Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki-Miyaura Cross-coupling

Article abstract of DOI:10.1021/acscatal.9b04354

A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki-Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. A series of axially chiral biaryl monophosphine oxides were obtained in good yields and with high enantioselectivities. The practicability of this reaction was validated in the straightforward synthesis of axially chiral biaryl monophosphine ligand and demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations of the product make it as a platform molecule for synthesis of other chiral biaryl phosphines.

Full text of DOI:10.1021/acscatal.9b04354

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Letter
Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/
WJ-Phos-Catalyzed Asymmetric Suzuki-Miyaura Cross-coupling
Wangqin Ji, Hai-Hong Wu, and Junliang Zhang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b04354 • Publication Date (Web): 03 Jan 2020
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ACS Catalysis
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Axially Chiral Biaryl Monophosphine Oxides Enabled by
Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki-Miyaura Cross-
coupling
Wangqin Ji†, Hai-Hong Wu*,†, and Junliang Zhang*,†,#
†
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular
Engineering, East China Normal University, 3663 N. Zhongshan Road, Shanghai 200062, P. R. China.
#Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai 200438, P. R. China.
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R'
Br
ABSTRACT: A highly enantioselective palladium/WJ-
Phos-catalyzed Suzuki-Miyaura coupling reaction for
efficient construction of axially chiral biaryl
monophosphine oxides was developed. A series of
axially chiral biaryl monophosphine oxides were
B(OH)2
FG
PPh2
P(O)R2
H
tBu
N
[Pd] /L*
FG
+
S
P(O)R2
Fe
Ar
O
R = OMe, OEt, Ar
R'
(
)-WJ5
SC, RFC, RS
90-98% ees
R = OMe. OEt, Ar
FG = H, OEt, Me, Et, Ph
100-gram scale synthesis
Broad substrate scope
Ar = 1-Naphthyl
obtained
in
good
yields
and
with
high
Good yields and high ees
enantioselectivities. The practicability of this reaction
was validated in the straightforward synthesis of axially
chiral biaryl monophosphine ligand and demonstrated by
serve as a "platform molecule"
a
100-gram-scale synthesis. Moreover, various
functionalizations of the product make it as a platform molecule for synthesis of other chiral biaryl phosphines.
KEYWORDS: Suzuki coupling, Palladium, axially chiral compounds, Asymmetric catalysis, Phosphine
containing axial chiral binaphthyl compounds, it would
The axially chiral biaryl monophosphines and their
be exciting to find a robust catalyst system to improve the
oxides have emerged as powerful chiral ligands and
substrate scope and especially applicable in large-scale
synthesis.
catalysts in asymmetric catalysis.[1,2] Therefore, the
development of new methods for their synthesis have
received much attention[1,2] and several strategies have
been developed. For example, the classic strategy for
synthesis of these compounds relies on multi-step
synthesis from chiral Binols (Scheme 1a).[1h] Very recently,
the group of Shi developed an elegant rhodium(I)-
catalyzed direct arylation of (R)-H-MOP without erosion
of the ee value, which provides a facile access to aryl-
substituted binapthyl monophosphines (Scheme 1b).[3] In
2016, Gu and co-workers developed an efficient
palladium-catalyzed asymmetric synthesis of axially chiral
1-vinylnaphthalen-2-yl phosphine oxides from aryl
bromides and hydrazones.[2j] Further oxidation of the
products allows to get the axially chiral biaryl compounds
by using DDQ with good chiral retention (Scheme 1c).
Besides the above strategies, the palladium-catalyzed
asymmetric Suzuki-Miyaura coupling of 1-bromo-naphth-
2-yl phosphine oxide or phosphonate with ortho-
substituted arylboronic acids have attracted much
attention. Early in 2000, Buchwald reported the first
example of this type of reaction, delivering the
corresponding phosphonate in 57-92% ees, which upon
further reaction with Grignard reagent to furnish the
desired aryl phosphine oxides (Scheme 1d).[2b]
Subsequently, Qiu and coworkers realized the Pd-
catalyzed direct asymmetric Suzuki-coupling between
a) via the sveral-step tranformation of binol
OH
OH
(1) Tf2O, pyridine
OTf
further
FG
P(O)Ar2
(2) Pd(OAc)2-dppb (cat)
Ar2POH, iPr2NEt
functionalization
P(O)Ar2
b) via the direct C-H arylation of H-MOP (Shi)
ArBr
[Rh(cod)Cl]2, LiOtBu
Ar
OH
OH
PPh2
PPh2
1,4-dioxane, 150 o
C
(R)-H-MOP (>99% ee)
(R)-Ar-MOP
c) via the cross-coupling reaction via the carbene intermediate (Gu)
R2
R2
Br
NNHTs
R2
P(O)Ar2
DDQ
Pd(OAc)2
P(O)Ar2
P(O)Ar2
+
L*
R1
R1
R1
24 examples
85-97% ee
d) via the Suzuki-Miyaura cross-coupling reaction (Buchwald, Qiu and this work)
R'
Br
[Pd] (cat.)
