Rhodium-Catalyzed Enantioposition-Selective Hydroarylation of Divinylphosphine Oxides with Aryl Boroxines

Article abstract of DOI:10.1002/anie.201712572

The rhodium-catalyzed hydroarylation of divinylphosphine oxides (RP(O)(CH=CH₂)₂) with aryl boroxines ((ArBO)₃) gives the corresponding monoarylation products (RP(O)(CH=CHAr)CH₂CH₃) in high yields. One of the two vinyl groups in the phosphine oxide undergoes oxidative arylation while the other one is reduced to an ethyl moiety. These reactions proceed with high selectivity in terms of the enantiotopic vinyl groups in the presence of (R)-DTBM-segphos/Rh to give the P-stereogenic monoarylation products with high enantioselectivity.

Full text of DOI:10.1002/anie.201712572

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Rhodium-Catalyzed Enantioposition Selective Hydroarylation of
Divinylphosphine Oxides with Arylboroxines
Authors: Zhe Wang and Tamio Hayashi
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201712572
Angew. Chem. 10.1002/ange.201712572
Link to VoR: http://dx.doi.org/10.1002/anie.201712572
http://dx.doi.org/10.1002/ange.201712572

10.1002/anie.201712572
Angewandte Chemie International Edition
COMMUNICATION
Rhodium-Catalyzed Enantioposition Selective Hydroarylation of
Divinylphosphine Oxides with Arylboroxines
Zhe Wang and Tamio Hayashi*
Abstract: Rhodium-catalyzed hydroarylation of divinylphosphine
(a) Desymmetrization of RP(O)AA into RP(O)AB
oxides (RP(O)(CH=CH2)2, 1) with arylboroxines ((ArBO)3, 2) gave
O
P
O
P
O
P
desymmetrization
high yields of monoarylation products (RP(O)(CH=CHAr)CH2CH3, 3),
where one of the two vinyl groups in 1 underwent oxidative arylation
and the other was reduced to ethyl. The reaction in the presence of
(R)-DTBM-segphos/Rh proceeded with high enantioposition-
selectivity to give P-stereogenic monoarylation products 3 with high
enantioselectivity.
A
A
B
R
R
R
A
B
B
achiral
chiral
A
achiral
O
P
O
P
O
O
P
A
A
A
P
R'
R'
O
R
R
R
R
A
[2+2+2]
cycloaddition
C–H
functionalization
B
Y
R'
A
B
R'
There have recently been considerable interests in catalytic
asymmetric synthesis of chiral phosphorus compounds with a
stereogenic center on the phosphorus atom.[1,2] One of the
extensively studied reactions for their catalytic asymmetric
synthesis is desymmetrization of symmetrically substituted
phosphine oxides RP(O)AA where one of the two enantiotopic
substituents A is converted into B leaving the other A unchanged
(Scheme 1a). Typical examples are those by asymmetric
cycloaddition of dialkynylphosphine oxides[3] and C-H activation
of diarylphosphine oxides.[4] One drawback on this type of
asymmetric transformation is over-reaction of RP(O)AB resulting
in RP(O)BB which is achiral. Here we wish to report a new type
of desymmetrization where one of the two enantiotopic
substituents A in RP(O)AA is converted into B and the other A is
converted into a different group C giving rise to a chiral product
RP(O)BC (Scheme 1b), which was realized by rhodium-
catalyzed asymmetric reaction of divinylphosphine oxides with
arylboroxines.
Rhodium-catalyzed asymmetric conjugate arylation of
electron deficient olefins has been recognized to be one of the
most efficient and reliable methods of introducing aromatic
groups with high enantioselectivity.[5] In most cases, the
asymmetric conjugate arylation has been used for creation of
new stereogenic centers at benzylic position by the addition to β-
substituted electron-deficient olefins, typically β-substituted α,β-
unsaturated carbonyl compounds. Several examples have been
also reported in the reaction of β-substituted nitro- and sulfonyl-
olefins.[5] To the contrary, the conjugate addition to
alkenylphosphine oxides has not been well developed[6]
irrespective of the importance of the enantioenriched
organophosphorus compounds.[1,2] This is mainly because β-
substituted alkenylphosphorus compounds, which would
generate new stereogenic center at the β-position, are not very
reactive towards the rhodium-catalyzed conjugate arylation. In
the present desymmetrization reaction of divinylphosphine
oxides, high reactivity is anticipated because the arylation takes
place on the unsubstituted vinyl group.
