Electronically deficient (Rax,S,S)-F12-C3-TunePhos and its applications in asymmetric 1,4-addition reactions

Article abstract of DOI:10.1016/j.tetlet.2016.03.072

A novel electronically deficient chiral diphosphine ligand (R_ax,S,S)-F₁₂-C₃-TunePhos has been concisely synthesized. The electron-poor ligand features both chiral centers and chiral axis bearing fluoro-functional groups on

Full text of DOI:10.1016/j.tetlet.2016.03.072

Tetrahedron Letters 57 (2016) 1925–1929
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Electronically deficient (Rax,S,S)-F12-C3-TunePhos and its applications
in asymmetric 1,4-addition reactions
⇑
Shu-Bo Hu, Zhang-Pei Chen, Ji Zhou, Yong-Gui Zhou
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel electronically deficient chiral diphosphine ligand (Rax,S,S)-F12-C3-TunePhos has been concisely
synthesized. The electron-poor ligand features both chiral centers and chiral axis bearing fluoro-func-
tional groups on each phosphorus phenyl ring based on C3-TunePhos backbone. The catalyst composed
of this ligand and rhodium showed excellent activities and enantioselectivities in asymmetric 1,4-addi-
Received 25 February 2016
Revised 20 March 2016
Accepted 22 March 2016
Available online 22 March 2016
tion reactions of arylboronic acids to diverse
a,b-unsaturated ketones with up to 99% ee.
Ó 2016 Elsevier Ltd. All rights reserved.
Keywords:
Fluorinated diphosphine ligand
Rhodium
1,4-Addition reactions
Chiral diphosphine ligands have attracted considerable atten-
tion due to their great significance in multifarious transition-
metal-catalyzed reactions in recent years.1 Subtle modifications
in steric, geometric, or electronic properties of chiral ligands could
dramatically affect the catalytic reactivity and stereocontrol of
metal–ligand complexes in specific reactions.2 Therefore, great
efforts have been made to design and synthesize novel chiral phos-
phine ligands with different scaffolds or electronic characters.3
Although studies were dominated in electron-rich diphosphine
ligands in the past decades, much attention has also been focused
on electron-deficient ligands recently.3d According to the foregoing
research, following features of electron-poor ligands may alter the
performance of the corresponding metal–ligand complexes in
asymmetric catalytic reactions. First of all, electronically deficient
substituted biphenyl ligands, trifluoromethylphosphine dinaph-
thalene ligand has also been prepared.2b,9 In 2003,
Weissensteiner and Spindler prepared another ferrocene-based
electronically deficient diphosphine ligand Walphos, which was
the fluorinated analogues of JosiPhos, and successfully employed
this ligand to Rh- and Ru-catalyzed asymmetric hydrogenation
reactions.10
Afterward, the famous ligand DifluorPhos was synthesized and
appropriate transition metals coordinated with this ligand could
catalyze numerous types of reactions with excellent enantioselec-
tivity.11 In 2009, Korenaga’s group developed a new fluorinated
ligand MeO-F12-BiPhep, which exhibited high efficiency in conju-
gated addition reactions of arylboronic acids to
a,b-unsaturated
ketones.12 Thereafter, various other kinds of electron-poor ligands
were reported gradually,13 for example the fluorinated SynPhos
analogue 3,5-diCF3-SynPhos.13d Recently, our group has also
prepared two kinds of electron-poor ligands TfO-BiPhep13e and
CF3O-BiPhep,13f which were applied to iridium-catalyzed
asymmetric hydrogenation of quinolines with high activity and
enantioselectivity. It is worth noting that the electron-poor
phosphine ligands with oxazoline moiety have also been
demonstrated as prepotent ligands in asymmetric allylic
alkylation reactions.14 Despite much progress has been made in
this field, since there is no omnipotent ligand for every reaction,
the needs for more efficient ligands are evident and the research
in the exploration of versatile ligands with sterically and electron-
ically diverse properties is of great significance. As the C3-Tune-
Phos backbone-based diphosphine ligands are privileged motif in
the chemistry of ligand design,15 and together with our ongoing
efforts in promoting the development of asymmetric catalysis,
phosphine ligands are good
p-acceptors, which would display
significant ligand trans influence upon coordination to
a
transition metal center and the transition metal with which
could be more reactive.4 What’s more, the electron-poor ligands
could promote reductive elimination compared with electron-rich
ones.5 In addition, the rate of transmetalation6 and migratory
insertion7 of conjugated addition reactions could be accelerated
by an electronically poor ligand-based catalyst.
