Asymmetric Hydrophosphination of Heterobicyclic Alkenes: Facile Access to Phosphine Ligands for Asymmetric Catalysis

Article abstract of DOI:10.1021/acscatal.8b04787

Asymmetric hydrophosphination is the most atomically economical and straightforward approach to the construction of chiral organophosphorus compounds. Good stereoselectivities have been achieved in asymmetric hydrophosphination of an electron-deficient C=

Full text of DOI:10.1021/acscatal.8b04787

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Article
Asymmetric Hydrophosphination of Heterobicyclic Alkenes:
Facile Access to Phosphine Ligands for Asymmetric Catalysis
Zhiwu Lu, Haoyang Zhang, Zhiping Yang, Ning Ding, Ling Meng, and Jun (Joelle) Wang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b04787 • Publication Date (Web): 07 Jan 2019
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ACS Catalysis
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Asymmetric Hydrophosphination of Heterobicyclic Alkenes:
Facile Access to Phosphine Ligands for Asymmetric Catalysis
Zhiwu Lu,† Haoyang Zhang,† Zhiping Yang,† Ning Ding,† Ling Meng†‡ and Jun (Joelle) Wang*†
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†Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen
518055, China.
‡Department of Chemistry, Hong Kong University of Science and Technology, Hong Kong
ABSTRACT: Asymmetric hydrophosphination is the most atomically economical and straightforward approach to the construction
of chiral organophosphorus compounds. Good stereoselectivities have been achieved in asymmetric hydrophosphination of an
electron-deficient C=C double bond, but substrates involving non-polar C=C bonds remain difficult and are rarely tackled. Herein,
we report asymmetric hydrophosphination of a non-electronically activated double bond with a remarkably high degree of stereo
control. This strategy offered an expedient and broadly applicable platform to prepare tertiary phosphines in high yields (up to 99%
yield) and enantioselectivities (up to 99% ee). Particularly noteworthy is that these tertiary phosphine products were then
successfully employed as phosphine ligands in enantioselective metal-catalyzed transformations with a high level of asymmetric
induction.
Pd/bisphosphine ligand
Ar
X
R
X
R
+
HP
Ar
high efficiency
PAr2
high enatioselectivity
exclusive exo-selectivity
insensitive to air product
readily scalable
X = O, N
up to 99% yield
up to 99% ee
modifiable phosphine ligand
applicable to asymmetric catalysis
KEYWORDS: Asymmetric Catalysis, Hydrophosphination, Chiral phosphine, Alkene, Ligand design.
(a)
1. hydrophosphonylation
O
2. hydrophosphinylation
O
Organophosphorus compounds are broadly utilized synthetic
building blocks for accessing bioactive molecules and
functional materials. Indeed, they also play significant roles in
metal-catalyzed and organocatalytic transformations.1 There
are three major types of P−C bond construction from addition
reactions to unsaturated compounds: 1) hydrophosphonylation
or the addition of dialkyl phosphites; 2) hydrophosphinylation
or the addition of secondary phosphine oxides; and 3)
hydrophosphination or the addition of secondary phosphines to
C=C double bonds (Scheme 1a). Of these three categories,
asymmetric hydrophosphination is the most straightforward
approach for generating optically active tertiary phosphines
which are highly useful ligands in asymmetric catalysis.2
Nevertheless, method of enantioselective addition of secondary
phosphine to C=C double bond remains rudimentary as
compared to the addition of dialkyl phosphates and secondary
phosphine oxides. The main challenge arises from the former is
that the new-born tertiary phosphine products would render the
original complex coordinative saturated which negatively
impacts catalyst efficiency and chiral induction ability. Thus,
the development of a catalyst system allowing efficient
asymmetric hydrophosphination of alkenes is highly desirable.
O
O
P(OR)2
H
PR2
PR2
R2
H
P(OR)2
R1
R1
R1
R2
3. hydrophosphination
PR2
R2
H-PR2
R1
R2
(b) 1. Previous works: asymmetric hydrophosphination to electron-deficient alkene
PAr2
Pt, Ni or Pd
EWG
+
HPAr2
EWG
*
R
organocatalyst
R
A. Pt(Me-Duphos), acrylonitrile and acrylate esters, up to 27% ee, 2000, ref 3
B. Ni(Pigiphos), methacrylonitrile, up to 94% ee, 2004, ref 4.
C. Pincer-Pd, enones, enals, enamides, nitroalkenes, carboxylic and sulfonic
esters, up to 94% ee, since 2010, ref 5-7.