(b) Desymmetrization of RP(O)AA into RP(O)BC (This Work)
O
P
O
P
desymmetrization
A
C
X
R
R
A
B
achiral
chiral
O
O
P
Ar
Rh/L* catalyst
A
C
+ (ArBO)3 + H2O
P
R
R
hydroarylation
A
B
Scheme 1. Asymmetric synthesis of P-stereogenic phosphorus compounds by
desymmetrization.
During our studies on the rhodium-catalyzed conjugate
arylation of olefins activated by a phosphinyl group, we found
that a new type of desymmetrization takes place in the reaction
of divinylphosphine oxide 1 with arylboron reagent 2, which
selectively yields the product 3 bearing ethyl and 2-arylethenyl
groups on the phosphorus atom. Thus, the reaction of
mesityldivinylphosphine oxide (1a) with (4-MeOC6H4BO)3 (2a) in
the presence of K3PO4 and 5 mol% of a rhodium catalyst
coordinated with (R)-DTBM-segphos[7] in toluene/H2O (10/1) at
80 °C for 14 h gave 91% yield of hydroarylation products
consisting of mesityl(2-(E)-arylethenyl)ethylphosphine oxide
(3aa) and mesityl(2-arylethyl)vinylphosphine oxide (4aa) in a
ratio of 96:4 (equation 1 and entry 1 in Table 1). The main
product 3aa was determined to be an R isomer[8] of 88% ee .
[RhCl(coe)2]2 (5 mol% Rh)
(R)-DTBM-segphos (5.5 mol%) Mes
Mes
+ (ArBO)3
P
P
(1)
K3PO4 (20 mol%)
toluene/H2O (10/1)
80 °C, 14 h
Ar
Ar
O
O
1a
2a
(R)-3aa
Mes = 2,4,6-Me3C6H2
Ar = 4-MeOC6H4
Mes
P
+
O
4aa
O
O
O
PAr2
PAr2
Ar =
OMe
91% yield
3aa:4aa = 96:4
3aa: 88% ee (R)
(R)-DTBM-segphos
O
<10% D
>90% D
D
H
The same conditions
Me
as in equation 1 except
Mes
(2)
1a + 2a
P
+ 4aa
toluene/D2O (10/1)
Ar
O
[*]
Dr. Z. Wang, Prof. Dr. T. Hayashi
3aa–d1
Division of Chemistry and Biological Chemistry
School of Physical and Mathematical Sciences
Nanyang Technological University
91% yield, 3aa:4aa = 96:4
The reaction in D2O instead of H2O (equation 2) gave the
deuterated product 3aa-d1 where one of the two diastereotopic
hydrogens at the ꢀ-position of ethyl group is selectively
deuterated. The product 3 is proposed to be formed through the
21 Nanyang Link, Singapore 637371 (Singapore)
E-mail: hayashi@ntu.edu.sg
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201712572
Angewandte Chemie International Edition
COMMUNICATION
catalytic cycle shown in Scheme 2, which is based on the
With keeping DTBM-segphos as a ligand on Rh, the effects
of bases and solvents on the chemoselectivity were also studied.
The selectivity in giving 3aa was high with Cs2CO3 as a base
instead of K3PO3, albeit in a slightly lower yield (entry 9). The
reaction was much slower with KOH, leaving most of the starting
1a unreacted (entry 10). The solvent system consisting of
toluene and H2O is very important for the selective formation of
3aa. The selectivity was much lower in dioxane/H2O (10/1),
which is one of the most commonly used solvent systems for the
rhodium-catalyzed asymmetric arylation reactions.[5] In addition
to 3aa and 4aa (38% total yield), other products 6–10 were
formed non-selectively in the dioxane/H2O solvent (entry 11).