Since the pioneering research on the design of C2 symmetric flu-
orinated diphosphine BIFUP reported in 1991 by Achiwa’s group,8
some electron-poor chiral phosphine ligands have been synthe-
sized and applied to a variety of asymmetric catalytic reactions.
Some privileged electronically deficient chiral phosphine ligands
are listed in Figure 1. Besides 6,60-difluorinated and trifluoromethyl
⇑
Corresponding author.
http://dx.doi.org/10.1016/j.tetlet.2016.03.072
0040-4039/Ó 2016 Elsevier Ltd. All rights reserved.

1926
S.-B. Hu et al. / Tetrahedron Letters 57 (2016) 1925–1929
CF3
F3C
F3C
PPh2
PPh2
F
F
PPh2
PPh2
F3C
F3C
PPh2
PPh2
P(CF3)2
PPh2
6,6'-Difluorinated
biphenyl ligand
Jendralla
6,6'-Difluoromethyl
biphenyl ligand
Gonda
Dinaphthalene
based ligand
CF3
(R)-BIFUP
Achiwa
Togni
O
O
PPh2
F
F
O
MeO
MeO
PAr2
PAr2
PPh2
PPh2
O
O
PAr2
PAr2
PAr2
O
O
Fe
F
F
O
Ar = 3,5-(CF3)2C6H3
(Rc,Rp)-Walphos
(R)-DifluorPhos
Genêt Dellis,
Ar = 3,4,5-F3C6H2
(R)-MeO-F12-BiPhep
Korenaga, Sakai
Ar = 3,5-(CF3)2-C6H2
(R)-3,5-diCF3-SynPhos
Ratovelomanana-Vidal
,
Weissensteiner Spindler
,
Ratovelomanana-Vidal
O
O
N
tBu
RO
RO
PPh2
PPh2
O
O
PAr2
PAr2
N
Fe
P(CF3)2
P(CF3)2
R = Tf (R)-TfO-BiPhep
R = CF3 (R)-CF3O-BiPhep
Zhou
Oxazolinylferrocene
based ligand
You,Sun
Phosphino-Oxazoline
tBu-FOX
Ar = 3,4,5-F3C6H2
(Rax,S,S)-F12-C3-TunePhos
This work
Shen
Figure 1. Some examples of electron-deficient phosphine ligands.
herein, we report the synthesis of an electronically deficient
diphosphine ligand (Rax,S,S)-F12-C3-TunePhos, and its application
in rhodium-catalyzed asymmetric 1,4-addition reactions to cyclic
and acyclic enones with high reactivity and enantioselectivity.
could be successfully performed to give the desired product ligand
L1 with 16% overall yield in three steps.
The application probability of the electronically deficient ligand
L1 prepared above was evaluated by the rhodium-catalyzed conju-
gated addition reaction of arylboronic acids to enones.18 The com-
pound 2-cyclohexenone (4a) was selected as the model substrate
for condition optimization. Gratifyingly, the exposure of 4a with
5a in the presence of potassium hydroxide catalyzed by rho-
dium-L1 complex at room temperature in dioxane provided 3-
phenylcyclohexanone 6aa with >99% ee and 32% yield (Table 1,
entry 1). Next, a series of solvents were examined. The complete
conversion was obtained in dichloromethane and toluene (Table 1,
entries 1–5). Notably, the reaction could also proceed in the
absence of potassium hydroxide to give 6aa with 59% yield (Table 1,
entry 6). Elevating the dosage of potassium hydroxide had an obvi-
ous promoting effect on the reactivity (Table 1, entries 4–8).