2. Our plan: asymmetric hydrophosphination of non-electronically activated alkene
PAr2
Pd
Z
R
+
HPAr2
R
*
Z
Z = O, NR
Scheme 1. (a) Classification of P−H bond addition reactions;
(b) Transition metal-catalyzed asymmetric
hydrophosphination of alkenes
In 2000, Glueck pioneering reported the Pt(Me-Duphos)-
catalyzed asymmetric addition of secondary phosphines to
acrylonitrile and acrylate esters, though with low
enantioselectivities (Scheme 1b).3 Successful metal-catalyzed
asymmetric hydrophosphination of methacrylonitrile was later
shown by Togni.4 In 2010, Duan5 and Leung6 reported the
hydrophosphination reaction of electron-deficient enones
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catalyzed by chiral PCP-pincer palladium complex and
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HN Boc
Boc
Boc
PPh2
+
*
Pd(OAc)2 / L*
toluene, 90°C
1
2
3
4
5
6
7
8
phosphapalladacycle catalyst, respectively. Since then,
examples of the palladium-catalyzed conjugate addition of
diarylphosphines to α,β-unsaturated carbonyl compounds have
emerged.7 Notable complementary examples of asymmetric
organocatalytic hydrophosphination of α,β-unsaturated
carbonyl compounds were presented by Córdova8 and
Melchiorre.9 While good stereoselectivities have been achieved
in metal-catalyzed and organocatalytic asymmetric
hydrophosphination of electron-deficient double bonds,
substrates such as those involving non-polar C=C bonds remain
challenging and are rarely tackled. The inherent difficulty of
this addition reaction is attributed to the lower reactivity of
simple/non-polar alkenes susceptible to nucleophilic attack
versus electronically activated alkenes. Han reported Pd-
catalyzed hydrophosphorylation of norbornenes with more
reactive five-membered cyclic (pinacolato)P(O)−H, suggesting
that bicyclic alkenes were good substrates in C-P bond
formation.10 In fact, the hydrophosphination of non-polar
alkenes is still challenging, and it would be highly desirable to
develop a catalyst system that facilitates this transformation,
especially with high enantioselectivity. Such a scheme would
directly afford a new series of chiral phosphine ligands.
N
HPPh2
N
+
2a
3aa
1a
4
R
P
R
R
PPh2
PPh2
R
R
P
P
P
R
R
R
L1
L2
L3
L4 (S,S)-Et-BPE (R = Et)
(R,R)-Ph-BPE (R = Ph)
(R)-Binap
(S,S)-Me-Duphos (R = Me)
(R,R)- Pr-Duphos (R = iPr)
i
L5
9
tBu
tBu
P
H
N
N
P
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H
Me
Me
P
P
P
H
H
tBu
P
tBu
tBu
tBu
L6
(S)-Binapine
L7
(Rc,Sp)-Duanphos
L8
(R,R)-QuinoxP
3aa
4
entry ligand
time yield ee
yield
(%)b
-
16
16
ee
(%)c
-
39
88
51
89
-
(h) (%)b (%)c
1
2
3
4
L1
L2
L3
L4
L5
L5
L6
L7
L8
72
12
12
6
45
71
70
70
82
95
53
81
92
97
17
82
93
79
98
97
96
86
81
99
16
Heterobicyclic alkenes are ideal substrates to be activated by
transition metal complexes due to the angle strain and the
proximal heteroatom coordination.11 Indeed, upon using the
proposed modular reaction between commercially available
alkene and HPR2, a new family of chiral phosphine ligands
would be made easily and effectively. Furthermore, N or O
atoms on the bridge of the heterobicyclic alkene might provide
an additional coordinating site to transition metal; this would
form a chiral bidentate complex for obtaining high level chiral
induction.12 Thus, we started to embark this investigation using
azabenzonorbornadiene and diphenylphosphine as model
substrates (Table 1). Initial screening of Pd precursors revealed
that Pd(OAc)2 was superior. Strongly chelating ligands result in
good enantioselective control. High ee values were observed
with bulkier ligands, i.e., L3, L5, and L6 (Table 1, entries 3, 7,
8). Some other bisphosphine ligands led to a fair amount of
reductive ring-opening product 4 where HPPh2 was the H
donor.13 (R,R)-Ph-BPE L5 gave an 82% yield of 3aa with the
best ee (98%), yet with 11% yield of byproduct 4 with 89% ee,
in toluene at 90C for 6 h. To our delight, the byproduct could
be suppressed by adding 10 mol % Fe(OAc)2 (the screening of
additive, see Table S1). With the optimized catalyst system, the
desired chiral phosphine product 3aa was obtained exclusively
in 95% yield with 97% ee (Table 1, entry 6). The yield and ee
were further improved to 97% and 99%, respectively, by
lowering the reaction temperature from 90°C to 70°C (Table 1,
entry 10). Other solvents such as DME, dioxane, and THF also
gave good yields and high ees (see the Supporting Information).