The reaction at a lower temperature (60 °C) did not improve the
enantioselectivity (entry 12).
catalytic
cycles
reported
for
the
rhodium-catalyzed
hydroarylation of conjugate enones and related olefinic
substrates.[5,9] Thus, the addition of an Ar–Rh intermediate A to
one of the two enantiotopic vinyl groups on 1 generates alkyl-Rh
species B. Protonolysis of B would give the product 4 which is a
minor product under the present conditions. Instead, β-hydrogen
elimination of B takes place to form H–Rh complex coordinated
with the 2-arylethenyl group C. Intramolecular migration of a H–
Rh species to the neighboring unsubstituted vinyl group giving
another olefin complex D. Hydrorhodation of D followed by
protonolysis of alkyl-rhodium intermediate E produces the main
product 3. The deuterium labeling study (equation 2) shows that
addition of the H–Rh species to the unsubstituted vinyl group in
D takes place selectively from one of the two diastereotopic
olefin faces, indicating that the H–Rh migration is an
intramolecular event.
Table 1. Rhodium-catalyzed hydroarylation of mesityldivinylphosphine oxide
(1a) with 4-methoxyphenylboroxine (2a).[a]
Rh catalyst (5 mol%)
Mes
Mes
Mes
+
+ (ArBO)3
P
P
P
R
P
Ar
Ar
(Ar-BO)3
O
1a
O
3aa
O
4aa
[Rh] Ar
O
1
2a
2
A
arylrhodation
protonolysis
Mes = 2,4,6-Me3C6H2, Ar = 4-MeOC6H4
transmetalation
Ar
Ar
[Rh]
Mes
Mes
Mes
Mes
Mes
Mes
R
P
[Rh] OH
P
P
P
P
P
P
R
P
Ar
Ar
Ar
Ar
O
O
O
O
O
O
Ar
F
O
Ar
R
O
4
5
6
7
8
9
10
P
B
Ar
O
3
O
β-H elimination
protonolysis
[Rh]
H
O
O
PPh2
PPh2
PPh2
PPh2
[Rh]
H
O
R
[Rh]
P
H
R
Ph
P
R
O
Ar
O
Me
P
Ph
Ar
O
O
C
E
Ar
O
(R,R)-Ph-bod
(R)-diene*
(R)-segphos
(R)-binap
hydrorhodation
D
Rh-H migration
Variations from standard
conditions (equation 1)
Conv
Yield
Ratio[b] % ee[d]
Entry
Scheme 2. Catalytic cycle for the reaction of divinylphosphine oxide 1 with
arylboron reagent 2 giving product 3.
(%)[b] (%)[c] of
of
of 3aa
of 1a 3aa+4aa 3aa:4aa
1
2
3
4
5
6
7
None
>99
87
91
78
96:4
93:7
95:5
98:2
93:7
—
88 (R)
87 (R)
89 (R)
43 (R)
63 (R)
—
Table 1 summarizes the results obtained at optimization of
the reaction conditions. The reaction giving 3aa also proceeded
with high chemoselectivity and enantioselectivity with ArB(OH)2
(Ar = 4-MeOC6H4), although the conversion of 1a was lower
(entry 2). With ArBF3K, the reaction was accompanied by
formation of a minor amount (7%) of bishydroarylation product 5
(entry 3). The selectivity producing 3aa is also high with (R)-
segphos[7] and (R)-binap[10] instead of (R)-DTBM-segphos ligand,
but the enantioselectivity was much lower (entries 4 and 5). With
DTBM-binap ligand, the hydroarylation reaction did not take
place (entry 6). Dienes are not the ligands of choice for the
present reaction. The starting divinylphosphine oxide 1a was all
consumed, but the selectivity in giving 3aa or 4aa was very low
with Ph-bod ligand[11] (entry 7). Main products are monoarylated-
diolefin 6 (33%) and reduced product 7 (37%). It is probable that
6 and 7 were formed through dissociation of the H–Rh species
from D (in Scheme 2) followed by its addition to the starting
divinylphosphine oxide 1. In addition, small amounts of
diarylated diolefin 8 and diethylphosphine oxide 9 were also
formed. A similar result giving various products was observed
with (R)-diene* ligand[12] (entry 8). The products 6–9 are all
formed through the intermolecular H–Rh shift, and it may be
concluded that the dissociation of olefin from rhodium is more
facile with diene ligands than with bisphosphine ligands.