Increasing the amount of 4a to decrease the percentage of catalyst
loading, the turnover frequency (TOF) reached 480 hꢀ1 in dichlor-
omethane and 760 hꢀ1 in toluene (Table 1, entries 9 and 10). These
Our synthetic approach to enantiopure ligand L1 ((Rax,S,S)-F12
-
C3-TunePhos) is depicted in Scheme 1. Initially, we tried to synthe-
size the ligand according to the literature report16 (equation a): the
bis(phosphonic dichlorides) was readily obtained in situ from com-
pound 1 by the treatment with thionyl chloride, which then under-
went tetrasubstitution with Grignard reagent to give the
phosphine oxide 2. However, due to some inseparable partially
defluorinated side products formed in the trichlorosilane reduction
of 2, the pure compound L1 could not be furnished. Subsequently,
we turned to another way that was represented in equation b.17 In
this conversion, compound 1 was reduced with lithium aluminum
hydride and chlorotrimethylsilane to give the bis(primary phos-
phine) intermediate, followed by treatment with triphosgene and
methyltrioctylazanium chloride to offer the bis(phosphornous
dichloride) 3. Finally, substitution of 3 with Grignard reagents
HSiCl3
1) SOCl2, DMF
2) ArMgBr
O
O
P(O)(OEt)2
P(O)(OEt)2
O
O
P(O)Ar2
P(O)Ar2
O
O
PAr2
PAr2
(eq. a)
DIPEA
1
(Rax,S,S)-
(Rax,S,S)-L1
(Rax,S,S)-2
Ar = 3,4,5-F3C6H2
Partially defluorinated
products formed
ArMgBr
1) LiAlH4, TMSCl
O
O
P(O)(OEt)2
P(O)(OEt)2
O
O
PCl2
PCl2
O
O
PAr2
PAr2
(eq. b)
2) CO(OCCl3)2,
Aliquat® 336
(Rax,S,S)-1
(Rax,S,S)-3
Ar = 3,4,5-F3C6H2
(Rax,S,S)-F12-C3-TunePhos L1
overall 16% yield
Scheme 1. Synthesis of ligand (Rax,S,S)-F12-C3-TunePhos.

S.-B. Hu et al. / Tetrahedron Letters 57 (2016) 1925–1929
1927
Table 1
Optimization of asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenonea
O
O
L
[RhCl(C2H4)2]2, , KOH
+
PhB(OH)2
Solvent, H2O, rt
Ph
4a
5a
6aa
Entry
Solvent
L
Yield (%)b
Ee (%)c
1
2
3
4
Dioxane
THF
Et2O
DCM
Toluene
DCM
DCM
Toluene
DCM
Toluene
Toluene
DCM
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L4
32
42
51
97
96
59
>99
>99
48
76
99
NR
NR
NR
NR
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
—
5
6d
7e
8e
9e,f
10e,f
11e,g
12e
13e
14e
15h
DCM
DCM
Toluene
—
—
—
O
O
PAr2
PAr2
O
O
PPh2
PPh2
PPh2 MeO
PPh2 MeO
PPh2
PPh2
L2
(Rax,S,S)-C3-TunePhos
L1
Ar = 3,4,5-F3-C6H2
L3
L4
(R)-BINAP
(R)-MeO-BiPhep
a
b
c
4a (0.6 mmol), 5a (0.72 mmol), [Rh(C2H4)2Cl]2 (0.5 mol %), L (1.05 mol %), solvent (0.8 mL), H2O (0.3 mL), KOH (20 mol %), rt, 1 h.
Isolated yield.
Determined by HPLC.
Without KOH.
d
e
f
KOH (40 mol %).
4a (6 mmol), 5a (7.2 mmol), [Rh(C2H4)2Cl]2 (0.05 mol %), L1 (0.105 mol %), Solvent (1.5 mL), H2O (1.0 mL).
4a (1.2 mmol), 5a (1.44 mmol), [Rh(C2H4)2Cl]2 (0.25 mol %), L1 (0.525 mol %).
The data were quoted from Ref. 12a. NR = no reaction.
g
h
results made it clear that the catalytic system in toluene was more
efficient than in dichloromethane, and thus, toluene was chosen as
the optimal solvent. To our delight, with the catalyst loading of
0.25 mol %, full conversion and excellent enantioselectivity were
achieved (Table 1, entry 11). In contrast, the rhodium complexes
with electronic-donating ligands L2, L3 or L4 showed no catalytic
activity in dichloromethane or toluene (Table 1, entries 12–15).
Consequently, the optimal conditions were established as: 4a
(1.2 mmol), 5a (1.44 mmol), [Rh(C2H4)2Cl]2 (0.25 mol %), L1
(0.525 mol %), potassium hydroxide (0.48 mmol), toluene (0.8 mL)
and water (0.3 mL), room temperature.
With the optimal conditions in hand, the exploration of sub-
strate scope was carried out (Table 2). All the meta- and para-sub-
stituted aryl boronic acids reacted with cyclic enone 4a smoothly
to afford the corresponding ketones in high yields (89–97%) and
excellent enantioselectivities (98–99% ee) (Table 2, entries 3–9).
For ortho-methyl substituted phenylboronic acid, the deterioration
in activity may be ascribed to the steric effect (Table 2, entry 2).
