a, the enantioselectivity increases
slightly, whereas the yield decreases to 83% (entry 3). Planar
21
83
a
Reactions were carried out on a 0.20 mmol scale using 5
mol% Ni(ClO4)2·6H2O, 7.5 mol% ligand and ArB(OH)2 (0.30
mmol) in unpurified TFE (2.0 mL) at 60 oC in a test tube for 48
b
c
h which was opened to air. Isolated yields. Ees were
determined by chiral HPLC.
chiral P-N ligands such as ferrocene-based-Phox ligands (L2a
,
With the optimized conditions in hand, the arylboronic acid
scope was examined, as shown in Table 2. The results showed
that arylboronic acids bearing both electron-donating and
electron-withdrawing substituents gave the corresponding
products with good to excellent yields and enantioselectivities
(Table 2, entries 2-16). Furthermore, the substitution position
on the benzene ring has little influence on the results, and
excellent yields and enantioselectivities could be obtained with
all examples (entries 2-16). It is noteworthy that the reaction
proceeded smoothly when a substituent was situated at the
ortho position of the arylboronic acid (entries 2, 9, 11). The
ortho substituent may coordinate with the nickel, thus reducing
the impact of the steric hindrance. Fused-ring aryl, heteroaryl
and disubstituted boronic acids also gave their corresponding
products with good to excellent yields and enantioselectivities
(entries 17-21).
L2b only gave low yields of product, although
)
enantioselectivities were excellent (entries 4-5). iPr- or tBu-
Phox ligand (L3a, L3b) gave moderate yields and high
enantioselectivities (entries 6-7). When the P-N ligand was
changed to the N-N ligand L4 or P-P ligand L5, only trace
amounts of product were obtained even after 48 h (entries 8
and 9). Different reaction temperatures were also investigated,
o
and the optimal temperature was found to be 60 C (entry 10,
also see ESI file for detail results). All the tested nickel salts, in
addition
to
Ni(ClO4)2·6H2O,
provided
excellent
enantioselectivities; however, the yields decreased,
presumably due to stronger coordination of the counteranion
with the nickel metal center (entries 11-13). The solubility of
NiBr2 in TFE was poor, thus the product was obtained with only
moderate yield. Other solvents such as MeOH, EtOH, DCE and
toluene gave only trace amounts of product (entry 14). If no
nickel salt was used, none of the desired product was obtained
(entry 15). When the reaction was conducted with Ni(COD)2
under N2 (entry 16), no product was obtained after 48 h,
indicating that Ni(0) is not able to catalyze this reaction under
our reaction conditions (see ESI). A Control experiment showed
The substrate scope was also investigated, the results of
which are summarized in Scheme 1. They show that substrates
possessing both electron-donating and electron-withdrawing
substituents gave the corresponding products with excellent
yields and enantioselectivities (3ba-3ha). Furthermore, the
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 4
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
coordinates with L1a, two possible configurations of the Ni(II)
View Article Online
complex can form: (aS)-L1a-Ni(II) and (aRD)O-LI:11a0-.1N0i3(9II/)C(6FCigCu0r8e7519)K.
Figure 1 Coordination behavior of L1a and X-ray structure of
complex (aS)-L1a-Ni(II)
.
The formation of (aR)-L1a-Ni(II) is disfavored due to the steric
hindrance of the iPr group and the anion coordinated to Ni(II).
However, the coordination behavior of the tropos phosphine-
oxazoline biphenyl-Ni(II) complex in solvent could not be
detected by NMR. The tropos phosphine-oxazoline biphenyl-
Ni(II) complex was crystallized from EtOAc and X-ray diffraction
analysis showed that its axial chirality has an S configuration and
the coordination configuration is tetrahedron. The calculations
show that in solution the configuration of the catalyst converts
from tetrahedron to planar (see ESI). The configuration of Ni(II)
of (aS)-L1a-Ni(II) is most likely different in solution and in the
solid state. Reported DFT calculations also show that the
configuration of Ni(II) in solution is planar.13
Scheme 1 Scope of cylic imines.
substitution on the ortho position of the benzene ring has little
influence on the results, and excellent yields and
enantioselectivities could also be obtained (3ba and 3da).
Additionally, when the benzene ring was changed to a
naphthalene ring, excellent enantioselectivities were also
observed but the yields decreased, mainly due to the poor
solubility of the substrates (3ia and 3ja). The high performance
of the L1a-Ni(II) catalyst was also observed for the asymmetric
addition of arylboronic acids to ketimines, the products of
which bear a chiral α-tertiary amine skeleton. The results show
that all the arylboronic acids tested were capable of providing
the corresponding products in good yields and with excellent
Scheme 2 Model for explaining the origin of asymmetric
induction.