4-MeOC6H4B(OH)2
4-MeOC6H4BF3K
(R)-segphos
>99
>99
>99
24
83[e]
92
(R)-binap
86
(R)-DTBM-binap
(R,R)-Ph-bod[f]
<3
>99
15[g]
84:16
3 (S)
8
9
(R)-diene*[h]
>99
94
16[i]
84
81:19
93:7
8 (R)
Cs2CO3 instead of K3PO4
87 (R)
KOH instead of K3PO4
dioxane/H2O (0.50/0.05 mL)
at 60 °C
10
11
12
36
>99
93
28
35[j]
84
94:6
84 (R)
88:12 73 (R)
97:3 88 (R)
[a] Reaction conditions: 1a (0.20 mmol), 2a (0.13 mmol, 0.40 mmol B), K3PO4
(0.040 mmol, 20 mol%), [{RhCl(coe)2}2] (0.005 mmol, 5 mol% of Rh), (R)-
DTBM-segphos (0.011 mmol), toluene (0.50 mL), and H2O (0.05 mL) at 80 °C
for 14 h. [b] The conversion and ratio were determined by 31P and 1H NMR of
the crude reaction mixture. [c] Isolated yield. [d] The % ee was determined by
HPLC on a chiral stationary phase column. [e] 5 (7%) was formed. [f]
[{RhCl((R,R)-Ph-bod)}2]. [g] 6 (33%), 7 (37%), 8 (9%), and 9 (2%) were
formed. [h] [{RhCl(diene*)}2]. [i] 6 (31%), 7 (38%), 8 (10%), and 9 (2%) were
formed. [j] 6 (14%), 7 (27%), 8 (3%), 9 (2%), and 10 (8%) were formed.
This article is protected by copyright. All rights reserved.

10.1002/anie.201712572
Angewandte Chemie International Edition
COMMUNICATION
Table 2. Rhodium-catalyzed asymmetric hydroarylation of divinylphosphine
oxides 1 with arylboroxines 2.[a]
(entries 7–14). The reaction with ortho-substituted phenyboron
reagents 2j, 2k, and 2l, proceeded with higher enantioselectivity
to give the corresponding arylation products 3 with 93–95% ee,
while the selectivity in giving 3 over 4 was lower (entries 15–17).
The ratio of 3:4 was about 1:1 with 1-naphthyl, and it was
reversed with 2-FC6H4 to give 4 as a main product (3:4 = 19:81).
Interestingly, the absolute configuration of the side products
4 is S[13] with very high enantiomeric purity (>99% ee), which
was determined for 4ac and 4ak (entries 8 and 16). The
difference of % ee between 3 and 4 indicates that a kinetic
resolution took place in the catalytic cycle (Scheme 3). Thus, the
[RhCl(coe)2]2 (5 mol% Rh)
(R)-DTBM-segphos (5.5 mol%)
R
R
R
+ (ArBO)3
P
P
P
+
Ar
Ar
O
(R)-3
O
(S)-4
O
1
K3PO4 (20 mol%)
toluene/H2O (10/1)
80 °C, 14 h
2
Yield[b] of 3+4, Ee (%)
Ratio[c] of 3:4 of 3[d]
Entry
1: R
2: Ar
1
2
3
4
5
1a: 2,4,6-Me3C6H2
1b: 2,6-Me2C6H3
1c: 2-methyl-1-naphthyl
1d: 1-naphthyl
2a: 4-MeOC6H4
91%, 96:4
87%, 93:7
86%, 92:8
91%, 96:4
85%, 96:4
88 (R)
88
2a
2a
2a
2a
Ar-Rh intermediate
A coordinated with (R)-DTBM-segphos
88
ligand adds mainly to pro-R vinyl group of divinylphosphine
oxide 1a to generate alkyl-Rh species (Sp)-B as a major
diastereomeric intermediate. The sequence of reactions
involving β-hydrogen elimination followed by Rh-H migration
gives the product 3a with R configuration. The intermediate (Sp)-
B also undergoes protonolysis to give 4a with S configuration,
the selectivity in giving 3a or 4a being dependent on the Ar
group. On the other hand, the other alkyl-Rh intermediate (Rp)-B,
which is generated as a minor diastereoisomer, does not
undergo the protonolysis giving (R)-4a but exclusively
undergoes the reactions starting with β-hydrogen elimination to
give (S)-3a, resulting in a high (>99) % ee of (S)-4a. It follows
that the enantiomeric purity of 3a is lower than the selectivity at
the arylrhodation forming intermediate B and that of 4a is higher.