chiral ligands
B(OH)2
FG
P(O)R2
FG
P(O)R2
*
+
solvent, temperature
R = OMe, OEt, Ar
R'
PPh2
H
tBu
N
This work
O
O
OCH3
PAr2
S
NMe2
PCy2
Fe
Ar
O
100-gram scale synthesis
Broad substrate scope
Ar = 1-Naphthyl
Ar = 3,5-(tBu)2-4-MeOC6H2
(
)-WJ5
SC, RFC, RS
22 examples
31-94% ees
9 examples
Good yields and high ees
90-98% ees
R = OMe. OEt, Ar
57-92% ees
R = OMe,OEt
FG = H
serve as a "platform molecule"
R = Ar
ortho-substituted
arylboronic
acids
and
2-
FG = H, OMe, CHO
FG = H, OEt, Me, Et, Ph
diarylphosphinyl-1-naphthyl bromides with the use of
chiral bridged atropisomeric monophosphine or Cy-MOP
as the chiral ligand.[2g] The existence of an ortho formyl or
alkoxy group in arylboronic acids is crucial for the
coupling efficiency and enantioselectivity (Scheme 1d).
Considering the broad applications of phosphine-
Scheme 1. Synthetic protocols for axially chiral biaryl
monophosphine (oxides).
Over the past few years, we designed and developed a
series of new chiral sulfinamidephosphine (Sadphos)
ligands such as Ming-Phos,[4] Xiang-Phos,[5] PC-Phos,[6]
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ACS Catalysis
Xu-Phos[7] and WJ-Phos[8] which have demonstrated good
Page 2 of 7
ferrocene derived WJ-Phos gave promising result and the
desired product 3aa was obtained in 50% yield and 89%
ee. Inspired by this result, we further developed a new
synthetic route for WJ-Phos, which could easily deliver a
pair of diastereomers. Gratifyingly, new synthesis of WJ-
Phos could be realized from commercially available
ferrocenecarboxaldehyde.[8,10] A series of WJ-Phos was
obtained with highly diastereoselective addition of ArLi,
AlkylLi or ArMgBr to chiral sulfinyl imine (Scheme 2),
which the absolute structure was established by the X-ray
structures of (RC, SFC, RS)-WJ5 and (SC, RFC, RS)-WJ5,
respectively (Scheme 2).[11]
performance in asymmetric transition metal catalysis.[9]
Inspired by these successes, we wondered whether these
preeminent chiral ligands could address the limited scope
of palladium-catalyzed Suzuki-Miyaura coupling reaction.
Herein, we present a highly enantioselective Suzuki
coupling reaction by using WJ-Phos as chiral ligand,
which provides a facile access to various substituents
atropisomers phosphine oxides in good yields and high ee
values (Scheme 1d).