Based on the structure of complex (aS)-L1a-Ni(II), the
stereochemical outcome can be explained using the model
shown in Scheme 2. The aryl group is bound to the Ni(II) center
and is trans to the oxazoline group of the ligand L1a; the imine
is bound at the position that is trans to the phosphine. In the
favored transition state, the -SO2- group of the cyclic imine is
oriented upward and thus positioned away from the chiral
group of the oxazoline. This leads to (R)-3aa as the major
product.
In summary, we have developed the first Ni(II)-catalyzed
asymmetric addition of arylboronic acids to cyclic aldimines and
ketimines with excellent yields (up to 99%) and
enantioselectivities (up to 99.8% ee) under mild reaction
conditions using our tropos phosphine-oxazoline ligand. The
ligands coordinates with Ni(II) to form a complex with S axial
chirality.
The National Nature Science Foundation of China (Nos.
21302124 and 21232004), Shanghai Chenguang Project
(No.14CG11), and Science and Technology Commission of
Shanghai Municipality (Nos. 14XD1402300 and 15Z111220016)
are acknowledged for financial support. The authors thank Prof.
Ilya D. Gridnev for helpful discussions, the High Performance
Computing center in SJTU and the Instrumental Analysis Center
of SJTU.
enantioselectivities (3ka
an ethyl ester group or fluorine group gave slightly lower yields,
although enantioselectivities remained excellent (3le 3me).
, 3ke-3ag). Ketimines substituted with
,
Other aryl-alkyl ketimines and aryl-aryl ketimines2l,2m and
acyclic aldimine2b were also tested as substrates, however,
these substrates showed very low reactivity or hydrolyzed
under our conditions, respectively.
To test the practicality of this methodology, a gram-scale
reaction using aldimine 1a was carried out (eq 1). The product
3aa was obtained with results comparable to those shown in
Table 2 using the same reaction conditions.
Based on our previous results, ligands exist as an equilibrium
mixture of diastereomers in solution due to rotation around the
internal bond of the biphenyl groups.12 Interestingly, when
these ligands coordinate to palladium or iridium, only one of
two possible diastereomeric complexes is formed. When nickel
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
J. Weix, J. Am. Chem. Soc., 2013, 135, 751; (d) J.-Q. He, C.
Chen, W.-B. Yu, R.-R. Liu, M. Xu, Y.-J. LiD, OJ.I-:R1.0G.10a3o9a/Cn6dCYC.0-X8.75Ji9aK,
Tetrahedron Lett., 2014, 55, 2805.
Notes and references
View Article Online
1
For a recent review, see: K. Yamada and K. Tomioka, Chem.
Rev., 2008, 108, 2874.
6
For Ni(0)-catalyzed addition of arylboron to carbonyl
compounds, see: (a) T. Arao, K. Kondo and T. Aoyama,
Tetrahedron Lett., 2007, 48, 4115; (b) K. Yamamoto, K.
Tsurumi, F. Sakurai, K. Kondo, T. Aoyama, Synthesis, 2008,
3585; (c) F. Sakurai, K. Kondo and T. Aoyama, Chem. Pharm.
Bull., 2009, 57, 511; (d) J. Bouffard and K. Itami, Org. Lett.,
2009, 11, 4410; (e) C.-H. Xing and Q.-S. Hu, Tetrahedron Lett.,
2010, 51, 924; (f) T. Maekawa, H. Sekizawa and K. Itami,
Angew. Chem., Int. Ed., 2011, 50, 7022; (g) C. Berini and O.
Navarro, Chem. Commun., 2012, 48, 1538; For Ni(0)-catalyzed
conjugate addition of arylboron to electron-deficient olefins,
see: (h) E. Shirakawa, Y. Yasuhara and T. Hayashi, Chem. Lett.,
2006, 35, 768; (i) Y.-C. Hong, P. Gandeepan, S. Mannathan,
W.-T. Lee and C.-H. Cheng, Org. Lett., 2014, 16, 2806.
2
For selected examples of Rh-catalyzed asymmetric addition of
organoboron reagents to imines, see: (a) M. Kuriyama, T.
Soeta, X. Hao, Q. Chen and K. Tomioka, J. Am. Chem. Soc.,
2004, 126, 8128; (b) N. Tokunaga, Y. Otomaru, K. Okamoto, K.
Ueyama, R. Shintani and T. Hayashi, J. Am. Chem. Soc., 2004,
126, 13584; (c) D. J. Weix, Y. Shi and J. A. Ellman, J. Am. Chem.
Soc., 2005, 127, 1092; (d) R. B. C. Jagt, P. Y. Toullec, D.
Geerdink, J. G. de Vries, B. L. Feringa and A. J. Minnaard,
Angew. Chem., Int. Ed., 2006, 45, 2789; (e) Z.-Q. Wang, C.-G.