76
1e: Ph
60
6
7
1f: tBu
2a
81%, >99:1
87%, 92:8
87%, 81:19
86%, 92:8
87%, 88:12
82%, 88:12
71%, 85:15
73%, 91:9
88%, 98:2
74%, 72:28
75%, 54:46
80%, 19:81
83
85
1a: 2,4,6-Me3C6H2
2b: Ph
8
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
2c: 4-FC6H4
2d: 3,5-Me2C6H3
2e: 3-MeOC6H4
2f: 3-FC6H4
88[e]
9
88
10
11
12[f]
13[f]
14
15[f]
16[f]
17
84
86
2g: 3-Me3SiC6H4
88
2h: 3,4-OCH2OC6H3
2i: 2-naphthyl
2j: 2-MeC6H4
87
86
[L*Rh]
93
pro-S
pro-R
Ar
Mes
P
Mes
Rh-H migration
95[e]
94[e]
Mes
P
Mes
+
2k: 1-naphthyl
2l: 2-FC6H4
P
O
P
Ar
1a
O
Ar
O
O
(Sp)-B: major
pro-R
pro-S
(R)-3a (88–95% ee)
(S)-3a
[Rh*L] Ar
A
[L*Rh]
Ar
[a] Reaction conditions: 1 (0.20 mmol), arylboroxine 2 (0.13 mmol, 0.40 mmol
of B), K3PO4 (0.04 mmol), [{RhCl(coe)2}2] (0.005 mmol, 5 mol% of Rh), (R)-
DTBM-segphos (0.011 mmol), toluene (0.50 mL), and H2O (0.05 mL) at
80 °C for 14 h. [b] Isolated yield. [c] The ratio was determined by 31P NMR of
the crude reaction mixture. [d] The % ee was determined by HPLC on chiral
stationary phase columns. [e] The ee of 4ac, 4ak, and 4al are 99.9%, 99.9%,
and 99.8%, respectively. [f] K3PO4 (0.10 mmol).
Mes
P
4-FC H
Mes
Ar =
6
4
P
1-naphthyl
Ar
O
O
(S)-4a (>99% ee)
(Rp)-B: minor
Scheme 3. Kinetic resolution of the aryl-rhodium intermediates B to give the
product (S)-4a of very high % ee.
Et
Mes
Et
Mes
Et
Mes
The condition optimized for the reaction shown in equation 1
was applied to several other divinylphosphine oxides 1 and
arylboroxines 2. The results are summarized in Table 2. High
enantioselectivity was observed in the reactions of arylboroxine
Ar
Ar
Ar
Ph2P(O)H, K3PO4
THF
P
P
P
+
O
O
P(O)Ph2
O
P(O)Ph2
(R)-3aa
88% ee
(Rp,Rc)-11a
(Rp,Sc)-11b
45% yield, 88% ee
(36% yield, 99% ee
by recrystallization)
45% yield, 88% ee
(36% yield, >99% ee
by recrystallization)
Ar = 4-MeOC6H4
2a with divinylphosphine oxides
demanding substituent. Those
1
bearing
a
sterically
HSiCl3/NEt3
MeCN
1) HSiCl3/NEt3, MeCN
2) [PdCl2(MeCN)2], CH2Cl2
substituted
with 2,6-
Mes
Et
Ar
PPh2
Mes
Et
[PdCl2(MeCN)2]
CH2Cl2
Ar
dimethylphenyl (1b) and 2-methyl-1-naphthyl (1c) gave the
corresponding hydroarylation products with 88% ee in high
yields (entries 2 and 3). The enantioselectivity was lower with
less bulky aromatic groups, 1-naphthyl (76% ee) and
unsubstituted phenyl (60% ee) (entries 4 and 5). Tert-butyl
group can be also used as the substituent on divinylphosphine
oxide. The chemoselectivity giving product 3 is very high,
although the enantioselectivity is somewhat lower (83% ee)
(entry 6). The reaction of divinylphosphine oxide 1a with
arylboroxines where the aryl groups are para- or meta-
substituted phenyls all gave the corresponding arylation
products 3 in high yields with the 3:4 selectivity higher than 8:2
irrespective of the electronic characters of the substituents. The
para- and meta-substituents did not have a significant effect on
the enantioselectivity, the % ee of 3 being kept as 84–88%
P
Mes
Ar
P
Et
P
Pd
Cl
PPh2
(Sp,Sc)-12b
Cl
Pd
Cl
Cl
PPh2
(Sp,Rc)-12a
Scheme 4. Conversion of the hydroarylation product (R)-3aa into chiral
bisphosphines with both P and C stereogenic centers.