Interestingly, both electron-donating and electron-withdrawing
groups at the meta-position or para-position of the aryl boronic
acids were well tolerated under standard conditions (Table 2,
entries 3–6 and 7–9). Subsequently, the addition reactions of
phenylboronic acid to the five-membered-ring 2-cyclopentenone
4b was also studied (Table 2, entry 10), and the slightly lower
enantioselectivity may be attributed to the flatness of the molecule
of 2-cyclopentenone substrate resulting in less sensitive to the chi-
ral circumstance.19
In order to further estimate the performance of this catalytic
system, the substrate scope was expanded to more challenging
acyclic unsaturated ketones20 (Table 2, entries 11–16). Particularly,
the s-cis and s-trans conformational interconversion of acyclic sub-
strates made the enantiocontrol difficult.19 Nevertheless, the excel-
lent results obtained with cyclic substrates above encouraged us to
investigate this enantioselective transformation. Arylboronic acid
substrates bearing diverse substituents at the 4-position were
reacted with a series of alkyl acyclic enones, providing the corre-
sponding b-aryl ketones with 93–99% yields and 91–99% ees
regardless of the steric effects of the alkyl group in enones (Table 2,
entries 11–15). It was noteworthy that 4-phenylbut-3-en-2-one 4f
was also suitable substrate and furnish the diaryl substituted
ketone 6fd with 83% yield and 87% ee (Table 2, entry 16).
Enantiomerically pure 2-aryltetralone derivatives have owned
considerable attraction due to such kind of motif played a great
important role in organic synthesis and medicinal chemistry.21
Apart from palladium- or nickel-catalyzed asymmetric
a-aryla-
tion22 and -alkenylation23 of carbonyl compounds, and catalytic
a
asymmetric protonation of enolates,24 asymmetric arylation of
quinone monoketals has provided another efficient way to 2-aryl-
tetralones. In 2007, Hayashi’s group reported an elegant rhodium/
chiral diene complex catalyzed asymmetric 1,4-addition of aryl-
and alkenylboron reagents to quinone monoketals, and further
concise derivatization of the enantiopure addition products could
afford the chiral 2-aryltetralones without loss of ee values.25 Con-
sidering the importance of the 2-aryltetralones moieties and the

1928
S.-B. Hu et al. / Tetrahedron Letters 57 (2016) 1925–1929
Table 2
O
O
Scope of 1,4-addition of arylboronic acids to enonesa
O
O
O
[RhCl(C2H4)2]2, L1, ArB(OH)2
ref. 25
O
O
KOH, Toluene, H2O, rt
O
Ar
L1
[RhCl(C2H4)2]2, , KOH
Ar = 3,4-dimethoxyphenyl
O
O
O
O
+
ArB(OH)2
5
Toluene, H2O, rt
7b
8bl, 94%, 95% ee
X
Ar
X
4
6
O
O
O
4c, R = CH3
O
O
O
H
4d, R = C5H11
ref. 21
OMe
OMe
OMe
R
i
O
4e
, R = Pr
, R = Ph
H
Bn
4f
O
(-)-9
N
4a
4b
OMe
(-)-10
Entry
t (h)
4
Ar of 5
Ph (5a)
Yield (%)b
Ee (%)c
Scheme 2. Synthesis of hexahydrobenzo[c]benzophenanthridine alkaloid 10.
1
0.5
30
0.5
1
1
3
0.5
0.5
2
0.5
4
1
4
0.5
1
13
4a
4a
4a
4a
4a
4a
4a
4a
4a
4b
4c
4c
4c
4d
4e
4f
99
79
96
91
94
97
94
92
89
99
95
90
99
99
93
83
99
95
99
99
99
99
99
99
98
90
91
92
91
93
99
87
2d
3
2-CH3C6H4 (5b)
3-CH3C6H4 (5c)
4-CH3C6H4 (5d)
3-CH3OC6H4 (5e)
4-CH3OC6H4 (5f)
3-FC6H4 (5g)
4-FC6H4 (5h)
4-CF3C6H4 (5i)
Ph (5a)
ligand/rhodium catalyst was comparable with that of Hayashi’s
chiral diene ligand/rhodium catalyst in this 1,4-addition reactions.