The resulting phosphine product 3aa was found highly air stable
which is in contrast to other reported phosphines generated via
1,4-addition, where those products were required to oxidize to
stable phosphine oxides in situ by H2O2 or to be reduced to
phosphine-borane by in situ reaction with NaBH4.5-9
5
6
6
6
12
12
6
11
trace
45
8
trace
trace
6 d
7
>99
-
-
8
9
10 d, e L5
-
aReaction conditions: Pd(OAc)2 (5 mol %) and Ligand (6 mol
%) in toluene (2 mL) were stirred at r.t. for 30 min under argon.
1a (0.1 mmol) and 2a (0.2 mmol) were added, and the reaction
mixtures were stirred at 90oC for time indicated. bIsolated yields.
cDetermined by HPLC analysis. d10 mol % Fe(OAc)2 was added
as additive. eThe reaction was performed at 70 oC.
With optimized conditions in hand, we next investigated the
substrate scope of both azabenzonorbornadienes and
diarylphosphines (Scheme 2). Aryl moieties (2b-2f) with a
variety of substituents were successfully applied to the reaction
with 1a, and gave the corresponding addition products 3ab-3af
in 56-98% yields with the enantioselectivities ranging from
87% to 99% ees. Diarylphosphine with an electron-
withdrawing CF3 group was found to be slightly sluggish under
these reaction conditions, and gave 3af in 56% yield with 87%
ee after prolonged reaction time. The reaction partner of
azabenzonorbornadienes 1b-f with various substituents at the
aromatic moiety proceeded well, and provided the products
3ba-3fa in 86-97% yield and 98-99% ee. The bromo group in
3ca remained intact under these conditions and allowed further
potential functionalization. The nature of the substituted group
on the nitrogen atom in azabenzonorbornadienes played a
critical role to the product yield. When the Ts group was used
instead of the Boc group, the product yield of 3ga decreased to
68% although the ee value remained excellent. To demonstrate
the practicability, we also performed a scale-up experiment
using 6.80 g (28 mmol) of azabenzonorbornadienes 1a as the
substrate. This protocol offered excellent product yield of 3aa
(10.94 g, 91%) without compromising the enantioselectivity
(99% ee). The absolute configuration of 3ac was determined by
Table 1. Ligand screening for Pd-catalyzed asymmetric
hydrophosphination of azabenzonorbornadienes with
diphenylphosphinesa
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X-ray diffraction analysis, and other products 3 were assigned
Pd(OAc)2
(R,R)-Quinoxp
by analogy.14
Ar
Ar
1
2
3
4
5
6
O
R
O
+
R
HP
Fe(OAc)2
toluene, 70 °C
PAr2
5a-i
6aa-6ia
6aa
2a-f
Boc
Boc
PAr2
Pd(OAc)2 / (R,R)-Ph-BPE
N
R
HPAr2
N
R
+
F
CH3
Fe(OAc)2, toluene, 70°C
O
O
O
2a-f
1a-g
3aa-3ga
P
F
P
P
CH3
6aa
6ac
F
6ab
7
8
9
99% yield, 90% ee (>99.9% ee)b
CH3
93% yield, 83% ee
94% yield, 83% ee
Boc
P
Boc
P
CH3
CF3
OCH3
N
N
O
O
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CH3
O
F
3ab
6 h, 91% yield, 99% ee
3ac
48 h, 90% yield, 97% ee
OCH3
P
P
P
CH3
6ad
6af
6ae
CF3
H3C
CH3
H3C
CH3
CF3
OCH3
92% yield, 86% ee (>99.9% ee)b
81% yield, 88% ee (>99% ee)b
81% yield, 81% ee
Boc
Boc
P
Boc
P
CH3
P
H3CO
H3C
H3C
Br
Br
N
O
N
N
O
O
H3CO
P
P
P
OCH3
CF3
3af
3ad
3ae
CH3
6da
6ba
6ca
72 h 56% yield, 87% eeb
40 h, 83% yield, 93% ee
6 h, 98% yield, 98% ee
92% yield, 86% ee