(Sp,Rc)-12a (5 mol%)
AgSbF6 (25 mol%)
K3PO4 (50 mol%)
O
O
Ar
(3)
+ (ArBO)3
Ph
Ph
Ar = 4-MeOC6H4
Ph
Ph
CH2Cl2/H2O (10/1)
25 °C, 24 h
91% yield, 92% ee (R)
Taking advantage of the structural features of the arylation
product 3, that is, the double bond in 3 is activated by phosphine
oxide for Michael addition, (R)-3aa (88% ee) was subjected to
the conjugate addition of diphenylphosphine oxide[14] (Scheme
This article is protected by copyright. All rights reserved.

10.1002/anie.201712572
Angewandte Chemie International Edition
COMMUNICATION
Johnson, T. Rovis, Angew. Chem. Int. Ed. 2008, 47, 840; Angew.
Chem. 2008, 120, 852; f) S. Darses, J.-P. Genet, Eur. J. Org. Chem.
2003, 4313; g) T. Hayashi, K. Yamasaki, Chem. Rev. 2003, 103, 2829;
h) K. Fagnou, M. Lautens, Chem. Rev. 2003, 103, 169; i) C. Bolm, J. P.
Hildebrand, K. Muñiz, N. Hermanns, Angew. Chem. Int. Ed. 2001, 40,
3284; Angew. Chem. 2001, 113, 1536.
4). The addition proceeded smoothly without racemization to
give a mixture (1/1) of two diastereoisomers 11a and 11b in high
yields. Separation of the isomers followed by enhancement of
the enantiomeric purity by recrystallization led to (Rp,Rc)-11a[15]
(99% ee) and (Rp,Sc)-11b (>99% ee). Chiral bisphosphines
[16]
obtained by reduction of the phosphine oxides with HSiCl3
[6]
To the best of our knowledge, there have been only a few reports on
the asymmetric arylation of alkenylphosphine oxides a) K. M.-H. Lim, T.
Hayashi, J. Am. Chem. Soc. 2017, 139, 8122; b) N. Lefevre, J.-L.
Brayer, B. Folléas, S. Darses, Org. Lett. 2013, 15, 4274; c) T. Hayashi,
T. Senda, Y. Takaya, M. Ogasawara, M. J. Am. Chem. Soc. 1999, 121,
11591.
were isolated as their palladium complexes 12. The
bisphosphines are unique in that they have both P- and C-
stereogenic centers.[17] The palladium complex (Sp,Rc)-12a[15]
demonstrated its high catalytic activity and enantioselectivity in
the asymmetric conjugate addition of arylboroxin[18] (eq 3).
[7]
[8]
[9]
T. Saito, T. Yokozawa, T. Ishizaki, T. Moroi, N. Sayo, T. Miura, H.
Kumobayashi, Adv. Synth. Catal. 2001, 343, 264.
The absolute configuration R of 3aa was determined by X-ray analysis
of (Rp,Rc)-11a (Scheme 4).
Acknowledgements
T. Hayashi, M. Takahashi, Y. Takaya, M. Ogasawara, J. Am. Chem.
Soc. 2002, 124, 5052.
We thank Nanyang Technological University and the Singapore
Ministry of Education for supporting this research.
[10] H. Takaya, K. Mashima, K. Koyano, M. Yagi, H. Kumobayashi, T.
Taketomi, S. Akutagawa, R. Noyori, J. Org. Chem. 1986, 51, 629.
[11] N. Tokunaga, Y. Otomaru, K. Okamoto, K. Ueyama, R. Shintani, T.
Hayashi, J. Am. Chem. Soc. 2004, 126, 13584.
Keywords: desymmetrization • P-stereogenic center •
asymmetric hydroarylation • chiral phosphine • rhodium catalyst
[12] K. Okamoto, T. Hayashi, V. H. Rawal, Chem. Commun. 2009, 4815.
[13] For the determination of configuration S, see Supporting Information.
[14] For examples, see: a) L. Liu, Y. Wang, Z. Zeng, P. Xu, Y. Gao, Y. Yin,
Y. Zhao, Adv. Synth. Catal. 2013, 355, 659; b) T. Bunlaksananusorn, P.
Knochel, Tetrahedron Lett. 2002, 43, 5817; c) K. M. Pietrusiewicz, M.
Zablocka, Tetrahedron Lett. 1988, 29, 1987.
[1]
[2]
For reviews on catalytic asymmetric synthesis of P-stereogenic
compounds: a) Y.-M. Cui, Y. Lin, L.-W. Xu, Coord. Chem. Rev. 2017,
330, 37; b) M. Dutartre, J. Bayardon, S. Jugé, Chem. Soc. Rev. 2016,
45, 5771; c) J. S. Harvey, V. Gouverneur, Chem. Commun. 2010, 46,
7477; d) D. S. Glueck, Chem. Eur. J. 2008, 14, 7108; e) D. S. Glueck,
Synlett 2007, 2627.
[15] The relative and absolute configurations were determined by X-ray
analysis: (Rp,Rc)-11a (CCDC 1586454), (Sp,Rc)-12a (CCDC 1586455).
[16] The reduction with HSiCl3/NR3 has been reported to proceed with
inversion of configuration at phosphorus: D. Hérault, D. H. Nguyen, D.
Nuel, G. Buono, Chem. Soc. Rev. 2015, 44, 2508.
Selected recent examples of catalytic asymmetric synthesis of P-chiral
phosphorus compounds, see: a) Y. Huang, Y. Li, P.-H. Leung, T.
Hayashi, J. Am. Chem. Soc. 2014, 136, 4865; b) T. W. Chapp, D. S.
Glueck, J. A. Golen, C. E. Moore, A. L. Rheingold, Organometallics
2010, 29, 378; c) V. S. Chan, M. Chiu, R. G. Bergman, F. D. Toste, J.
Am. Chem. Soc. 2009, 131, 6021; d) J. S. Harvey, S. J. Malcolmson, K.
S. Dunne, S. J. Meek, A. L. Thompson, R. R. Schrock, A. H. Hoveyda,
V. Gouverneur, Angew. Chem. Int. Ed. 2009, 48, 762; Angew. Chem.
2009, 121, 776. e) N. F. Blank, J. R. Moncarz, T. J. Brunker, C. Scriban,
B. J. Anderson, O. Amir, D. S. Glueck, L. N. Zakharov, J. A. Golen, C.
D. Incarvito, A. L. Rheingold, J. Am. Chem. Soc. 2007, 129, 6847; f) A.
D. Sadow, A. Togni, J. Am. Chem. Soc. 2005, 127, 17012.
[17] Examples of chiral bisphosphine ligands with both P- and C-
stereogenic centers: a) C. Chen, H. Wang, Z. Zhang, S. Jin, S. Wen, J.
Ji, L. W. Chung, X.-Q. Dong, X. Zhang, Chem. Sci. 2016, 7, 6669; b) W.
Chen, F. Spindler, B. Pugin, U. Nettekoven, Angew. Chem. Int. Ed.
2013, 52, 8652; Angew. Chem. 2013, 125, 8814; c) W. Tang, B. Qu, A.
G. Capacci, S. Rodriguez, X. Wei, N. Haddad, B. Narayanan, S. Ma, N.
Grinberg, N. K. Yee, D. Krishnamurthy, C. H. Senanayake, Org. Lett.
2010, 12, 176; d) Y. Zhang, S. A. Pullarkat, Y. Li, P.-H. Leung, Inorg.
Chem. 2009, 48, 5535; e) H. Shimizu, T. Saito, H. Kumobayashi, Adv.
Synth. Catal. 2003, 345, 185; f) P. Barbaro, C. Bianchini, G.
Giambastiani, A. Togni, Eur. J. Inorg. Chem. 2003, 4166; g) W. Tang, X.
Zhang, Angew. Chem. Int. Ed. 2002, 41, 1612; Angew. Chem. 2002,
114, 1682; h) D. Carmichael, H. Doucet, J. M. Brown, Chem. Commun.
1999, 261; i) F. Robin, F. Mercier, L. Ricard, F. Mathey, M. Spagnol,
Chem. Eur. J. 1997, 3, 1365.
[3]
[4]
G. Nishida, K. Noguchi, M. Hirano, K. Tanaka, Angew. Chem. Int. Ed.
2008, 47, 3410; Angew. Chem. 2008, 120, 3458.
a) Y.-S. Jang, M. Dieckmann, N. Cramer, Angew. Chem. Int. Ed. 2017,
56, 15088; Angew. Chem. 2017, 129, 15284; b) Z.-J. Du, J. Guan, G.-J.
Wu, P. Xu, L.-X. Gao, F.-S. Han, J. Am. Chem. Soc. 2015, 137, 632;
see also c) Y. Sun, N. Cramer, Angew. Chem. Int. Ed. 2017, 56, 364;
Angew. Chem. 2017, 129, 370; d) Z.-Q. Lin, W.-Z. Wang, S.-B. Yan,
W.-L. Duan, Angew. Chem. Int. Ed. 2015, 54, 6265; Angew. Chem.
2015, 127, 6363; e) L. Liu, A.-A. Zhang, Y. Wang, F. Zhang, Z. Zuo,
W.-X. Zhao, C.-L. Feng, W. Ma, Org. Lett. 2015, 17, 2046.
[18] Reviews on Pd-catalyzed asymmetric conjugate addition, see: a) S. E.
Shockley, J. C. Holder, B. M. Stoltz, Org. Process Res. Dev. 2015, 19,
974; b) Y.-W. Sun, P.-L. Zhu, Q. Xu, M. Shi, RSC Adv. 2013, 3, 3153;
c) G. Berthon-Gelloz, T. Hayashi, Rhodium- and Palladium-Catalyzed
Asymmetric Conjugate Addition of Organoboronic Acid, in: Boronic
Acids (Ed.: D. G. Hall), Wiley-VCH, Weinheim, Germany, 2011, pp.
263-313; d) N. Miyaura, Synlett. 2009, 2039; e) A. Gutnov, Eur. J. Org.
Chem. 2008, 4547.
[5]
For pertinent reviews, see: a) M. M. Heravi, M. Dehghani, V. Zadsirjan,
Tetrahedron: Asymmetry 2016, 27, 513; b) P. Tian, H.-Q. Dong, G.-Q.
Lin, ACS Catal. 2012, 2, 95; c) G. Berthon, T. Hayashi in Catalytic
Asymmetric Conjugate Reactions, Vol. 1 (Ed.: A. Córdova), Wiley-VCH,
Weinheim, 2010, pp. 1-70; d) H. J. Edwards, J. D. Hargrave, S. D.
Penrose, C. G. Frost, Chem. Soc. Rev. 2010, 39, 2093; e) J. B.
This article is protected by copyright. All rights reserved.

10.1002/anie.201712572
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Text for Table of Contents
Zhe Wang and Tamio Hayashi*
Page No. – Page No.
Rhodium-Catalyzed Enantioposition
Selective Hydroarylation of
Divinylphosphine Oxides with
Arylboroxines
((Insert TOC Graphic here))
Layout 2:
COMMUNICATION
Zhe Wang and Tamio Hayashi*
Page No. – Page No.
Rhodium-Catalyzed Enantioposition
Selective Hydroarylation of
Divinylphosphine Oxides with
Arylboroxines
Rhodium-catalyzed hydroarylation of divinylphosphine oxides (RP(O)(CH=CH2)2, 1)
with arylboroxines ((ArBO)3, 2) gave high yields of monoarylation products
(RP(O)(CH=CHAr)CH2CH3, 3), where one of the two vinyl groups in 1 underwent
oxidative arylation and the other was reduced to ethyl. The reaction in the presence
of (R)-DTBM-segphos/Rh proceeded with high enantioposition-selectivity to give P-
stereogenic monoarylation products 3 with high enantioselectivity.
This article is protected by copyright. All rights reserved.