For the sake of evaluating the practicability in the synthesis of
natural products, the asymmetric conjugated addition of (3,4-
dimethoxyphenyl)boronic acid to naphthoquinone monoketal 7b
was also investigated. The reaction took place smoothly and pro-
duced 8bl in 94% yield and 95% ee. Reduction of the carbonyl group
and followed by deprotection of the ketal compound could give the
2-aryltetralone 9 without loss of enantioselectivity,25 which is the
key intermediate to the synthesis of hexahydrobenzo[c]ben-
zophenanthridine alkaloid 10 (Scheme 2).21
4
5
6
7
8
9
10
11
12
13
14
15e
16
Ph (5a)
4-ClC6H4 (5j)
4-CH3C6H4 (5d)
Ph (5a)
Ph (5a)
4-CH3C6H4 (5d)
In summary, we have prepared a new electronically deficient
chiral diphosphine ligand (Rax,S,S)-F12-C3-TunePhos with both cen-
tral and axial chiral elements, which enriched the diversity of elec-
tron-poor ligands. Moreover, the ligand was successfully employed
in rhodium-catalyzed asymmetric 1,4-addition reactions of aryl-
a
4
(1.2 mmol), 5 (1.44 mmol), [Rh(C2H4)2Cl]2 (0.25 mol %), L1 (0.525 mol %),
toluene (0.8 mL), H2O (0.3 mL), rt.
b
Isolated yield.
Determined by HPLC.
4a (0.6 mmol), 5a (0.9 mmol), [Rh(C2H4)2Cl]2 (0.5 mol %), L1 (1.05 mol %).
PhB(OH)2 (1.8 mmol).
c
d
e
boronic acids to diverse
a
,b-unsaturated carbonyls including cyclic
,b-unsaturated ketones, and
a,b-unsaturated ketones, acyclic
a
naphthoquinone monoketals, providing versatile chiral cyclic and
acyclic b-arylated ketones with up to 99% ee.
Table 3
Scope of 1,4-addition of arylboronic acids to naphthoquinone monoketala
O
O
Acknowledgment
[RhCl(C2H4)2]2, L1, KOH
+
ArB(OH)2
Toluene, H2O, rt
Ar
We thank the financial support from the National Natural
Science Foundation of China (21372220 & 21532006).
O
O
O
8
O
7a
5
Entry
t (h)
Ar of 5
Yield (%)b
Ee (%)c
Supplementary data
1
1
2
28
2
3
Ph (5a)
4-FC6H4 (5h)
2-CH3C6H4 (5b)
4-CH3OC6H4 (5f)
3-ClC6H4 (5k)
3,4-(CH3O)2C6H3 (5l)
93
91
86
87
99
93
99
97
85
97
98
97
2d
3d
4
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetlet.2016.03.
072.
5e
6f
12
a
7a (0.6 mmol),
5 (0.72 mmol), [Rh(C2H4)2Cl]2 (0.5 mol %), L1 (1.05 mol %),
References and notes
toluene (0.8 mL), H2O (0.3 mL), rt.
b
Isolated yield.
Determined by HPLC.
7a (0.3 mmol), 5 (0.36 mmol), [Rh(C2H4)2Cl]2 (1.0 mol %), L1 (2.1 mol %).
7a (0.3 mmol), 5a (0.6 mmol), [Rh(C2H4)2Cl]2 (1.0 mol %), L1 (2.1 mol %).
1. Noyori, R. In Asymmetric Catalysis in Organic Synthesis; Wiley & Sons: New York,
1994; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. In Comprehensive Asymmetric
Catalyses; Springer: Berlin, 1999; Ojima, I. In Catalysis Asymmetric Synthesis;
John Wiley & Sons: New York, 2000; Zhou, Q.-L. In Privileged Chiral Ligands and
Catalysts; John Wiley & Sons: Weinheim, 2011.
c
d
e
f
7a (0.3 mmol), 5l (0.6 mmol), [Rh(C2H4)2Cl]2 (2.5 mol %), L1 (5.25 mol %).
2. (a) Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585; (b) Jendralla, H.; Li,
C. H.; Paulus, E. Tetrahedron Asymmetry 1994, 5, 1297; (c) Benincori, T.; Brenna,
E.; Sannicolò, F.; Trimarco, L.; Antognazza, P.; Cesarotti, E. J. Chem. Soc., Chem.
Commun. 1995, 685; (d) Benincori, T.; Brenna, E.; Sannicolò, F.; Trimarco, L.;
Antognazza, P.; Cesarotti, E.; Demartin, F.; Pilati, T. J. Org. Chem. 1996, 61, 6244;
(e) Kojima, A.; Boden, C. D. J.; Shibasaki, M. Tetrahedron Lett. 1997, 38, 3459; (f)
Kojima, A.; Honzawa, S.; Boden, C. D. J.; Shibasaki, M. Tetrahedron Lett. 1997, 38,
3455; (g) McCarthy, M.; Guiry, P. J. Tetrahedron 2001, 57, 3809; (h) Scalone, M.;
Waldmeier, P. Org. Process Res. Dev. 2003, 7, 418; (i) Drieben-Hölscher, B.;
Kralik, J.; Agel, F.; Steffens, C.; Hu, C. Adv. Synth. Catal. 2004, 346, 979; (j)
Flanagan, S. P.; Guiry, P. J. J. Organomet. Chem. 2006, 691, 2125.
practicability of asymmetric 1,4-addition reactions, we tested our
catalytic system in the 1,4-addition reactions of arylboronic acids
to naphthoquinone monoketal compound (Table 3). To our delight,
the addition of phenylboronic acid to naphthoquinone monoketal
7a was rather efficient and gave the desired product in 93% yield
and 99% ee in less than one hour (Table 3, entry 1). The sterically
hindered ortho-methyl-substituted substrate gave the product
8ab with slightly lower yield and moderate 85% ee (Table 3, entry
3). In general, the catalytic efficiency of our electronically deficient
3. (a) Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029; (b) Xie, J.-H.; Zhou, Q.-L. Acc.
Chem. Res. 2008, 41, 581; (c) Sun, X.; Li, W.; Hou, G.; Zhou, L.; Zhang, X. Adv.
Synth. Catal. 2009, 351, 2553; For related works see 2g. For reviews, see: (d)
Genêt, J.-P.; Ayad, T.; Ratovelomanana-Vidal, V. Chem. Rev. 2014, 114, 2824.

S.-B. Hu et al. / Tetrahedron Letters 57 (2016) 1925–1929
1929
4. (a) You, S.-L.; Hou, X.-L.; Dai, L.-X.; Yu, Y.-H.; Xia, W. J. Org. Chem. 2002, 67,
4684; (b) Wawrzyniak, P.; Slawin, A. M. Z.; Woollins, J. D.; Kilian, P. Dalton
Trans. 2010, 39, 85.
16. Sun, X.; Zhou, L.; Li, W.; Zhang, X. J. Org. Chem. 2008, 73, 1143.
17. (a) Korenaga, T; Sakai, T; Ko, A. Patent US2013/331576 A1, 2013.; (b) Schmid,
R.; Broger, E. A.; Cereghetti, M.; Crameri, Y.; Foricher, J.; Lalonde, M.; Müller, R.
K.; Scalone, M.; Schoettel, G.; Zutter, U. Pure Appl. Chem. 1996, 68, 131.
18. For reviews see: (a) Hayashi, T. Synlett 2001, 879; (b) Fagnou, K.; Lautens, M.
Chem. Rev. 2003, 103, 169; (c) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103,
2829; (d) Wang, H.; Yang, D.-Q.; Mo, H.-H. Chin. J. Org. Chem. 2007, 27, 806; (e)
Miyaura, N. Bull. Chem. Soc. Jpn. 2008, 81, 1535; (f) Defieber, C.; Grutzmacher,
H.; Carreira, E. M. Angew. Chem., Int. Ed. 2008, 47, 4482; (g) Edwards, H. J.;
Hargrave, J. D.; Penrose, S. D.; Frost, C. G. Chem. Soc. Rev. 2010, 39, 2093; (h)
Tian, P.; Dong, H.-Q.; Lin, G.-Q. ACS Catal. 2012, 2, 95; (i) Li, Y.; Xu, M.-H. Chem.
Commun. 2014, 3771; For selected examples see: (j) Hayashi, T.; Takahashi, M.;
Takaya, Y.; Ogasawara, M. J. Am. Chem. Soc. 2002, 124, 5052; (k) Chen, F.-X.;
Kina, A.; Hayashi, T. Org. Lett. 2006, 8, 341; (l) Shintani, R.; Hayashi, T. Org. Lett.
2011, 13, 350; (m) Chen, G.; Gui, J.; Li, L.; Liao, J. Angew. Chem., Int. Ed. 2011, 50,
7681; (n) Khiar, N.; Salvador, Á.; Valdivia, V.; Chelouan, A.; Alcudia, A.; Álvarez,
E.; Fernández, I. J. Org. Chem. 2013, 78, 6510; (o) Falkowski, J. M.; Sawano, T.;
Zhang, T.; Tsun, G.; Chen, Y.; Lockard, J. V.; Lin, W. J. Am. Chem. Soc. 2014, 136,
5213; (p) Ogasawara, M.; Tseng, Y.-Y.; Arae, S.; Morita, T.; Nakaya, T.; Wu, W.-
Y.; Takahashi, T.; Kamikawa, K. J. Am. Chem. Soc. 2014, 136, 9377; (q) Gandi, V.