1
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3
4
5
6
7
8
9
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19
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O
OMe
PPh2
O
O
PAr2
PAr2
MeO
MeO
PAr2
PAr2
PAr2
PAr2
Table 1. Optimization of reaction conditions.[a]
O
L4
L2
L1
L3
Ar = 3,5-(tBu)2-4-MeOC6H2
(R)-DTBM-BIPHEP, NR
(R)-MOP
42% yield, 32% ee
Ar = 4-MeC6H4
(S)-BINAP, NR
Br
O
P
Ar = 3,5-(CH3)2C6H3
(R)-DM-SEGPHOS, trace
B(OH)2
Ph
Ph
O
P
/L
[Pd] (4 mol%) (4.8 mol%)
Ph
Ph
iPr
+
tBu
tBu
O
O
K3PO4 (3.0 eq.), solvent
50 oC, 36 h
O
N
S
S
NMe2
R
NH
R
NH
PPh2
1a
2a
3aa
PPh2
Fe
PPh2
PR'2
Fe
Yield (Ee)
[%]b,c
Trace (--)
Entry
[M]
L
Solvent
L6
Xiang-Phos:
trace
=
Me, R'= Ad
R
L5
(S,S)-iPr-FOXAP
(R, S)-PPFA
Ming-Phos
trace
(S, R)-
: R = Ph
1
2
PhMe
Xu-Phos:
=
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd(OAc)2
(RC, SFC, RS)-WJ4
(SC, RFC, RS)-WJ4
(RC, SFC, RS)-WJ5
(SC, RFC, RS)-WJ5
(SC, RFC, RS)-WJ6
(SC, SFC, RS)-WJ7
(RC, RFC, RS)-WJ7
(SC, SFC, RS)-WJ8
(RC, RFC, RS)-WJ8
(SC, RFC, RS)-WJ5
R
Ph, R'= Cy
40% yield, 49% ee
trace
trace
tBu
O
R
O
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
DCE
20 (-7)
Trace (--)
55 (90)
45 (92)
Trace (--)
47 (79)
Trace (--)
53 (82)
R
O
S
S
R
NH
PPh2
WJ1
(SC, SFc, SS)- : R = 9-Phen
HN
S
N
3
H
45% yield, -86% ee
tBu
O
PPh2
Fe
WJ2
(SC, SFC, SS)-
: R = 1-Pyrenyl
4
PPh2
50% yield, -83% ee
Ming-Phos:
(SC, SFc, SS)-WJ3: R = 1-Naphthyl
50% yield, -89% ee
(R, R)-
5
WJ-Phos
(Sc, SFC, SS)-
PC-Phos
R = 4-MeOC6H4
NR
R = Ph
10% yield, 77% ee
6
7
Figure 1. Screened ligands.
8
OH
O
O
S
tBu
S
CHO
PPh2
N
H2N
OH
9
tBu
+
N
CHO
PPh2
PPh2
CHO
tBu
1) PTSA, toluene
PPh2
S
Ti(OiPr)4
Fe
+
Fe
Fe
Fe
Fe
2) tBuOK, tBuLi
10
11
O
77 (92)
NR (--)
35 (86)
NR (--)
30 (89)
50 (91)
THF
R
Ph2PCl, THF
3) PTSA
acetone : H2O
(SFC, RS
)
( RFC, RS
)
(S)
(R)
Pd(PPh3)2Cl2 (SC, RFC, RS)-WJ5
O
S
PPh2
O
12
13
14
15
16
17
18d
19de
20de
Pd(PhCN)2Cl2
H
tBu
(SC, RFC, RS)-WJ5
N
S
tBu
+
PPh2
N
S
N
tBu
+
N
PPh2
S
tBu
H
PPh2
RLi
-78 oC,THF
Fe
R
O
Fe
Pd(PPh3)4
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
(SC, RFC, RS)-WJ5
(SC, RFC, RS)-WJ5
(SC, RFC, RS)-WJ5
(SC, RFC, RS)-WJ5
Fe
Fe
O
WJ
(SC, RFC, RS)-
WJ
(RC, SFC, RS)-
(SFC, RS
)
( RFC, RS
)
WJ4 (
WJ4
R = Me, d.r. = 1.5:1, (RC, SFC, RS)-
29% yield), (SC, RFC, RS)-
(19% yield)
THF
WJ5
R=1-Naphthyl, d.r. = 1.9:1, (RC, SFC, RS)-
WJ5
(19% yield), (SC, RFC, RS)-
(36% yield)
(17% yield)
R = 3,5-(tBu)2-4-MeOC6H2, d.r. >20:1, (SC, RFC, RS)-
WJ6
EtOH
69 (94)
O
S
PPh2
R'
O
S
(SC, RFC, RS)-WJ5 PhMe/ EtOH = 1:1 76 (94)
(SC, RFC, RS)-WJ5 PhMe/ EtOH = 1:1 80 (94)
(SC, RFC, RS)-WJ5 PhMe/ EtOH = 1:1 84 (94)
H
tBu
PPh2
N
N
tBu
+
tBu
N
PPh2
N
tBu
S
H
R'MgBr
-78 oC,THF
PPh2
Fe
S
R'
O
+
Fe
Fe
Fe
O
Pd(OAc)2
Pd(OAc)2
WJ
(RC, RFC, RS)-
(SFC, RS
)
( RFC, RS
)
WJ
(SC, SFC, RS)-
(SC, RFC, RS)-WJ6 PhMe/ EtOH = 1:1
78 (95)
WJ7
R' = Ph, d.r. = 1.3:1, (SC, SFC, RS)-
WJ7
(38% yield), (RC, RFC, RS)-
(29% yield)
[a]Unless otherwise noted, all reactions were carried out with 0.2
mmol of 1a, 0.4 mmol of 2a, 3.0 equiv of K3PO4, 4 mol% of catalyst
([Pd] to L = 1:1.2) in 2.0 mL solvent at 50 ºC for 36 h. [b]Isolated yield.