Feng, M.-H. Xu and G.-Q. Lin, J. Am. Chem. Soc., 2007, 129
,
5336; (f) M. Trincado and J. A. Ellman, Angew. Chem., Int. Ed.,
2008, 47, 5623; (g) K. Kurihara, Y. Yamamoto and N. Miyaura,
Adv. Synth. Catal., 2009, 351, 260; (h) R. Shintani, M. Takeda,
T. Tsuji and T. Hayashi, J. Am. Chem. Soc., 2010, 132, 13168;
7
For Ni(II)-catalyzed asymmetric addition of hard
organometallic reagents, see: (a) C. Bolm and M. Ewald,
Tetrahedron Lett., 1990, 31, 5011; (b) J. F. G. A. Jansen and B.
(i) Y. Luo and A. J. Carnell, Angew. Chem., Int. Ed., 2010, 49
,
2750; (j) Z. Cui, H.-J. Yu, R.-F. Yang, W.-Y. Gao, C.-G. Feng and
G.-Q. Lin, J. Am. Chem. Soc., 2011, 133, 12394; (k) R. Shintani,
M. Takeda, Y.-T. Soh, T. Ito and T. Hayashi, Org. Lett., 2011,
13, 2977; (l) T. Nishimura, A. Noishiki, G. C. Tsui and T.
Hayashi, J. Am. Chem. Soc., 2012, 134, 5056; (m) Y. Luo, A. J.
Carnell and H. W. Lam, Angew. Chem., Int. Ed., 2012, 51, 6762;
(n) Y. Luo, H. B. Hepburn, N. Chotsaeng and H. W. Lam, Angew.
Chem., Int. Ed., 2012, 51, 8309; (o) H. Wang, T. Jiang and M.-
H. Xu, J. Am. Chem. Soc., 2013, 135, 971; (p) T. Nishimura, A.
Noishiki, Y. Ebe and T. Hayashi, Angew. Chem., Int. Ed., 2013,
L. Feringa, Tetrahedron: Asymmetry, 1992, 3, 581; (c) M. I.
Burguete, M. Collado, J. Escorihuela, F. Galindo, E. García-
Verdugo, S. V. Luis and M. J. Vicent, Tetrahedron Lett., 2003,
44, 6891; (d) Y. S. Kwak and E. J. Corey, Org. Lett., 2004,
6
,
,
3385; (e) O. V. Larionov and E. J. Corey, Org. Lett., 2010, 12
300.
8
9
For Ni(II)-catalyzed addition of arylboron to aldehydes, see: (a)
L. Zhou, X. Du, R. He, Z. Ci and M. Bao, Tetrahedron Lett., 2009,
50, 406; (b) W. Chen, M. Baghbanzadeh and C. O. Kappe,
Tetrahedron Lett., 2011, 52, 1677; (c) N. T. S. Phan, T. T.
Nguyen and A. H. Ta, J. Mol. Chem. A, 2012, 365, 95.
For Ni(II)-catalyzed addition of arylboron to electron-deficient
olefins, see: (a) P.-S. Lin, M. Jeganmohan and C.-H. Cheng,
52, 1777; (q) H. Wang, Y. Li and M.-H. Xu, Org. Lett., 2014, 16
,
3962; (r) J. D. Sieber, D. Chennamadhavuni, K. R. Fandrick, B.
Qu, Z. S. Han, J. Savoie, S. Ma, L. P. Samankumara, N. Grinberg,
H. Lee, J. J. Song and C. H. Senanayake, Org. Lett., 2014, 16
5494; (s) T. Jiang, Z. Wang and M.-H. Xu, Org. Lett., 2015, 17
,
,
Chem. Asian J., 2007,
2, 1409; (b) W. Chen, L. Sun, X. Huang, J.
528; (t) J. Kong, M. McLaughlin, K. Belyk and R. Mondschein,
Org. Lett., 2015, 17, 5520; (u) R. Takechi and T. Nishimura,
Org. Biomol. Chem., 2015, 13, 4918; (v) Y. Wang, Y. Liu, D.
Zhang, W. Wei, M. Shi and F. Wang, Angew. Chem., Int. Ed.,
2016, 55, 3776.
Wang, Y. Peng and G. Song, Adv. Synth. Catal., 2015, 357
,
1474; For Ni(II)-catalyzed cyclizations of alkynyl electrophiles
generated from the addition of arylboronic acids to alkynes,
see: (c) C. Clarke, C. A. Incerti-Pradillos, H. W. Lam, J. Am.
Chem. Soc., 2016, 138, 8068.