R.; Lu, Y.; Hayashi, T. Tetrahedron Asymmetry 2015, 26, 679.
5. Hartwig, J. F. Inorg. Chem. 1936, 2007, 46.
6. (a) Sergeev, A. G.; Artamkina, G. A.; Beletskaya, I. P. Tetrahedron Lett. 2003, 44,
4719; (b) Clarke, M. L.; Heydt, M. Organometallics 2005, 24, 6475; (c) Hicks, J.
D.; Hyde, A. M.; Cuezva, A. M.; Buchwald, S. L. J. Am. Chem. Soc. 2009, 131,
16720; (d) Park, N. H.; Vinogradova, E. V.; Surry, D. S.; Buchwald, S. L. Angew.
Chem., Int. Ed. 2015, 54, 8259.
7. Chen, Q.; Lin, B.-L.; Fu, Y.; Liu, L.; Guo, Q.-X. Res. Chem. Intermed. 2005, 31, 759.
8. Murata, M.; Morimoto, T.; Achiwa, K. Synlett 1991, 827.
9. (a) Gonda, Y.; Hori, Y.; Yamaguchi, A.; Hagiwara, T. Patent US6075154 A1,
2000.; (b) Armanino, N.; Koller, R.; Togni, A. Organometallics 2010, 29, 1771.
10. Sturm, T.; Weissensteiner, W.; Spindler, F. Adv. Synth. Catal. 2003, 345, 160.
11. For related works, see 3d Jeulin, S.; Duprat de Paule, S.; Ratovelomanana-Vidal,
V.; Genêt, J.-P.; Champion, N.; Dellis, P. Angew. Chem., Int. Ed. 2004, 43, 320.
12. (a) Korenaga, T.; Osaki, K.; Maenishi, R.; Sakai, T. Org. Lett. 2009, 11, 2325; (b)
Korenaga, T.; Maenishi, R.; Hayashi, K.; Sakai, T. Adv. Synth. Catal. 2010, 352,
3247.
13. For related works see 3d. For selected examples see: (a) Shaughnessy, K. H.
Chem. Rev. 2009, 109, 643; (b) Leseurre, L.; Le Boucher d’Herouville, F.;
Püntener, K.; Scalone, M.; Genêt, J. P.; Michelet, V. Org. Lett. 2011, 13, 3250; (c)
Leseurre, L.; Le Boucher d’Herouville, F.; Millet, A.; Genêt, J.-P.; Scalone, M.;
Michelet, V. Catal. Commun. 2015, 69, 129; (d) Berhal, F.; Esseiva, O.; Martin, C.-
H.; Tone, H.; Genêt, J. P.; Ayad, T.; Ratovelomana-Vidal, V. Org. Lett. 2011, 13,
2806; (e) Zhang, D.-Y.; Wang, D.-S.; Wang, M.-C.; Yu, C.-B.; Gao, K.; Zhou, Y.-G.
Synthesis 2011, 17, 2796; (f) Zhang, D.-Y.; Yu, C.-B.; Wang, M.-C.; Gao, K.; Zhou,
Y.-G. Tetrahedron Lett. 2012, 53, 2556.
19. Alexakis, A.; Bäckvall, J. E.; Krause, N.; Pàmies, O.; Diéguez, M. Chem. Rev. 2008,
108, 2796.
20. (a) Okamoto, K.; Hayashi, T.; Rawal, V. H. Org. Lett. 2008, 10, 4387; (b) Feng, C.-
G.; Wang, Z.-Q.; Shao, C.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2008, 10, 4101; (c)
Brown, M. K.; Corey, E. J. Org. Lett. 2010, 12, 172; (d) Luo, Y.; Carnell, A. J. Angew.
Chem., Int. Ed. 2010, 49, 2750; (e) Berhal, F.; Wu, Z.; Genêt, J.-P.; Ayad, T.;
Ratovelomanana-Vidal, V. J. Org. Chem. 2011, 76, 6320; (f) Liu, C.-C.; Janmanchi,
D.; Chen, C.-C.; Wu, H. L. Eur. J. Org. Chem. 2012, 2503; (g) Narui, R.; Hayashi, S.;
Otomo, H.; Shintani, R.; Hayashi, T. Tetrahedron Asymmetry 2012, 23, 284.
21. Vicario, J. L.; Badía, D.; Domínguez, E.; Carrillo, L. Tetrahedron Asymmetry 2000,
11, 1227.
14. (a) McDougal, N. T.; Streuff, J.; Mukherjee, H.; Virgil, S. C.; Stoltz, B. M.
Tetrahedron Lett. 2010, 51, 5550; (b) Hu, Z.; Li, Y.; Liu, K.; Shen, Q. J. Org. Chem.
2012, 77, 7957; (c) Lai, Z.-W.; Yang, R.-F.; Ye, K.-Y.; Sun, H.; You, S.-L. Beilstein J.
Org. Chem. 2014, 10, 1261.
15. (a) Zhang, Z.; Qian, H.; Longmire, J.; Zhang, X. J. Org. Chem. 2000, 65, 6223; (b)
Qiu, L.; Wu, J.; Chan, S.; Au-Yeung, T. T.-L.; Ji, J.-X.; Guo, R.; Pai, C.-C.; Zhou, Z.;
Li, X.; Fan, Q.-H.; Chan, A. S. C. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5815; (c)
Qiu, L.; Kwong, F. Y.; Wu, J.; Lam, W. H.; Chan, S.; Yu, W.-Y.; Li, Y.-M.; Guo, R.;
Zhou, Z.; Chan, A. S. C. J. Am. Chem. Soc. 2006, 128, 5955; (d) Li, W.; Sun, X.;
Zhou, L.; Hou, G.; Yu, S.; Zhang, X. J. Org. Chem. 2009, 74, 1397; (e) Wang, C.-J.;
Wang, C.-B.; Chen, D.; Yang, G.; Wu, Z.; Zhang, X. Tetrahedron Lett. 2009, 1038,
50; (f) Zou, Y.; Geng, H.; Zhang, W.; Yu, S.; Zhang, X. Tetrahedron Lett. 2009, 50,
5777; (g) Gou, F.-R.; Li, W.; Zhang, X.; Liang, Y.-M. Adv. Synth. Catal. 2010, 352,
2441; (h) Wang, C.-J.; Wang, C.-B.; Chen, D.; Yang, G.; Wu, Z.; Zhang, X.
Tetrahedron Lett. 2011, 52, 468; (i) Gao, K.; Yu, C.-B.; Li, W.; Zhou, Y.-G.; Zhang,
X. Chem. Commun. 2011, 7845; (j) Zhou, X.-Y.; Wang, D.-S.; Bao, M.; Zhou, Y.-G.
Tetrahedron Lett. 2011, 52, 2826; (k) Pan, S.; Endo, K.; Shibata, T. Org. Lett. 2012,
14, 780; (l) Liu, T.-L.; Li, W.; Geng, H.; Wang, C.-J.; Zhang, X. Org. Lett. 2013, 15,
1740; (m) Huang, K.; Guan, Z.-H.; Zhang, X. Tetrahedron Lett. 2014, 55, 1686; (n)
Huang, W.-X.; Yu, C.-B.; Shi, L.; Zhou, Y.-G. Org. Lett. 2014, 16, 3324.
22. For palladium-catalyzed reactions, see: (a) Åhman, J.; Wolfe, J. P.; Troutman, M.
V.; Palucki, M.; Buchwald, S. L. J. Am. Chem. Soc. 1918, 1998, 120; (b) Hamada,
T.; Chieffi, A.; Åhman, J.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 1261; For
nickel-catalyzed reactions (c) Spielvogel, D. J.; Buchwald, S. L. J. Am. Chem. Soc.
2002, 124, 3500.
23. Chieffi, A.; Kamikawa, K.; Åhman, J.; Fox, J. M.; Buchwald, S. L. Org. Lett. 1897,
2001, 3.
24. (a) Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2001, 40, 3726; (b) Eames, J.;
Weerasooriya, N. Tetrahedron Asymmetry 2001, 12, 1; (c) Duhamel, L.;
Duhamel, P.; Plaquevent, J.-C. Tetrahedron Asymmetry 2004, 15, 3653; (d)
Yanagisawa, A.; Touge, T.; Arai, T. Angew. Chem., Int. Ed. 2005, 44, 1546; (e)
Mohr, J. T.; Nishimata, T.; Behenna, D. C.; Stoltz, B. M. J. Am. Chem. Soc. 2006,
128, 11348.
25. Tokunaga, N.; Hayashi, T. Adv. Synth. Catal. 2007, 349, 513.