OCH3
90% yield, 82% ee
86% yield, 88% ee
O
O
O
Boc
Boc
Boc
H3C
H3C
P
O
O
P
Br
Br
P
O
O
O
N
N
N
O
P
P
P
OCH3
6ea
6fa
3ba
3ca
3da
6ga
6 h, 97% yield, 98% ee
6 h, 87% yield, 98% ee
6 h, 96% yield, 99% ee
96% yield, 86% ee (>99% ee)b
96% yield, 86% ee
99% yield, 76% ee
CH3
Boc
P
Boc
Ts
P
H3CO
H3CO
P
O
O
O
N
N
N
P
P
O
CH3
3ea
3fa
3ga
6ha
6ia
36% yield, 77% eec
12 h, 68% yield, 99% eeb
6 h, 92% yield, 98% ee
6 h, 86% yield, 98% ee
aReaction conditions: Pd(OAc)2 (5 mol %), Fe(OAc)2 (10 mol %),
and (R,R)-Ph-BPE (6 mol %) in toluene (2 mL) were stirred at r.t.
for 30 min under argon. 1a-j (0.1 mmol) and 2a-f (0.2 mmol) were
added, and the reaction mixtures were stirred at the 70°C for
indicated period of time. Isolated yields were shown; ees were
determined by HPLC analysis. bThe reaction was not completed.
97% yield, 83% ee
aReaction conditions: Pd(OAc)2 (5 mol %), Fe(OAc)2 (10 mol %),
and (R,R)-QuinoxP (6 mol %) in toluene (2 mL) was stirred at r.t.
for 30 min under argon. 5a-j (0.15 mmol) and 2a-f (0.3 mmol) were
added, and the reaction mixtures were stirred at the 70°C for 12 h.
Isolated yields were shown; ees were determined by HPLC
analysis. bees after recrystallization are parentheses. cThe reaction
was not completed.
Scheme 2. Substrate scope of azabenzonorbornadiene and
diarylphosphinesa
Scheme 3. Substrate scope of oxabenzonorbornadiene and
diarylphosphinesa
Encouraged
by
the
capacity
for
asymmetric
hydrophosphination of azabenzonorbornadienes, we next
focused on oxabenzonorbornadienes (Scheme 3).15 The optimal
reaction conditions for asymmetric hydrophosphination of
oxabenzonorbornadienes was in toluene at 70°C with 5 mol %
Pd(OAc)2, 6 mol % (R,R)-QuinoxP, and 10 mol % Fe(OAc)2
(see Supporting Information for screening details). In addition
to diphenylphosphine, both electron-rich and -poor
diarylphosphines 2b-2f were found applicable nucleophiles in
reacting with oxabenzonorbornadiene (5a). This reaction
afforded the corresponding chiral phosphines 6aa-6af in
excellent yields and high enantioselectivities (81-99% yield,
81-90% ee) (Scheme 3). Essentially no significant electronic
effect was observed on the substituted oxabenzonorbornadiene
substrates, and the desired adducts 6ba-6ha were given in high
yields (86-99%) with consistently good enantioselectivities (76-
88% ee). Substrate 5h has an extended aromatic structure also
3
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of arylboronic acids to aryl aldehydes, unlike the extensive
Page 4 of 7
gave
a
high yield and good ee. Steric hindered
5i reacted smoothly with
1
2
3
4
5
6
7
8
oxabenzonorbornadienes
studies of the asymmetric arylation of α,β-unsaturated carbonyl
compounds and imines. Only chiral rhodium17 and two
ruthenium catalysts18 have been described. Certainly, aldehydes
are more difficult substrates than imines or activated ketones for
achieving high enantioselectivities. To our delight, initial test in
diphenylphosphine to give the desired product with 77% ee, yet
in low conversion. To show the synthetic utility of this method,
we performed a gram-scale experiment with 3 mol % of Pd
catalyst. Product 6aa was afforded in excellent yield (1.704 g,
86%) and ee (90%) from substrate 1a (6 mmol, 0.864 g).
Although the product enantioslectivities were slightly lower
Table
2 showed monophosphine ligand 6aa with an
oxabenzonorbornadiene backbone provided the arylation
product 9aa in 99% yield with 85% ee (Table 2, entry 4). The
more sterically hindered Oxaphos 6ad with a xylyl group in the
phosphino moiety gave comparable yield and ee (Table 2, entry
5). The reaction rate decreased when the ratio of Ru and ligand
was 1:2, only 72% yield and 82% ee were obtained even in 90
h (Table 2, entry 7 vs 4). To better understand the structure of
the active Ru catalyst for this transformation, a Ru-Oxaphos
complex was prepared at a 1:1 ratio (see the Supporting
Information). Similar yield and ee value were obtained when
the complex was used as a catalyst, suggesting that Oxaphos
6aa acted as a mixed bidentate ligand (Table 2, entry 8).
when
compared
with
the
products
from
azabenzonorbornadienes, the final adducts can be easily
recrystallized to give the enantiopure form, and the ee levels of
6aa, 6ad, 6af, 6ga were all improved to >99%, in which they
are ready to serve as chiral ligands for further applications in
asymmetric catalysis.
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On the basis of a preliminary NMR study (see the Supporting
Information), we proposed a mechanistic pathway for this
catalysis (Scheme 4). Chiral palladium complex A is formed by
the Pd(OAc)2 and (R,R)-QuinoxP. The formation of
intermediate A was observed and confirmed by 31P NMR
experiments. Transphosphination between the diarylphosphine
and the chiral palladium A probably affords the palladium
phosphido complex B. Then, oxabenzonorbornadiene 5a
coordinates to complex B and produces the Pd-phosphido-
alkene complex C. Subsequent nucleophilic attack of the
diarylphosphido group on palladium to the C=C double bond of
oxabenzonorbornadiene provides intermediate D. Protonlysis
with diarylphosphine affords the phosphine product 6aa and
regenerates the active palladium complex B. The catalytic cycle
consists of transphosphination, coordination, phosphine
addition, and protonolysis.
Table 2. Ligand screening for Ru-catalyzed asymmetric
addition of phenylboronic acid to 2-naphthaldehydea
O
OH
4 mol % Ru cat.
H
4.8 mol % ligand
*
PhB(OH)2
1 equiv. K3PO4
dioxane, 70°C
7a
8a
9aa
entry ligand
time
(h)
24
24
24
12
24
48
90
12
yield ee
(%)b (%)c
1
2
3
4
5
6
(R)-Azaphos 3aa
98
94
92
99
99
80
72
92
67
60
61
85
84
80
82
84
(R)-4-F-Azaphos 3ac
(R)-4-MeO-Azaphos 3ae
(R)-Oxaphos 6aa
P
31P NMR: 52.4 ppm
Pd(OAc)2
A
ESI-HRMS: m/z [M-OAc]+ 499.0882
*
(R)-3,5-Me2-Oxaphos 6ad
(R)-CF3-Oxaphos 6af
P
2HPPh2
2HOAc
PPh2
transphosphination
7d (R)-Oxaphos 6aa
8e
(R)-Oxaphos 6aa complex
O
O
Ph2P
H
+
P
aReaction conditions: [RuCl2(cymene)]2 (2 mol %), ligand (4.8 mol
%) in the dioxane (2 mL) was stirred at r.t. for 30 min under argon.
7a (0.15 mmol), K3PO4 (0.15 mmol) and 8a (0.3 mmol) were added.
Pd
*
HOAc
PPh2
P
6aa
+
HOAc
B
5a
isolated as the oxidized form:
31P NMR: 57.8, 31.0 ppm
ESI-HRMS: m/z [M+H]+ 843.1760
o
The reaction mixture was stirred at 70 C for the time indicated.
2HPPh2
HPPh2
c
bIsolated yields. Determined by HPLC analysis. dLigand (R)-
e
Oxaphos 6aa (9.6 mol %, Ru:ligand = 1:2) was used. Formerly
OAc
PPh2
Pd
OAc
P
prepared Ru-Oxaphos complex (Ru:ligand = 1:1) was used.
PPh2
P
P
Pd
*
O
*
P
O
The scope of the Ru-catalyzed addition of arylboronic acids
to aldehydes was presented in Scheme 5. Naphthaldehydes
provided good yields and selectivities (9aa, 9ba, 9ca, and 9da).
The enantioselectivities of the phenylation of aldehydes having
ortho-substituents on the arene ring were lower than those
obtained with meta or para-substituted aromatic aldehydes (9ga
vs 9ea, 9fa). Higher yields and ee values were observed when
pi-extended aromatic aldehydes were employed (9ja, 9ka, 9la,
and 9ma). In the Ru-catalyzed asymmetric addition of
arylboronic acids to anthracene-9-carbaldehyde, excellent
yields and ees were achieved regardless of the electronic
properties and substitution pattern of arylboronic acids (9ma-
9mh). Thus, the present catalytic system is highly effective in
the asymmetric synthesis of diarylmethanols having
polynuclear aromatic rings (>96% ee for most polynuclear
aromatic aldehydes).
D
C
addition
Scheme 4. Proposed mechanism.
The investigation of efficient chiral ligands remains the
center of research in asymmetric catalysis. The most developed
and explored chiral monophosphine ligands are often focused
on biaryl, spiro, ferrocenyl, TADDOLs, and other
frameworks.16
Enjoying
the
effective
asymmetric
hydrophosphination of aza- and oxabenzonorbornadienes,
many aza-monophosphine ligands 3aa-3ga and oxa-
monophosphine ligands 6aa-6ia were obtained in high yields
with excellent enantioselectivities in one step. We thus
attempted to apply these oxa- and aza-benzonorbornadiene-
backbone chiral ligands in Ru-catalyzed arylation of aldehydes.
In fact, there are limited examples of the asymmetric addition
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All authors have given approval to the final version of the
manuscript.
4 mol % Ru
4.8 mol % Oxaphos
OH
O
1
2
3
4
5
6
7
8
O
6aa
Ar2B(OH)2
*
P
+
H
Ar1
Ar2
Ar1
7a-m
K3PO4
dioxane, 70 °C
8a-h
9aa-9mh
20 examples
ACKNOWLEDGMENT
6aa
Oxaphos
HO
This work is supported by Shenzhen Basic Research Program
(JCYJ20170817112532779 and JCYJ20170412152435366) and
the Shenzhen Nobel Prize Scientists Laboratory Project
(C17213101). Dr. Xiaoyong Chang from SUSTech is gratefully
acknowledged for X-ray crystallographic analysis.
Ar2
Scope of aldehyde:
Scope of arylboronic acid:
OH
Ar1
, Ar1 = 2-naphthyl, 99% yield, 85% ee
, Ar1 = 1-naphthyl, 99% yield, 88% ee
, Ar1 = 4-Br-1-naphthyl, 99% yield, 87% ee
, Ar1 = 4-Me-1-naphthyl, 87% yield, 85% ee
, Ar1 = 4-Br-C6H4, 94% yield, 80% ee
, Ar1 = 3-Br-C6H4, 90% yield, 75% ee
, Ar1 = 2-Br-C6H4, 52% yield, 73% ee
, Ar1 = 4-F-C6H4, 90% yield, 80% ee
, Ar1 = 4-CF3-C6H4, 98% yield, 75% ee
, Ar1 = 9-phenanthrenyl, 99% yield, 93% ee
9aa
9ba
9ca
9da
9ea
9ma, Ar2 = Ph, 99% yield, 97% ee
9mb, Ar2 = 4-Me-C6H4, 94% yield, 96% ee
9mc, Ar2 = 4-MeO-C6H4, 70% yield, 87% ee
9md, Ar2 = 4CF3-C6H4, 96% yield, 96% ee
9me, Ar2 = 4-Br-C6H4, 98% yield, 97% ee
9mf, Ar2 = 3-Br-C6H4, 98% yield, 97% ee
9mg, Ar2 = 4-CO2Me-C6H4, 86% yield, 96% ee
9mh, Ar2 = 2-naphthyl, 98% yield, 96% ee
9
REFERENCES
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9fa
9ga
9ha
9ia
9ja
, Ar1 = 10-Me-9-anthracenyl, 98% yield, 96% ee
, Ar1 = 1-pyrenyl, 98% yield, 90% ee
9ka
9la
aReaction conditions: [RuCl2(cymene)]2 (2 mol %) and (R)-
Oxaphos 6aa (4.8 mol %) in the dioxane (2 mL) were stirred at r.t.
for 30 min under argon. 7a-m (0.15 mmol), K3PO4 (0.15 mmol),
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stirred at 70°C for the indicated period of time. Isolated yields; ee
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Scheme 5. Ru-catalyzed asymmetric addition of
phenylboronic acid to aryl aldehydesa
In
conclusion,
unlike
hydrophosphinylation
and
hydrophosphonylation in generating phosphine oxides and
phosphites, respectively, the hydrophosphination is still less
developed. Here, we report
a
general asymmetric
hydrophosphination of heterobicyclic benzonorbornadienes
with diarylphosphines.19 This method offered a direct and atom
efficient access to chiral tertiary phosphines in high yields (up
to 99% yield) with excellent enantioselectivities (up to 99% ee).
Particularly noteworthy is that the resulting new family of chiral
phosphine products have been successfully applied to the Ru-
catalyzed asymmetric arylation of aldehydes with arylboronic
acids, which highlighted their considerable potential for
asymmetric catalysis. The modular structure and easy
accessibility of monophosphines bearing aza- or oxa-
benzonorbornadiene backbones makes it possible to optimize
the ligand structure for a wide range of reactions catalyzed by a
variety of transition metals. We anticipate that these unique
monophosphines will open up a new platform in developing
new chiral phosphine ligands.
R.;
Stern,
C.
L.;
Marks,
of
T.
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Intramolecular
and
Hydrophosphination/Cyclization
Phosphinoalkenes
Phosphinoalkynes Catalyzed by Organolanthanides: Scope, Selectivity,
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ASSOCIATED CONTENT
Supporting Information. This material is available free of charge
via the Internet at http://pubs.acs.org. Experimental procedures,
screening of reaction conditions, mechanistic study and
characterization data for all new compounds (PDF).
(3) Kovacik, I.; Wicht, D. K.; Grewal, N. S.; Glueck, D. S.; Incarvito,
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AUTHOR INFORMATION
(4) (a) Sadow, A. D.; Haller, I.; Fadini, L.; Togni, A. Nickel(II)-
Catalyzed Highly Enantioselective Hydrophosphination of
Methacrylonitrile. J. Am. Chem. Soc. 2004, 126, 14704-14705. (b)
Sadow, A. D.; Togni, A. Enantioselective Addition of Secondary
Phosphines to Methacrylonitrile: ꢀCatalysis and Mechanism. J. Am.
Chem. Soc. 2005, 127, 17012-17024.
Corresponding Author
wang.j@sustc.edu.cn
Author Contributions
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(14) CCDC 1814628 [for 3ac], 1589459 [for 6aa] and CCDC
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Crystallographic
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via
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Catal. 2016, 6, 4814-4858. (b) Gladiali, S.; Alberico, E.; Junge, K.;
Beller, M. BINEPINES: Chiral Binaphthalene-Core Monophosphepine
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(17) For Rh-catalyzed asymmetric addition of arylboronic acids to
aryl aldehydes, see: (a) Sakai, M.; Ueda, M.; Miyaura, N. Rhodium-
Catalyzed Addition of Organoboronic Acids to Aldehydes. Angew.
Chem., Int. Ed. 1998, 37, 3279-3281. (b) Jagt, R. B. C.; Toullec, P. Y.;
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775. (c) Nishimura, T.; Kumamoto, H.; Nagaosa, M.; Hayashi, T. The
Concise Synthesis of Chiral tfb Ligands and Their Application to the
Rhodium-Catalyzed Asymmetric Arylation of Aldehydes. Chem.
Commun. 2009, 5713-5715. (d) Duan, H.-F.; Xie, J.-H.; Shi, W.-J.;
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of Arylboronic Acids to Aldehydes using Chiral Spiro Monophosphite
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