[c]Determined by chiral HPLC. [d]3.0 equiv of K2CO3. [e]5 mol% of
WJ8
R' = 4-MeOC6H4, d.r. = 1.1:1, (SC, SFC, RS)-
WJ8
(20% yield), (RC, RFC, RS)-
(22% yield)
Scheme 2. Synthesis of different diastereoisomers of
WJ-Phos ligands.
With 2-diphenylphosphinyl-1-naphthyl bromide 1a and
1-naphthylboronic acid 2a as model substrates, a series of
chiral ligands were investigated (Figure 1). It was observed
that, axially chiral bisphosphine ligands L1-L3 are
inefficient. However, the product 3aa was obtained in
42% yield and 32% ee when axially chiral monophosphine
ligand (R)-MOP (L4) was used as chiral ligand. Next,
ferrocene-based N, P ligands L5-L6 were investigated and
only (R)-(S)-PPFA gave the product 3aa in 40% yield with
49% ee. Then we focus on our developed Sadphos as
chiral ligand, among which the palladium catalyzed
derived from Ming-Phos, Xiang-Phos, Xu-Phos and PC-
Phos all showed low catalytic activity. Fortunately, the
catalyst ([Pd] to
dibenzylideneacetone, DCE = 1,2-dichloroethane.
L
=
1:1.2). NR
=
no reaction. dba
=
We firstly investigated the performance of this series of
new WJ-Phos in the asymmetric suzuki coupling reaction
(Table 1, entries 1-9). (SC, RFC, RS)-WJ5 bearing 1-naphthyl
group gave the best result, delivering product 3aa in 55%
yield with 90% ee (Table 1, entry 4). Although the ee value
can reach 92% when (SC, RFC, RS)-WJ6 was used, the yield
of the reaction was low (Table 1, entry 5). With the use of
(SC, RFC, RS)-WJ5 as the chiral ligand, different palladium
salts were then investigated (Table 1, entries 10-13). The
yield of 3aa was significant increased to 77% with 92% ee
ACS Paragon Plus Environment

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one catalytic system. We were very glad to make up for
when Pd(OAc)2 was used (Table 1, entry 10). Next, the
solvent effect were studied (Table 1, entries 14–17) and a
mixture of PhMe/EtOH(1:1) could deliver the product 3aa
in 76% yield with 94% ee. Further changing the base to
K2CO3 and slightly increasing the catalyst loading
delivered 3aa in 84% yield with the same ee value (Table 1,
entries 18–19). Under these conditions, 78% yield of 3aa
could be obtained by using (SC, RFC, RS)-WJ6 as the ligand
(Table 1, entries 20).
1
2
3
4
5
6
7
8
this shortcoming by using (SC, RFC, RS)-WJ5 chiral ligand.
R2
Pd(OAc)2 (5 mol%)
WJ5
Br
O
P
B(OH)2
R2
R1
R1
(SC, RFC, RS)-
(6 mol%)
O
P
*
R1
R1
+
K2CO3 (3.0 eq.)
PhMe/ EtOH = 1:1
50 oC, 36 h
1
2
3
3aa,
3ba,
3ca,
3da,
3ea,
3fa,
R = H, 84%, 94% ee
R = Me, 78%, 95% ee
R = iPr, 85%, 94% ee
R = tBu, 80%, 96% ee
R = Ph, 87%, 96% ee
R = OMe, 85%, 96% ee
R = Cl, 75%, 94% ee
R = OCF3, 80%, 95% ee
R
3ia,
3ja,
3ka
3la,
R = Me, 80%, 96% ee
R = iPr, 88%, 94% ee
, R = OMe, 88%, 94% ee
R = F, 75%, 97% ee
R
O
P
O
P
9
R
3ma,
R = Cl, 77%, 95% ee
Having established the optimized reaction conditions,
we next set out to test the scope of the palladium-
catalyzed Suzuki-Miyaura cross-coupling reaction
(Scheme 3). The reactions of 2-diarylphosphinyl-1-
naphthyl bromide with either electron-donating groups
3ga,
3ha,
R
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
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27
28
29
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31
32
33
34
35
36
37
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
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57
58
59
60
R
Me
O
O
3oa
3pa
3qa
3ra
R = Me, 95%, 96% ee
R = OMe, 83%, 94% ee
R = Cl, 70%, 95% ee
R = CF3, 82%, 98% ee
78%, 94% eeb
P
3na
P
R
R
Me
i
t
R
(e.g., Me, Pr, Bu, Ph and OMe), or electron-withdrawing
groups (e.g., Cl, OCF3) at the para-position of the phenyl
ring could furnish the corresponding products 3ba–3ha in
75-87% yields with 94–96% ees. As highlighted in Scheme
3, the meta-substituent of the phenyl ring were also
compatible to furnish the products 3ia–3ma in 75–88%
yields with 94–97% ees. It is worth to note that the
reaction with ortho-substituent of the phenyl ring could
deliver the product 3na in 78% yield with 94% ee by the
use of (SC, SFC, SS)-WJ3 as the chiral ligand. Both the
disubstituted arylphosphine oxide and the β-naphthyl
phosphine oxides worked smoothly to give the
corresponding products 3oa–3sa in 70–95% yields with
93–98% ees. To our delight, the reactions of dimethyl 1-
bromo-2-naphthylphosphonate and diethyl 1-bromo-2-
naphthylphosphonate with 1-naphthylboronic furnished
3ta and 3ub in moderate yields with 90$ and 93% ee,
respectively. With respect to other substituents of
arylphosphine oxide with 4-methyl-1-naphthaleneboronic
acid could also participate in this reaction, delivering the
products (3ab–3gb) in 79–95% yields with 94–96% ees.
Me
3ub
3ab
3db
3gb
R = OEt, 80%, 93% ee
O
3sa
3ta
R = 2-Naphthyl, 78%, 93% ee
, R = OMe, 78%, 90% ee
, R = Ph, 95%, 96% ee
R
O
P
P
t
R
R
, R = 4- BuC6H4, 88%, 94% ee
R
, R = 4-ClC6H4, 79%, 96% ee
F
Me
Me
O
P
P(O)Ar2
O
P(O)(Ph)2
Ph
Ph
Ph
P
Ph
b
b
3be
, Ar = 4-MeC6H4, 77%, 90% ee
3af
, 75%, 90% ee
3ac
, 90%, 90% ee
3ad
, 95%, 97% ee
, R = Ph, R1 = 4-tBuC6H4, 66%, 97% ee
, R = Ph, R1 = 4-OMeC6H4, 70%, 93% ee
, R = Ph, R1 = 3-MeC6H4, 62%, 91% ee
, R = Ph, R1 = 3-FC6H4, 71%, 91% ee
, R = Ph, R1 =3-ClC6H4, 67%, 97% ee
, R = Ph, R1 =OEt, 62%, 93% ee
3dh
3fh
Ph
Et
R
3ih
P(O)(R1)2 3lh
P(O)(Ph)2
P(O)(Ph)2
3mh
3uh
3ah
, 55%, 91% ee
3ag
, 65%, 91% ee
R
F3CO
MeO
EtO
P(O)(Ph)2
P(O)(Ph)2
P(O)(Ph)2
P(O)(Ph)2
3al
, R = CHO, NR
c
3aj
3ak
, 68%, 83% ee
, 66%, 85% ee
3ai
, 79%, 31% ee
3am
, R = CO2Et, trace
[a]
Condition: Unless otherwise noted, all reactions were carried out
with 0.2 mmol of 1, 0.4 mmol of 2, 3.0 equiv of K2CO3, 5 mol% of
catalyst ([Pd] to L = 1:1.2) in 2.0 mL solvent at 50 ºC for 36 h. [b] with
the use of (SC, SFC, SS)-WJ3 as the chiral ligand. [c] with the use of (SC,
RFC, RS)-WJ6 as the chiral ligand.
Both
9-phenanthracenylboronic
acid
and
1-
pyrenylboronic acid with diphenylphosphine oxides were
tolerated under the reaction conditions, providing the
products 3ac and 3ad in 90–95% yields with excellent
enantioselectivity ( 90–97% ees). It is noteworthy that
different ortho substituted phenylboronic acids were also
suitable for this reaction and the corresponding coupling
products 3be–3mh were obtained in good yields with up
to 97% ee. In addition, when diethyl 1-bromo-2-
naphthylphosphonate with 2-biphenylboronic acid were
employed as the coupling partners, the product 3uh was
furnished in moderate yield with 93% ee. The ortho-
Scheme 3. Substrate scope with respect to the
phosphine oxides and boronic acids.[a]
Br
O
P
B(OH)2
Pd(OAc)2 (2.5 mol%)
Ph
Ph
O
P
WJ5
(SC, RFC, RS)-
(3 mol%)
Ph
Ph
+
K2CO3 (3.0 eq.) 60 oC, 72 h
toluene : EtOH (1:1)
350 mmol, 142.5 g
2.0 eq.
2a
1a
62% (98.6 g), 94% ee
3aa
53%, >99% ee after recrystallization
1a
recovered : 28% (39.9 g)
methoxy,
ethoxy,
trifluoromethoxy
substituted
phenylboronic acids were examined under the standard
condition and the corresponding products 3ai–3ak were
obtained in good yields with up to 85% ee. Unfortunately,
the aldehyde or ester derived phenylboronic acids were
not suitable for this reaction (3al–3am). The brominated
substrates based on phenyl ring were also investigated
under standard conditions. Although the reaction
proceeded smoothly, the products did not show any ee
due to the low rotation barrier (see Supporting
Information). At present, there are few reports on the
coupling of 2-diarylphosphinyl-1-naphthyl bromide or 2-
dialkoxyphosphinyl-1-naphthyl bromide with naphthalene
boronic acid or ortho substituted phenylboronic acid in
the product
raw material recovery
the reaction
Scheme 4. 100-gram scale synthesis.
As an indication of the possible practical potential of
this catalyst system, the screening reactions were carried
out on a 100-gram-scale synthesis (Scheme 4). A 350
mmol scale reaction of 1a (142.5 g) with two equivalents of
2a worked smoothly under the catalysis of 2.5 mol% of
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Pd(OAc)2/(SC, RFC, RS)-WJ5, delivering 98.6 g of 3aa in
Page 4 of 7
catalyzed asymmetric hydrosilylation of olefins (Scheme
7).[16] It is interesting to find that most of these ligands
could deliver the product in high yields with high
enantioselectivity.
1
2
3
4
5
6
7
8
62% yield with 94% ee (53% yield, >99% ee after
recrystallization) and 28% of 1a was recovered. The
absolute configuration was determined by X-ray
diffaction analysis of product 3aa.[11] To demonstrate that
product 3aa could be used as a “platform molecule“,
several transformations were then carried out (Scheme 5).
Firstly, the product 3aa could be reduced[12] then oxidized
in the presence of sulfur to obtained the phosphine
sulfide product 4a in a high yield without loss the
enantiopurity.[13] Secondly, the phosphine compounds 4b,
4c, 4d and 4e were achieved in >99% ee[14] by Pd(II)-
HSiCl3 (5.0 eq.), NEt3 (24 eq.)
toluene, 110 oC, 18 h
O
P
Ar
Ar
Ar
P
Ar
3
,
(0.2 mmol) >99% ee
5
R
R
9
Ph
P
P
P
Ph
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
R
R
i
5a
5d
5e
, R = Pr, 92%, 98% ee
5b
5c,
, R = OMe, 90%, >99% ee
catalyzed
Ph2(O)P-directed
C-H
acetoxylation,
88%, >99% ee
R = OCF3, 93%, >99% ee
, R = F, 93%, 98% ee
hydroxylation and olefination of 3aa, respectively. The
Ph2(O)P group not only acts as the directing group but
also serves to construct the alkene-phosphine ligands.
The products 4f, 4g, 4h, 4i with high enantioselectivity
delivered by the product 4e[12, 15] under the corresponding
conditions.
R
P
R
Ph
P
Ph
P
R
Ph
Ph
R
5i
5f, R = OMe, 96%, 92% ee
5g
, 95%, 97% ee
5h
, 90%, 98% ee
, R = CF3, 94%, 98% ee
Scheme 6. Synthesis of Binaphthyl monophosphines
via the reduction of 3.
S
PPh2
OAc
SiCl3
OH
[PdCl(-C3H5)]2 (0.1 mol%)
P(O)Ph2
L* (0.2 mol%)
H2O2, KF
KHCO3
Me
Me
OH
4a
HSiCl3
88%, >99% ee
PPh2
4b
6a
7a
(1.0 mmol)
8a
90%, >99% ee
4i
A
73%, >99% ee
CO2Et
P(O)Ph2
OMe
OCF3
B
L
*:
P
P
PPh2
I
C
5a
5b
5c
4c
70%, >99% ee
OMe
PPh2
O
P
OMe
OCF3
CO2Et
8a
, 88%, 90% ee
8a
8a, 87%, 90% ee
, 90%, 94% ee
Ph
Ph
H
CF3
D
P(O)(OEt)2
P(O)Ph2
4h
68%, >99% ee
3aa
, >99% ee
P(O)(OEt)2
P
Ph
Ph
G
CF3
CF3
Ph
Ph
E
P
P
F
4d
92%, >99% ee
F3C
5g
5h
5i
OMe
8a
, 91%, 90% ee
8a
, 94%, 90% ee
8a
, 92%, 90% ee
P(O)Ph2
OH
P(O)Ph2
Scheme 7. Testing the developed phosphine ligand
libraries.
4g
70%, 98% ee
OTf
P(O)(Ph)2
4e
79%, >99% ee
4f
75%, 99% ee
In light of the absolute configurations of the chiral
ligand (SC, RFC, RS)-WJ5 and the product S-3aa, a chirality
induction model of palladium atom clamped into an 8-
o
Conditions: [A]: 1) HSiCl3 (5.0 eq.), NEt3 (24 eq.), toluene, 110 C, 18
h; 2) S, THF, rt. [B]: Pd(OAc)2 (10 mol%), PhI(OAc)2 (3.0 eq.). [C]:
Ac-Gly-OH (20 mol%), Pd(OAc)2 (10 mol%), AgOAc (5.0 eq.). [D]:
Ac-Gly-OH (20 mol%), Pd(OAc)2 (10 mol%), AgOAc (5.0 eq.). [E]:
(CF3CO2)2Pd (10 mol%), PhI(CF3CO2)2 (1.5 eq.), CH3NO2. [F]: 1)
(CF3CO2)2Pd (10 mol%), PhI(CF3CO2)2 (1.5 eq.), CH3NO2; 2) Tf2O, Py,
DCM. [G]: 1) (CF3CO2)2Pd (10 mol%), PhI(CF3CO2)2 (1.5 eq.); 2) CH3I,
K2CO3. [H]: 1) (CF3CO2)2Pd (10 mol%), PhI(CF3COO)2 (1.5 eq.); 2)
CH3I, K2CO3; 3) HSiCl3, NEt3. [I]: 1) (CF3CO2)2Pd (10 mol%),
PhI(CF3CO2)2 (1.5 eq.), CH3NO2; 2) HSiCl3, NEt3.
membered ring by P and O coordination was proposed
8, 17]
(Scheme 8).[4c,
In this transition state, the steric
resistance between naphthyl ring of substrate 2a and
diphenylphosphine oxide of substrate 1a is more smaller,
which upon reductive elimination should release the
product S-3aa.
Scheme 5. Transformations of 3aa.
O
P
Ph
Gratifying, the products of this palladium-catalyzed
suzuki coupling reaction could also be readily reduced
under mild reaction conditions delivered the
monophosphine ligand with good yield and high ee value
(Scheme 6).[12] Notably, the reduced products 5a-5c were
achieved in 88%-93% yield without loss of ees. But the
products 5d-5e, 5g-5i were delivered in 90%-96% yield
with slightly declined ees. Unfortunately, the [1,1'-
binaphthalen]-2-ylbis(3,5-dimethoxyphenyl)phosphine
was obtained in 96% yield with 92% ee. These
monphophines ligands could be used in palladium-
Ph
-3aa
S
Scheme 8. Proposed Asymmetric Induction Model.
In summary, we have developed operational
a
simplicity, highly enantioselective palladium-catalyzed
Suzuki-Miyaura cross-coupling reaction by using WJ-
Phos as chiral ligand, which provides a facile access to
various substituents axially chiral biaryl monophosphine
oxides in good yields and high ee values. In light of the
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ACS Catalysis
Catalyzed Enantioselective Construction of γ-Butenolides
synthetic applications of the axially chiral biaryl
monophosphine ligand, this approach can be expected to
applying in wide-ranging synthetic applications.
Through Substitution of Morita−Baylis−Hillman Acetates with 2-
Trimethylsilyloxy Furan. J. Am. Chem. Soc. 2008, 130, 7202-7203.
(n) Cao, Z.; Liu, Y.; Liu, Z.; Feng, X.; Zhuang, M.; Du, H. Pd-
Catalyzed Asymmetric Allylic Alkylation of Indoles and Pyrroles
by Chiral Alkene-Phosphine Ligands. Org. Lett. 2011, 13, 2164-
2167. (o) Zhu, Y.; Buchwald, S. L. Ligand-Controlled Asymmetric
Arylation of Aliphatic α-Amino Anion Equivalents. J. Am. Chem.
Soc. 2014, 136, 4500-4503. (p) Sakai, M.; Ueda, M.; Miyaura, N.
Rhodium-Catalyzed Addition of Organoboronic Acids to
Aldehydes. Angew. Chem. Int. Ed. 1998, 37, 3279-3281. (q) Ma, Y.-
N.; Yang, S.-D. Asymmetric Suzuki-Miyaura Cross-Coupling for
the Synthesis of Chiral Biaryl Compounds as Potential
Monophosphine Ligands. Chem. Eur. J. 2015, 21, 6673-6677. (r)
Takahashi, I.; Morita, F.; Kusagaya, S.; Fukaya, H.; Kitagawa, O.
Catalytic Enantioselective Synthesis of Atropisomeric 2-Aryl-4-
quinolinone Derivatives with an N–C Chiral Axis. Tetrahedron:
Asymmetry, 2012, 23, 1657-1662.
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AUTHOR INFORMATION
Corresponding Author
*E-mail: hhwu@chem.ecnu.edu；
junliangzhang@fudan.edu.cn
Notes
9
The authors declare no competing financial interests.
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ASSOCIATED CONTENT
Supporting Information: Experimental procedures,
spectroscopic data for the substrates and products (PDF).
This material is available free of charge via the Internet at
http://pubs.acs.org.
(2) (a) Bringmann, G.; Walter, R.; Weirich, R. The Directed
Synthesis of Biaryl Compounds: Modern Concepts and Strategies.
Angew. Chem. Int. Ed. Engl. 1990, 29, 977-991. (b) Yin, J.;
Buchwald, S. L. A Catalytic Asymmetric Suzuki Coupling for the
Synthesis of Axially Chiral Biaryl Compounds. J. Am. Chem. Soc.
2000, 122, 12051-12052. (c) Shen, X.; Jones, G. O.; Watson, D. A.;
Bhayana, B.; Buchwald, S. L. Enantioselective Synthesis of Axially
Chiral Biaryls by the Pd-Catalyzed Suzuki−Miyaura Reaction:
Substrate Scope and Quantum Mechanical Investigations. J. Am.
Chem. Soc. 2010, 132, 11278-11287. (d) Wang, S.; Li, J.; Miao, T.;
Wu, W.; Li, Q.; Zhuang, Y.; Zhou, Z.; Qiu, L. Highly Efficient
Synthesis of a Class of Novel Chiral-Bridged Atropisomeric
Monophosphine Ligands via Simple Desymmetrization and
Their Applications in Asymmetric Suzuki–Miyaura Coupling
Reaction. Org. Lett. 2012, 14, 1966-1969. (e) Wu, W.; Wang, S.;
Zhou, Y.; He, Y.; Zhuang, Y.; Li, L.; Wan, P.; Wang, L.; Zhou, Z.;
Qiu, L. Highly Diastereoselective Synthesis of Atropisomeric
Bridged P,N-Ligands and Their Applications in Asymmetric
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Axially Chiral Multifunctionalized Biaryls via Asymmetric
Suzuki–Miyaura Coupling. Org. Lett. 2013, 15, 5508-5511. (g) Zhou,
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Chiral Biaryl Monophosphine Oxides via Direct Asymmetric
ACKNOWLEDGMENT
We gratefully acknowledge the funding support from NSFC
(21425205, 21573073), 973 Program (2015CB856600), and the
Program of Eastern Scholar at Shanghai Institutions of
Higher Learning and Program for Changjiang Scholars and
Innovative Research Team (IRT-16R25).
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