3
For Pd-catalyzed asymmetric addition of organoboron
reagents to imines, see: (a) H. Dai, M. Yang and X. Lu, Adv.
Synth. Catal., 2008, 350, 249; (b) Q. Zhang, J. Chen, M. Wu, J.
Cheng, C. Qin, W. Su and J. Ding, Synlett, 2008, 935; (c) H. Dai
and X. Lu, Tetrahedron Lett., 2009, 50, 3478; (d) G.-N. Ma, T.
Zhang and M. Shi, Org. Lett., 2009, 11, 875; (e) C. S. Marques
and A. J. Burke, Eur. J. Org. Chem., 2010, 1639; (f) Z. Liu and
M. Shi, Tetrahedron, 2010, 66, 2619; (g) J. Chen, X. Lu, W. Lou,
Y. Ye, H. Jiang and W. Zeng, J. Org. Chem., 2012, 77, 8541; (h)
G. Yang and W. Zhang, Angew. Chem., Int. Ed., 2013, 52, 7540;
(i) C. Jiang, Y. Lu and T. Hayashi, Angew. Chem., Int. Ed., 2014,
53, 9936; (j) C. Schrapel and R. Peters, Angew. Chem., Int. Ed.,
2015, 54, 10289; (k) M. Quan, G. Yang, F. Xie, I. D. Gridnev and
10 For Co-catalyzed addition of organoboron reagents to double
bonds, see: (a) J. Karthikeyan, M. Jeganmohan and C.-H.
Cheng, Chem. Eur. J., 2010, 16, 8989; (b) M.-H. Chen, S.
Mannathan, P.-S. Lin and C.-H. Cheng, Chem. Eur. J., 2012, 18
,
14918; The Zhao group recently reported a Co(II)-catalyzed
asymmetric addition of alkenylboronic acids to aldimines
during the preparation of this article, see: (c) Y. Huang, R.-Z.
Huang and Y. Zhao, J. Am. Chem. Soc., 2016, 138, 6571.
11 Q. He, F. Xie, G. Fu, M. Quan, C. Shen, G. Yang, I. D. Gridnev,
and W. Zhang, Org. Lett., 2015, 17, 2250.
12 (a) F. Tian, D. Yao, Y. Zhang and W. Zhang, Tetrahedron, 2009,
65, 9609; (b) F. Tian, D. Yao, Y. Liu, F. Xie and W. Zhang, Adv.
Synth. Catal., 2010, 352, 1841; (c) Y. Liu, D. Yao, K. Li, F. Tian,
F. Xie and W. Zhang, Tetrahedron, 2011, 67, 8445; (d) Y. Liu
and W. Zhang, Angew. Chem., Int. Ed., 2013, 52, 2203; (e) Y.
Liu, I. D. Gridnev and W. Zhang, Angew. Chem., Int. Ed., 2014,
53, 1901.
13 (a) K. W. Quasdorf, A. Antoft-Finch, P. Liu, A. L. Silberstein, A.
Komaromi, T. Blackburn, S. D. Ramgren, K. N. Houk, V.
Snieckus and N. K. Garg, J. Am. Chem. Soc., 2011, 133, 6352;
(b) T. Sperger, I. A. Sanhueza, I. Kalvet and F. Schoenebeck,
Chem. Rev. 2015, 115, 9532.
W. Zhang, Org. Chem. Front., 2015, 2, 398; (l) T. Beisel and G.
Manolikakes, Org. Lett., 2015, 17, 3162; (m) Q. He, L. Wu, X.
Kou, N. Butt, G. Yang and W. Zhang, Org. Lett., 2016, 18, 288;
(n) B. Zhou, C. Jiang, V. R. Gandi, Y. Lu and T. Hayashi, Chem.
Eur. J., 2016, 22, 13068; (o) Z. Yan, B. Wu, X. Gao and Y.-G.
Zhou, Chem. Commun., 2016, 52, 10882.
4
5
For selected Ni-catalyzed enantioselective coupling reactions,
see: (a) T. Hayashi and M. Kumada, Acc. Chem. Res., 1982, 15
,
395; (b) S. J. Patel and T. F. Jamison, Angew. Chem., Int. Ed.,
2004, 43, 3941; (c) C. Fischer and G. C. Fu, J. Am. Chem. Soc.,
2005, 127, 4594; (d) A. H. Cherney, N. T. Kadunce and S. E.
Reisman, J. Am. Chem. Soc., 2013, 135, 7442.
For selected examples of using halohydrocarbons as
nucleophilic reagents, see: (a) K. K. Majumdar and C.-H.
Cheng, Org. Lett., 2000,
2, 2295; (b) R. Shrestha and D. J. Weix,
Org. Lett., 2011, 13, 2766; (c) R. Shrestha, S. C. M. Dorn and D.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins