Stereoselective synthesis of o-bromo (or iodo)aryl P-chirogenic phosphines based on aryne chemistry

Article abstract of DOI:10.1021/jo300910w

The efficient synthesis of chiral or achiral tertiary phosphines bearing an o-bromo (or iodo)aryl substituent is described. The key step of this synthesis is based on the reaction of a secondary phosphine borane with the 1,2-dibromo (or diiodo)arene, owing to the formation in situ of an aryne species in the presence of n-butyllithium. When P-chirogenic secondary phosphine boranes were used, the corresponding o-halogeno-arylphosphine boranes were obtained without racemization in moderate to good yields and with ee up to 99%. The stereochemistry of the reaction, with complete retention of the configuration at the P atom, has been established by X-ray structures of P-chirogenic o-halogenophenyl phosphine borane complexes. The decomplexation of the borane was easily achieved without racemization using DABCO to obtain the free o-halogeno-arylphosphines in high yields.

Full text of DOI:10.1021/jo300910w

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Article
Stereoselective Synthesis of o-Bromo (or Iodo)aryl P-
Chirogenic Phosphines Based on Aryne Chemistry
Jérôme Bayardon, Hugo Laureano, Vincent Diemer, Mathieu Dutartre, Utpal Das, Yoann
Rousselin, Jean-Christophe Henry, Françoise Colobert, Frederic R. Leroux, and Sylvain Jugé
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo300910w • Publication Date (Web): 18 Jun 2012
Downloaded from http://pubs.acs.org on June 19, 2012
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The Journal of Organic Chemistry
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Stereoselective Synthesis of oꢀBromo (or Iodo)aryl Pꢀ
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Chirogenic Phosphines Based on Aryne Chemistry
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†
†
‡
†
†
Jérôme Bayardon, Hugo Laureano, Vincent Diemer, Mathieu Dutartre, Utpal Das, Yoann
†
§
‡
‡* †*
Rousselin, Jean-Christophe Henry, Françoise Colobert, Frédéric R. Leroux and Sylvain Jugé
†
Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUBꢀ StereochIMꢀ
UMR CNRS 6302), 9 avenue A. Savary BP47870, 21078 Dijon Cedex, France
‡
Laboratoire de Chimie Moléculaire (UMR CNRS 7509), Université de Strasbourg, ECPM, 25 rue
Becquerel, 67087 Strasbourg, France
§
Synthelor SAS, 13 rue du bois de la champelle, 54500, Vandoeuvre les Nancy, France
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
CORRESPONDING AUTHOR FOOTNOTE
[*] To whom correspondence should be addressed. Eꢀmail: sylvain.juge@uꢀbourgogne.fr, Tel: +33
(0)3 80 39 61 13. Eꢀmail: frederic.leroux@unistra.fr, Tel: 33 (0)3 68 85 26 40
ABSTRACT
The efficient synthesis of chiral or achiral tertiary phosphines bearing an oꢀbromo (or iodo)aryl
substituent, is described. The key step of this synthesis is based on the reaction of a secondary
phosphine borane with the 1,2ꢀdibromoꢀ (or diiodo)arene, owing to the formation in situ of an aryne
species in presence of nꢀbutyllithium. When Pꢀchirogenic secondary phosphine boranes were used, the
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corresponding oꢀhalogenoꢀarylphosphine boranes were obtained without racemization, in moderate to
good yields and with e.e. up to 99%. The stereochemistry of the reaction with complete retention of the
configuration at the Pꢀatom, has been established by Xꢀray structures of Pꢀchirogenic oꢀhalogenophenyl
phosphine borane complexes. The decomplexation of the borane was easily achieved without
racemization using DABCO®, to afford in high yields the free oꢀhalogenoꢀarylphosphines.
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KEYWORDS
Pꢀchirogenic phosphines; secondary phosphine boranes: oꢀhalogeno arylphosphines; aryne chemistry;
stereoselective synthesis.
Introduction
Chiral tertiary phosphines are the most popular organophosphorus compounds finding numerous
applications as ligands in asymmetric catalyzed reactions by transition metal complexes,1,2 or for
coordinating polymers,3 as precursors of quaternary phosphonium salts4 or Wittig reagents,5 and also as
organocatalysts.6 The interest for the phosphines comes from their easy structural designing by
electrophilic or nucleophilic reactions on the phosphorus atom, or in α or β position of an aliphatic
substituent.2,7,8 Despite of this abundant chemistry, the synthesis of Pꢀchirogenic phosphines such as 1,
bearing a heteroatom or a functional group in ortho position, remains a challenge and very few
stereoselective methods lead to these compounds.
a
b
c
d
e
f
g
h
i
j
k
Y
1
R
P
R2
R1
R*
N
R
*
Y
CO2H CHO OH Br I
O
NHR*
R
O
*
*
*
*
P
R
R
N
O
P
O
O
N
Figure 1. Different types of oꢀsubstituted or oꢀfunctionalized chiral phosphines
Mostly, the chiral oꢀfunctionalized phosphines derive from the diphenylphosphinoaryl precursor 1a-d
with R1= R2= Ph, and bear the chirality on the carbon backbone. Such phosphines have hybrid structures
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with chelating arms such as 1fꢀk: amide,9 imine,10 oxazoline11 or heterocycle,12 phosphinite,13 amino14
or phospholano15 group (Figure 1). The hybrid chiral ligands 1fꢀk have widely demonstrated their
efficiency in numerous asymmetric reactions catalyzed by transitionꢀmetal complexes.1,2,9ꢀ15 In addition,
oꢀfunctionalized phosphines 1 can be used as reagent for chemoselective coupling of biomolecular
fragments by Staudinger ligation,16 and as directing group in stereoselective hydroformylation of acyclic
substrates.17 Moreover, the oꢀhalogeno phosphines 1d,e, or their oxide derivatives, can also be used for
the preparation of challenging ligands such as ambiphilic phosphineꢀboranes,18 or bearing a bisaryl as
substituent or bridge.19,20
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Usually, the oꢀfunctionalized phosphines 1 are obtained using two strategies involving PꢀC or CꢀY
bond formation (Scheme 1). In the first case, the synthesis is based either on the coupling reaction of
secondary phosphine derivatives 2 with an activated aromatic precursor 3, by direct substitution,11a,h,14bꢀ
e,20
or catalysis with a transition metal complex11h,12b,15f,19b,21 (Scheme 1a), or the reaction of a
chlorophosphine 4 with an organometallic aryl reagent 511a,d,12a,14a (Scheme 1b). In the second case, the
oꢀfunctionalization of a phosphine can also be achieved from the corresponding oxide precursor, either
by direct substitution of 6 bearing a leaving group X in ortho position14b,c (Scheme 1c), or by oꢀlithiation
and then trapping of 7 by electrophilic reagent (Scheme 1d).22
Scheme 1. Methods for the synthesis of oꢀfunctionalized phosphines
Y
O
X
(Z)
R2P
R2P
X
+
Y
(a)
(b)
(c)
+
+
Y
L
R2P
2
3
6
Y
O
(d)
Ph2P
1
Y
R2PCl
+
4
5
7
X = F, Br, OTf, OMe ; Z = lone pair, O; L = H, TMS, (n-Bu)3Sn
Y = Br, I, CHO, oxazoline, imino, heterocyclic, amino, phosphino...
In the last decades, the interest of phosphines bearing chirality on the phosphorus atom (Pꢀ
chirogenic), greatly expanded thanks to the development of new stereoselective synthetic methods,
using the chemistry of their borane complexes.2,8,23,24 However, the stereoselective synthesis of oꢀ
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functionalized Pꢀchirogenic phosphines is scarcely reported,25 because the methods (a) and (b) reported
on Scheme 1, involve either a racemization of the Pꢀcenter or a lack of reactivity of the electrophilic Pꢀ
building blocks.26 To date, only the enantioselective oꢀlithiation/ functionalization of prochiral
organophosphorus compounds in presence of sparteine has been described, but in the phosphinamide
series.27 On another hand, the Pꢀchirogenic oꢀhydroxy derivatives 1c (Y= OH) can be stereoselectively
prepared by the ephedrineꢀborane complex methodology, either via a Fries rearrangement28 of an aryl
phosphinite, or using an oꢀlithiated phenate reagent.29
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Consequently, the development of stereoselective synthesis of oꢀfunctionalized Pꢀchirogenic
phosphines 1 must be mainly based on the strategies (b) and (c) (Scheme 1), and consequently the
access to the oꢀhalogenophenyl phosphines 1d,e, as chiral synthons (Figure 1).
We recently described an efficient stereoselective synthesis of Pꢀchirogenic quaternary phosphonium
triflates, by quaternization of phosphines using aryne chemistry.4d Arynes (1,2ꢀdehydrobenzenes) are
highly reactive intermediates which have attracted increasing interest in recent past, due to their wide
synthetic applications.30 They undergo numerous reactions such as aryl coupling, DielsꢀAlder, 1,3ꢀ
dipolar cycloaddition, transition metal catalyzed reactions,30,31 and addition with a variety of Sꢀ, Nꢀ, Oꢀ,
Sꢀ, Seꢀ and Pꢀnucleophiles.4d,32,33
As the reaction of secondary phosphines with an aryne led easily to the quaternary phosphonium
salt,4d we report herein the use of their borane complexes for the efficient synthesis of oꢀbromoꢀ or oꢀ
iodoarylphosphines, using the aryne chemistry.34 In addition, the stereoselective synthesis of Pꢀ
chirogenic oꢀbromoꢀ or oꢀiodoarylphosphines is described without racemization, using chiral secondary
phosphine borane.
Results and discussion
In our laboratory, we have recently developed the stereoselective synthesis of Pꢀchirogenic secondary
phosphine boranes 8, using the ephedrine methodology.24b After deprotonation with nꢀbutyllithium,
resulting phosphides react with different primary alkylhalides at ꢀ78°C, to afford stereoselectively the
corresponding tertiary Pꢀchirogenic phosphine boranes, with e.e. up to 99%.24b In continuation of this
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work, we have extended this reaction to the preparation of Pꢀchirogenic arylphosphines bearing
functional groups in ortho position, using the arynes as electrophilic reagents. Firstly, we investigated
the reaction of secondary chiral and achiral phosphine boranes 8 with 1,2ꢀdihalogenoarene 9, as aryne
precursor.35 The results are summarized in Table 1.
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Table 1. Synthesis of oꢀhalogenophenylphosphine boranes 10 from secondary phosphine boranes 8
entry
R1R2P(BH3)H
ArXX'
X,X' R3
R1R2P(BH3)oꢀXAr
R1
R2
Ph
Yields (%) a ee (%)b
1
2
Ph
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
I
H
H
H
H
H
H
H
H
Me
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
75
63
42
55
60
34
40c
0
ꢀ
ꢀ
8a
8b
9a
9a
9a
9a
9a
9a
9a
9a
9b
9b
9c
9c
9d
9e
9a
9a
9c
9a
9a
9c
9a
9a
9a
10a
10b
cꢀHex
Me
cꢀHex
Me
3
ꢀ
8c
10c
4
iꢀPr
Ph
iꢀPr
pꢀAn
tꢀBu
oꢀTol
tꢀBu
Ph
ꢀ
8d
10d
5
(±)ꢀ8e
(±)ꢀ8f
8g
(±)ꢀ10e
(±)ꢀ10f
10g
ꢀ
6
Ph
ꢀ
7
oꢀTol
tꢀBu
Ph
ꢀ
8
ꢀ
8h
10h
9
56
53
50
56
0
ꢀ
8a
10i
10
11
12
13
14
15
16
17
18
19
20
21
22
23
cꢀHex
Ph
cꢀHex
Ph
ꢀ
8b
10j
ꢀ
8a
10k
cꢀHex
Ph
cꢀHex
Ph
I
ꢀ
8b
10l
Cl
I,Br
Br
Br
I
ꢀ
8a
10m
Ph
Ph
10a,10kh
(R)ꢀ10n
(S)ꢀ10n
(R)ꢀ10o
(S)ꢀ10p
(R)ꢀ10p
(S)ꢀ10q
(S)ꢀ10r
(R)ꢀ10r
(S)ꢀ10s
72
53
53
42c
47
50
55
48
48
47
ꢀ
8a
(S)ꢀ8id
(R)ꢀ8ie
(S)ꢀ8id
(S)ꢀ8jd
(R)ꢀ8je
(S)ꢀ8jd
(R)ꢀ8kd
(S)ꢀ8ke
oꢀAn
Ph
Ph
95
95
95f
99g
99g
99g
95
95
95
oꢀAn
Ph
oꢀAn
Fc
Ph
Br
Br
I
Ph
Fc
Fc
Ph
iꢀPr
Ph
Br
Br
Br
Ph
iꢀPr
Ph
(R)ꢀ8ld cꢀHex
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24
25
(S)ꢀ8le
Ph
Ph
cꢀHex
oꢀTol
Br
Br
H
(R)ꢀ10s
(S)ꢀ10t
63
66c
95
73
9a
9a
1
2
3
4
5
6
7
(R)ꢀ8me
H
c
a
b
Isolated yields. Determined by HPLC on chiral column. Isolated after decomplexation. d Prepared
from (ꢀ)ꢀephedrine. e prepared from (+)ꢀephedrine. f ee values determined by 1H and/or 31P NMR of the
g
corresponding phosphine oxide with (R)ꢀ3,5ꢀdinitroꢀNꢀ(1ꢀphenylꢀethyl)ꢀbenzamide as chiral reagent.
After recrystallization. h 10a, 10k ratio 1 : 9 determined by 31P NMR.
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The reaction of the secondary alkylꢀ or arylphosphine boranes 8a-f with nꢀBuLi (1.2 equiv.) and
dibromobenzene 9a (1.4 equiv.), affords the corresponding oꢀbromophenylphosphine boranes 10a-f in
satisfying to good yield, ranging from 34 to 75% (entries 1ꢀ6).35 When the di(oꢀtolyl)phosphine borane
8g reacts with 9a, a mixture of oꢀbromophenylphosphine borane 10g and the corresponding free
phosphine is obtained (entry 7). The steric hindrance of the phosphine boranes 8g and 10g, due to the
tolyl and bromophenyl substituents, explains the moderate yield and the partial decomplexation of the
borane, as already observed with a tolylphosphine borane.36 This is again demonstrated by the use of the
di(tertꢀbutyl)phosphine borane 8h, which does not afford the product 10h, in these conditions (entry 8).
On the other hand, in these conditions the reaction of the diphenylphosphine borane 8a (or
dicyclohexylphosphine borane 8b) with the 4,5ꢀdibromoꢀoꢀxylene 9b, leads under these conditions to
the phosphine boranes 10i (or 10j) in 56% and 53% yield, respectively (entries 9,10). In addition, the
secondary phosphine boranes 8a (or 8b) react with 1,2 diiodobenzene 9c, to afford the corresponding oꢀ
iodophenylphosphine boranes 10k (or 10l), in 50 and 56% yield, respectively (entries 11,12).
The synthesis of the oꢀhalogenophenylphosphine boranes 10 was explained by a mechanism
involving an aryne intermediate (Scheme 2). Thus, the reaction begins by the deprotonation of the
secondary phosphine borane 8 giving the corresponding phosphide 11, while the excess of nꢀBuLi (0.2
equiv.) promotes the halogenꢀmetal exchange with the 1,2ꢀdihalogenoarene 9, generating the anion 12
and then the aryne 13 by LiX elimination (Scheme 2). The reaction of the phosphide borane 11 with the
aryne 13 leads then to the oꢀlithiated phosphine borane 14, which gives a new halogenꢀmetal exchange
with the 1,2ꢀdihalogenobenzene 9 to afford on one hand, the corresponding oꢀhalophenylphosphine
borane 10, and on the other hand the aryne 13 from the anion 12, continuing thus the reaction. This
mechanism was supported by the absence of reaction without an excess of base, or by using the 1,2ꢀ
dichlorobenzene 9d, because no halogenꢀmetal exchange occurs under these conditions (entry 13). A
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further evidence of the aryne mechanism is given by the use of 1ꢀbromoꢀ2ꢀiodobenzene 9e, which leads
to a mixture of oꢀbromo and oꢀiodophenylphosphine borane 10a and 10k in 1 : 9 ratio, proving thus a
better halogenꢀmetal exchange of the anion 14 with the iodo than with the bromo substituent of the
reagent 9e (entry 14).
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Scheme 2. Proposed mechanism for the formation of oꢀbromophosphine boranes 10
Interestingly under these conditions, the Pꢀchirogenic phosphine boranes 8i-m reacted with the 1,2ꢀ
dihalogenobenzene 9a (or 9c) to afford the corresponding oꢀhalogenophenyl phosphine boranes 10n-t in
42ꢀ66% yields, and with enantiomeric excesses up to 99 % (entries 15ꢀ25). The analysis by HPLC on
chiral column of the starting secondary phosphine boranes 8 and their oꢀhalogenophenyl derivatives 10,
proves that the reaction proceeds without racemisation. As typical example, the (S)ꢀ
ferrocenylphenylphosphine borane 8j (94% e.e.) reacts with the 1,2ꢀdibromobenzene 9a to afford the
(S)ꢀoꢀbromophenylferrocenylphosphine borane 10p in 47% yield and an enantiomeric purity superior to
99% after recrystallization (entry 18). Crystals of 10p were grown from methylene chloride/hexane as
solvent and its ORTEP drawing is shown in Figure 2. The crystal contains discrete molecules of 10p
with normal nonꢀbonded interactions. The distorted tetrahedral geometry of the P atom is typical of
phosphine borane adducts. The Cp rings are parallel within 0.93(22)° and the (S)ꢀconfiguration of the P
atoms is supported by refinement of the Flack x parameter. Consequently, the (S)ꢀabsolute
configurations of the starting secondary phosphine borane 8j and the product 10p, proves a reaction
mechanism with retention of configuration at the Pꢀcenter.
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Figure 2. ORTEP37 view of (S)ꢀ10p showing thermal ellipsoids at the 50 % probability level.
Selected bond lengths [Å], angles [°] and dihedral angles [°]: P–B 1.930(3), C1–P 1.784(3), C11–P
1.811 (3), C17–P 1.831(3); C1–P–C11 104.44(13), C1–P–C17 103.29(13), C11–P–C17 107.12(13),
C1–P–B 112.53(15); C2–C1–P–B ꢀ161.56(25), C12–C11–P–B (19.58(30), C22–C17–P–B 70.80(28).
As well, in the case of the reaction of the ferrocenylphenylphosphine borane (S)ꢀ8j having 94% e.e.
with the 1,2ꢀdiodobenzene 9c, the oꢀiodophenylphosphine borane 10q is obtained in 55% yield and with
an enantiomeric excess of 99%, after recrystallization (entry 20). The structure of 10q has also been
determined by single crystal Xꢀray diffraction, and is similar to the bromo derivatives 10p (Figure 3).
The crystal contains discrete molecules of compound 10q with normal nonꢀbonded interactions. The
distorted tetrahedral geometry of the Pꢀatom is typical of phosphine borane adducts. The Cp rings are
parallel within 0.76(31)° and the (S)ꢀconfiguration of the Pꢀatom is supported by refinement of the
Flack x parameter.
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Figure 3. ORTEP37 view of compound (S)ꢀ10q showing thermal ellipsoids at the 50 % probability
level. Selected bond lengths [Å], angles [°] and dihedral angles [°]: P–B 1.931(5), C1–P 1.828(4), C13–
P 1.791 (4), C7–P 1.814 (4); C13–P–C1 104.11(18), C7–P–C1 106.89(18), C13–P–C7 105.03(18), C1–
P–B 110.9(2); C2–C1–P–B ꢀ103.95(35), C8–C7–P–B 14.26(41), C17–C13–P–B 16.76(40).
The decomplexation of the oꢀhalogenophenylphosphine borane 10 was achieved using DABCO®,
and affords the corresponding free phosphines 11 in good to excellent yields and with enantiomeric
excess up to 99%, after recrystallization. The results are reported in the Table 2.
Table 2. Decomplexation in free oꢀhalogenoaryl phosphines 11
Phosphine boranes 10
Phosphines 11
entry
R1
Ph
R2
R3
X
Br
Br
Br
I
Rdt (%) ee (%)
1
2
3
4
5
6
7
Ph
H
79
40a
84
ꢀ
ꢀ
10a
10g
11a
11b
oꢀTol
Ph
oꢀTol
Ph
H
Me
H
ꢀ
10i
11c
Ph
Ph
83
ꢀ
10k
11d
(R)ꢀ10n
(R)ꢀ10o
(S)ꢀ10p
oꢀAn
oꢀAn
Fc
Ph
H
Br
I
(R)ꢀ11e
(R)ꢀ11f
(S)ꢀ11g
90
42b
99
95
99
Ph
H
Ph
H
Br
75
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8
9
(S)ꢀ10r
(S)ꢀ10t
iꢀPr
Ph
H
H
Br
Br
(S)ꢀ11h
82
66c
95
73
1
2
3
4
Ph
oꢀTol
(S)ꢀ11i
b
a
Overall yield starting from secondary phosphine borane 8g. Overall yield starting from
secondary phosphine borane 8i. c Overall yield starting from secondary phosphine borane 8m.
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8
9
Interestingly, the free phosphine (R)ꢀ11e has been obtained in 45 % yield and with 99% e.e., by a two
steps reaction sequence starting from the secondary phosphine borane (S)ꢀ8i, i.e. reaction with the 1,2ꢀ
bromobenzene 9a and then decomplexation. The structure of the (R)ꢀ(2ꢀbromophenyl)ꢀ(2ꢀ
methoxyphenyl)ꢀphenylphosphine 11e has been determined by single crystal Xꢀray diffraction (Figure
4). The compound crystallizes in a nonꢀcentrosymmetric space group P21 with an absolute (R)ꢀ
configuration on the phosphorus atom. The structure adopts a propellerꢀshaped conformation with the
phenyl rings twisted away to the base of the PC3 pyramid by 59.49(10), 44.44(11) and 43.56(11)°. The
bromide is located cis to the phosphorus lone pair. The PꢀC bond lengths and the CꢀPꢀC bond angles,
mean value 1.841(3) Å and 101.4(6)°, are similar to those recorded for triphenylphosphine, mean value
1.831(2) Å and 102.8(5)°.38 The molecules are linked in the crystal lattice through edgeꢀtoꢀface Cꢀ
H…π interactions between the phenyl groups.39
10
11
12
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Figure 4. ORTEP37 view of (R)ꢀ(2ꢀbromophenyl)ꢀ(2ꢀmethoxyphenyl)ꢀphenylphosphine 11e showing
thermal ellipsoids at the 50 % probability level. Selected bond lengths [Å], angles [°] and dihedral
angles [°]: C1–P 1.838(3); C7–P 1.844(3), C13–P 1.841(3); C1–P–C7 100.78(12), C1–P–C13
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102.08(12), C13–P–C7 101.47(12); O–C18–C13–P 6.08(33), Br–C12–C7–P 0.63(32), C6–C1–P–C13 ꢀ
96.74(22).
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8
9
Finally, this synthetic strategy was preliminary extended to secondary phosphine oxide. Interestingly
in the conditions where the aryne is promoted from the 1,2ꢀdibromobenzene 9a by reaction with the nꢀ
butyllithium, the Pꢀchirogenic phosphine oxide 12 leads to the corresponding oꢀbromophenyl phosphine
oxide 13 in 65% yield (Scheme 3). The analysis by HPLC on chiral column of the starting secondary
phosphine boranes 12 and the oꢀbromophenyl derivative 13, proves that the reaction proceeds without
racemization.
10
11
12
13
14
15
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17
18
19
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Scheme 3. (S)ꢀoꢀAnisylꢀoꢀbromophenylphenylphosphine oxide 13 from the secondary phosphine
oxide 12.
Conclusion
In conclusion, we have developed an efficient synthesis of oꢀhalogenoaryl tertiary phosphines. This
synthesis is based on the reaction between a secondary phosphine borane and an aryne, generated in situ
from 1,2ꢀdibromoꢀ or 1,2ꢀdiiodoarene and nꢀbutyllithium, as base. Interestingly, under these conditions,
the use of Pꢀchirogenic secondary phosphine boranes led to the corresponding o-bromoꢀ or o-
iodoarylphosphine boranes in good yields and with enantiomeric excesses up to 99%. The
stereochemistry of the reaction with retention at the Pꢀatom has been determined by the Xꢀray structure
of the Pꢀchirogenic phosphine boranes. The free oꢀhalogenoarylphosphines are obtained in yields up to
90% and without racemization, by decomplexation of their borane complexes using the DABCO® at
room temperature. Interestingly, the free oꢀhalogenoarylphosphines can be prepared by a two steps
reaction sequence starting from the secondary phosphine borane, i.e. reaction with the nꢀbutyllithium
and the1,2ꢀhalogenobenzene, and then decomplexation. The interest of these compounds for the
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preparation of various chiral and achiral oꢀfunctionalized phosphines useful in catalysis and
1
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3
organocatalysis, will prompt further exploration in other development soon.
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7
EXPERIMENTAL SECTION
8
9
General experimental methods. All reactions were carried out using standard Schlenk techniques
under inert atmosphere. Solvents were dried and purified by conventional methods prior to use.
Tetrahydrofuran (THF), toluene, diethyl ether (Et2O) were distilled from sodium/benzophenone and
stored under argon. Methyl alcohol (MeOH) was distilled from sodium. Methylene chloride (CH2Cl2)
was distilled from CaH2 under argon prior to use. Hexane and 2ꢀpropanol for HPLC were of
chromatographic grade and used without purification. nꢀbutyllithium, 1,2ꢀdibromobenzene, 1,2ꢀ
diiodobenzene, 4,5ꢀdibromoꢀoꢀxylene, boraneꢀdimethylsulfur complex, DABCO® and diphenylꢀ, diꢀoꢀ
tolylꢀ, diꢀcꢀhexylꢀ, diꢀiꢀpropyl, tꢀbutylphenylphosphine were purchased from commercial sources and
used without purification. The secondary phosphine borane 8 which were prepared by reaction of the
corresponding secondary phosphine with borane dimethylsulfure complex in THF, are in agreement
with the data of the literature.40 The dimethylphosphine borane 8b, which was prepared by reaction of
dimethylchlorophosphine with LiAlH4, then complexation with borane dimethylsulfure, corresponds to
what is described in literature.40b The Pꢀchirogenic secondary phosphine boranes 8i-m, were prepared
using the ephedrine methodology.24b,41 The oꢀanisylphenylphosphine oxide 12 was prepared according
to the literature.42 Reactions were monitored by thinꢀlayer chromatography (TLC) using 0.25 mm E.
Merck precoated silica gel plates. Flash chromatography was performed with the indicated solvents
10
11
12
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60
1
using silica gel 60 (60AAC, 35ꢀ70 ꢁm; SDS). H and (1H decoupled) 13C and 31P nuclear magnetic
resonance (NMR) spectra were recorded at 500 or 300 MHz and 125 or 75.5 MHz and 121 or 202 MHz,
1
respectively at ambient temperature using TMS as internal reference for H and 13C NMR, and 85%
31
phosphoric acid as external reference for P NMR. Data are reported as s = singlet, d = doublet, t =
triplet, q = quartet, m = multiplet, br.s = broad singlet, coupling constant(s) in Hertz, integration. HPLC
analyses were performed on a chromatograph equipped with a UV detector at λ = 210 nm and λ = 254
nm. Infraꢀred spectra were recorded on a FTꢀIR instrument. Melting points were measured on a Kofler
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melting points apparatus and are uncorrected. Optical rotation values were measured on polarimeter at
589 nm (sodium lamp). High Resolution Mass Spectra (HRMS) were recorded on mass spectrometer
under electron spray ionization (ESI) conditions, with a microꢀQꢀTOF or Orbitrap detector.
1
2
3
4
5
6
7
8
Crystal Structure Determination
9
10
11
12
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Diffraction data were collected on a diffractometer equipped with a nitrogen jet stream lowꢀ
temperature system. The Xꢀray source was graphiteꢀmonochromated MoꢀKα radiation (λ = 0.71073 Å)
from a sealed tube. The lattice parameters were obtained by leastꢀsquares fit to the optimized setting
angles of the entire set of collected reflections. No significant temperature drift was observed during the
data collections. Data were reduced by using DENZO43 software without applying absorption
corrections; the missing absorption corrections were partially compensated by the data scaling
procedure in the data reduction. Excepted for compound 10b multiꢀscan absorption corrections were
applied.44 The structure was solved by direct methods using the SIR9245 program. Refinements were
carried out by fullꢀmatrix leastꢀsquares on F2 using the SHELXL9746 program on the complete set of
reflections. Absolute configurations of all compounds were determined reliably from anomalous
scattering, using the Flack method.47 For all compound, anisotropic thermal parameters were used for
nonꢀhydrogen atoms. All H atoms, on carbon atom, were placed at calculated positions using a riding
model with CꢀH = 0.95 Å (aromatic), 0.98 Å (methyl), 0.99 Å (methylene) or 1.00 Å (methine) with
Uiso(H) = 1.2Ueq(CH), Uiso(H) = 1.5Ueq(CH3) or Uiso(H) = 1.2Ueq(CH2). All H atoms, on boron atom,
were placed at calculated positions using a riding model with BꢀH = 0.98 Å with Uiso(H) = 1.5Ueq(BH3).
Preparation of (4-methoxyphenyl)-phenylphosphine borane (8e).
(4ꢀMethoxyphenyl)ꢀphenylphosphine borane was prepared according to a method adapted from
Imamoto.48
To a solution of dichlorophenylphosphine (5.37 g, 30.0 mmol) in THF was added under argon, at ꢀ78
°C over a period of 3 hours a 0.25 M solution of 4ꢀmethoxyphenylmagnesium bromide in THF (120.0
mL, 30.0 mmol) (prepared by dilution of a commercially available 1.0 M solution). Then a 1.0 M
solution of LiAlH4 in THF (30.0 mL, 30.0 mmol) was added dropwise at ꢀ78 °C and the mixture was
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allowed to reach 25 °C. After 2 additional hours stirring at 25 °C, a 1.0 M solution of BH3ꢂTHF in
THF (36.0 mL, 36.0 mmol) was added dropwise. Ten minutes later, the mixture was poured into a
vigorously stirred mixture of 1 M HCl (300mL), CH2Cl2 (300 mL) and ice (300 g). At 25 °C, the
mixture was diluted with CH2Cl2 (300 mL) and the aqueous layer was separated and extracted with
CH2Cl2 (2 × 150 mL). All the organic layers were combined, dried over Na2SO4 and evaporated
under reduced pressure. Purification of the residue by column chromatography (cyclohexane/CH2Cl2
6:4) provided (4ꢀmethoxyphenyl)ꢀphenylphosphine borane as a colourless solid. Yield 19 % (1.31 g).
1H NMR (300 MHz, CDCl3) δ 1.03 (br q, J = 114 Hz, 3H), 3.84 (s, 3 H), 6.29 (dq, J = 378, 6.9 Hz,
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1H), 6.95ꢀ6.99 (m, 2H), 7.40ꢀ7.53 (m, 3H), 7.57ꢀ7.67 (m, 4H); C NMR (75.5 MHz, CDCl3): δ =
55.4, 114.8 (d, J = 11.2 Hz), 116.4 (d, J = 61.5 Hz), 127.1 (d, J = 57.2 Hz), 129.0 (d, J = 10.3 Hz),
31
131.4 (d, J = 2.5 Hz), 132.7 (d, J = 9.4 Hz), 134.9 (d, J = 10.5 Hz), 162.4 (d, J = 2.3 Hz); P NMR
(121 MHz, CDCl3): δ ꢀ 0.7 (br.s).
General procedure for the synthesis of o-halogenoarylphosphine borane (10). To a solution of
secondary phosphine borane 8 (0.83 mmol) in dry THF (2 mL), was added nꢀBuLi (0.83 mmol)
dropwise under argon at ꢀ78°C. The resulting solution was stirred at this temperature during one hour
and 1,2ꢀdihalogenoarene 9 (1.16 mmol) was then added dropwise followed by nꢀBuLi (0.17 mmol).
After one hour at ꢀ78°C, the reaction mixture was quenched with water (10 mL) and extracted with
methylene chloride (3x10 mL). The organic phases were dried over MgSO4, filtered and the solvent
evaporated giving a residue, which was purified by column chromatography on silica gel and/or by
recrystallization.
(2-Bromophenyl)-diphenylphosphine borane (10a)49. Purification: column chromatography
(elution with 2:1 petroleum ether/ethyl acetate) and/or recrystallization in methylene chloride/hexane.
Colourless solid; Yield 75% (0.22 g); mp 134ꢀ136°C; Rf 0.62 (petroleum ether/ethyl acetate 2:1); IR
(neat) 3052, 2924, 2854, 2814, 2379, 2340, 1558, 1480, 1436, 1424, 1128, 1106, 1058, 1025, 998, 738,
13
690 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 7.20ꢀ7.31 (m, 3H), 7.36ꢀ7.49 (m, 6H), 7.57ꢀ7.64 (m, 5H); C
NMR (75.5 MHz, CDCl3) δ 127.3 (d, J = 9.1 Hz), 128.0 (d, J = 5.9 Hz), 128.1 (d, J = 58.7 Hz), 128.8
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(d, J = 10.4 Hz), 130.1 (d, J = 57.3 Hz), 131.3 (d, J = 2.4 Hz), 132.7 (d, J = 2.1 Hz), 133.3 (d, J = 9.6
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3
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Hz), 135.1 (d, J = 5.9 Hz), 136.6 (d, J = 10.1 Hz); P NMR (121 MHz, CDCl3) δ 26.6 (br.s); HRMS
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5
6
7
(ESIꢀQꢀTOF) calcd for C18H17PBBrNa [M+Na]+ 377.0240, found 377.0227; Anal calcd for
C18H17PBBr: C, 60.90; H, 4.83; found: C, 61.06; H, 5.13.
8
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(2-Bromophenyl)-dicyclohexylphosphine borane (10b). The same general procedure as above was
used except that after adding nꢀBuLi at ꢀ78°C, the resulting solution was stirred 30 minutes at this
temperature then 30 minutes at room temperature. Purification: column chromatography (elution with
3:1 petroleum ether/methylene chloride) and/or recrystallization in methylene chloride/methyl alcohol.
Colourless solid; Yield 63% (0.19 g); mp 134ꢀ136°C; Rf 0.24 (petroleum ether/methylene chloride 3:1);
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IR(neat) 2930, 2851, 2379, 1446, 1418, 1274, 1061, 890, 854, 758, 736 cmꢀ1; H NMR (300 MHz,
CDCl3) δ 1.16ꢀ1.37 (m, 10H), 1.55ꢀ1.70 (m, 6H), 1.80ꢀ1.85 (m, 2H), 1.93ꢀ1.97 (m, 2H), 2.77ꢀ2.85 (m,
13
2H), 7.27ꢀ7.40 (m, 2H), 7.60 (dt, J = 1.8, 7.7 Hz), 8.07 (ddd, J = 1.7, 7.6, 12.6 Hz); C NMR (75.5
MHz, CDCl3) δ 25.7 (d, J = 1.3 Hz), 26.8 (d, J = 9.5 Hz), 27.0 (d, J = 8.5 Hz), 27.8, 28.8, 32.9 (d, J =
32.3 Hz), 127.1 (d, J = 3.1 Hz), 127.3 (d, J = 10.9 Hz), 128.0 (d, J = 46.3 Hz), 132.4 (d, J = 2.1 Hz),
134.0 (d, J = 4.4 Hz), 140.1 (d, J = 15.0 Hz); 31P NMR (121 MHz, CDCl3) δ 40.9 (br.s); HRMS (ESIꢀQꢀ
TOF) calcd for C18H29PBrBNa [M+Na]+ 389.1179, found 389.1157; Anal calcd for C18H29PBrB: C,
58.89; H, 7.96; found: C, 58.68; H, 8.29.
(2-Bromophenyl)-dimethylphosphine borane (10c). The same general procedure as above was
used except that after adding nꢀBuLi at ꢀ78°C, the resulting solution was stirred 30 minutes at this
temperature then 30 minutes at room temperature. Purification: column chromatography (elution with
3:1 petroleum ether/ethyl acetate). Colourless oil; Yield 42% (0.080 g); Rf 0.49 (petroleum ether/ethyl
acetate 3:1); IR (neat) 3077, 2375, 2360, 2335, 1580, 1559, 1453, 1413, 1302, 1289, 1273, 1256, 1144,
1
1109, 1071, 1022, 946, 919, 755 cmꢀ1; H NMR (300 MHz, Acetone d6) δ 1.55 (d, J = 10.4 Hz, 6H),
7.24ꢀ7.33 (m, 2H), 7.52ꢀ7.59 (m, 1H), 7.70ꢀ7.77 (m, 1H); 13C NMR (75.5 MHz, Acetone d6) δ 12.0 (d, J
= 40.1 Hz), 127.5, 128.6 (d, J = 10.9 Hz), 131.8 (d, J = 50.6 Hz), 134.2 (d, J = 2.2 Hz), 135.4 (d, J = 4.7
31
Hz), 137.0 (d, J = 15.7 Hz); P NMR (121 MHz, Acetone d6) δ 11.1ꢀ12.5 (m); HRMS (ESIꢀQꢀTOF)
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calcd for C8H13PBrBNa [M+Na]+ 252.9925, found 252.9923; Anal calcd forC8H13PBrB: C, 41.62; H,
5.68; found: C, 41.29; H, 6.07.
1
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7
8
(2-Bromophenyl)-diisopropylphosphine borane (10d). The same general procedure as above was
used except that after adding nꢀBuLi at ꢀ78°C, the resulting solution was stirred 30 minutes at this
temperature then 30 minutes at room temperature. Purification: column chromatography (elution with
3:1 petroleum ether/methylene chloride). Colourless solid; Yield 55% (0.13 g); mp 92ꢀ94°C; Rf 0.26
(petroleum ether/methylene chloride 3:1); IR (neat) 2974, 2932, 2871, 2393, 2373, 2349, 1574, 1557,
9
10
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1453, 1422, 1389, 1370, 1261, 1110, 1071, 1046, 1021, 931 cmꢀ1; H NMR (300 MHz, CDCl3) δ 0.86
(dd, J = 7.1, 15.9 Hz, 6H), 1.27 (dd, J = 7.0, 15.8 Hz, 6H), 2.95ꢀ3.09 (m, 2H), 7.22ꢀ7.35 (m, 2H), 7.55
(tt, J = 1.8, 7.7 Hz, 1H), 8.04 (ddd, J = 1.5, 7.5, 12.6 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) δ 18.5 (d, J
= 2.8 Hz), 18.7, 22.8 (d, J = 33.1 Hz) 126.7 (d, J = 3.1 Hz), 127.3 (d, J = 10.9 Hz), 128.7 (d, J = 46.6
Hz), 132.6 (d, J = 2.2 Hz), 134.2 (d, J = 4.4 Hz), 139.8 (d, J = 14.8 Hz); 31P NMR (121 MHz, CDCl3) δ
48.4ꢀ49.9 (m); HRMS (ESIꢀQꢀTOF) calcd for C12H21PBrBNa [M+Na]+ 309.0552, found 309.0545;
Anal calcd forC12H21PBrB: C, 50.22; H, 7.38; found: C, 50.57; H, 7.53.
(±)-(2-Bromophenyl)-(4-methoxyphenyl)-phenylphosphine borane (10e). Purification by column
chromatography with a mixture cyclohexane/CH2Cl2 6:4, as eluent. Analytical pure sample can be
obtained by crystallization from EtOAc at ꢀ20°C. Colourless solid; Yield 60 % (0.19 g); mp 133ꢀ136°C;
1H NMR (300 MHz, CDCl3) δ 0.60ꢀ2.10 (m, 3H), 3.85 (s, 3H), 6.96ꢀ7.00 (m, 2H), 7.21ꢀ7.37 (m, 3H),
7.41ꢀ7.55 (m, 3H), 7.57ꢀ7.69 (m, 5H); 13C NMR (75.5 MHz, CDCl3) δ 55.3, 114.5 (d, J = 11.2 Hz),
118.5 (d, J = 63.2 Hz), 127.3 (d, J = 8.9 Hz), 127.9 (d, J = 6.0 Hz), 128.8 (d, J = 58.9 Hz), 128.8 (d, J =
10.4 Hz), 130.7 (d, J = 57.2 Hz), 131.1 (d, J = 2.3 Hz), 132.6 (d, J = 2.0 Hz), 133.1 (d, J = 9.6 Hz),
135.1 (d, J = 4.4 Hz), 135.2 (d, J = 10.7 Hz), 136.4 (d, J = 9.8 Hz), 162.1 (d, J = 2.3 Hz); 31P NMR (121
MHz, CDCl3) δ 25.3 (br.s). Anal. calcd for C19H19BBrOP: C, 59.27; H, 4.97, found: C, 59.17; H, 4.91.
(±)-2-Bromophenyl)-tert-butyl-phenylphosphine borane (10f). Purification by column
chromatography with a mixture cyclohexane/CH2Cl2 8 : 2 as eluent, followed by crystallization from
acetonitrile. Colourless solid; Yield 34% (0.095 g); mp 134ꢀ136°C; 1H NMR (300 MHz, CDCl3) δ 0.40ꢀ
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1.70 (m, 3H), 1.44 (d, J = 14.1 Hz, 9H), 7.31 (br t, J = 7.6 Hz, 1H), 7.37ꢀ7.50 (m, 4H), 7.58ꢀ7.67 (m,
3H), 8.10 (ddd, J = 10.5, 7.8, 1.6 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) δ 27.5 (d, J = 2.2 Hz), 32.1 (d,
J = 29.5 Hz), 126.7 (d, J = 9.2 Hz), 128.1 (d, J = 1.0 Hz), 128.4 (d, J = 9.7 Hz), 128.9 (d, J = 53.1 Hz),
129.6 (d, J = 43.8 Hz), 130.4 (d, J = 2.2 Hz), 132.2 (d, J = 1.8 Hz), 132.9 (d, J = 8.1 Hz), 135.9 (d, J =
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5.1 Hz), 137.0 (d, J = 10.7 Hz); P (121 MHz, CDCl3) δ 42.1 (br.s). Anal. calcd for C16H21BBrP: C,
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57.36; H, 6.32, found: C, 57.54; H, 6.54.
(2-Bromo-4,5-dimethylphenyl)-diphenylphosphine borane (10i). To
a
solution of
diphenylphosphine borane 8a (0.17 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon
at ꢀ78°C nꢀBuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour and
4,5ꢀdibromoꢀoꢀxylene 9b (0.31 g, 1.16 mmol) was then added followed by nꢀBuLi (0.17 mmol). After
stirring to room temperature during one hour, the reaction mixture was quenched with water (10 mL)
and extracted with methylene chloride (3x10 mL). The organic phases were dried over MgSO4, filtered
and the solvent evaporated giving a residue which was purified by column chromatography on silica gel
using petroleum ether/methylene chloride 3:1 as eluent. Analytical pure sample can be obtained by
recrystallization in methylene chloride/hexane. Colourless solid; Yield 56% (0.18 g); mp 152ꢀ154°C; Rf
0.45 (petroleum ether/ethyl acetate 3:1); IR (neat) 3050, 2986, 2946, 2917, 2417, 2388, 2357, 1588,
1481, 1471, 1436, 1343, 1136, 1125, 1102, 1062, 1028, 999, 923, 877, 749, 734, 701, 692 cmꢀ1; H
1
NMR (300 MHz, CDCl3) δ 2.17 (s, 3H, CH3), 2.29 (s, 3H), 7.21 (d, J = 12.3 Hz), 7.43ꢀ7.56 (m, 7H),
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7.65ꢀ7.72 (m, 4H); C NMR (75.5 MHz, CDCl3) δ 19.4, 19.5, 124.7 (d, J = 4.4 Hz), 131.1 (d, J = 2.5
Hz), 133.2 (d, J = 9.6 Hz), 135.9 (d, J = 6.1 Hz), 136.3 (d, J = 9.9 Hz), 137.8 (d, J = 11.8 Hz), 142.6 (d,
31
J = 2.2 Hz); P NMR (121 MHz, CDCl3) δ 25.5 (br.s); HRMS (ESIꢀQꢀTOF) calcd for C20H21PBBrNa
[M+Na]+ 405.0553, found 405.0563; Anal calcd for C20H21PBBr: C, 62.71; H, 5.53; found: C, 62.86; H,
5.58.
(2-Bromo-4,5-dimethyl-phenyl)-dicyclohexylphosphine borane (10j). The same procedure as for
10i was applied starting from dicyclohexylphosphine borane 8b and 1,2ꢀdibromoꢀoꢀxylene 9b.
Purification by column chromatography (elution with cyclohexane/CH2Cl2 8:2) followed by
crystallization in acetonitrile. Colourless solid; Yield 53% (0.17 g); mp 164ꢀ166°C; 1H NMR (300 MHz,
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CDCl3) δ 0.00ꢀ1.30 (m, 3H), 1.10ꢀ1.76 (m, 16H), 1.76ꢀ1.87 (m, 2H), 1.87ꢀ1.99 (m, 2H), 2.23 (s, 3 H),
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2.24 (s, 3H), 2.69ꢀ2.87 (m, 2H), 7.37 (d, J = 1.8 Hz, 1H), 7.77 (d, J = 12.7 Hz, 1H); C (75.5 MHz,
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6
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CDCl3) δ 19.1, 19.3, 25.8, 26.8ꢀ27.0 (m), 27.8, 28.7, 33.0 (d, J = 32.6 Hz), 123.8 (d, J = 2.8 Hz), 124.3
(d, J = 48.5 Hz), 135.0 (d, J = 4.9 Hz), 136.1 (d, J = 10.9 Hz), 140.7 (d, J = 15.0 Hz), 141.9 (d, J = 1.9
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Hz); P NMR (121, CDCl3 MHz) δ 38.7 (br.s). Anal. calcd for C20H33BBrP: C, 60.79; H, 8.42, found:
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C, 60.41; H, 8.06.
(2-Iodophenyl)-diphenylphosphine borane (10k). The same general procedure as above was used,
but using the diiodobenzene 9c. Purification: column chromatography (elution with 1:1 petroleum
ether/methylene chloride) and/or recrystallization in ethyl acetate. Colourless solid; Yield 50% (0.17 g);
mp 182ꢀ184°C; Rf 0.45 (petroleum ether/methylene chloride 1:1); IR (neat) 3051, 2401, 2342, 2245,
1570, 1555, 1480, 1436, 1420, 1311, 1255, 1188, 1165, 1126, 1101, 1054, 1028, 999, 972, 737, 688 cmꢀ
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1; H NMR (300 MHz, CDCl3) δ 7.13ꢀ7.19 (m, 1H), 7.20ꢀ7.27 (m, 1H), 7.33ꢀ7.40 (m, 1H), 7.46ꢀ7.60
(m, 6H), 7.68ꢀ7.75 (m, 4H), 8.03 (ddd, J = 1.1, 3.2, 7.8 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) δ 101.2
(d, J = 8.4 Hz), 127.9 (d, J = 9.0 Hz), 128.1 (d, J = 58.8 Hz), 128.9 (d, J = 10.2 Hz), 131.3 (d, J = 2.4
Hz), 132.3 (d, J = 2.2 Hz), 133.3 (d, J = 58.6 Hz), 133.6 (d, J = 9.5 Hz), 136.5 (d, J = 10.5 Hz), 142.7
(d, J = 7.1 Hz); 31P NMR (121 MHz, CDCl3) δ 30.5 (br.s); HRMS (ESIꢀQꢀTOF) calcd for C18H17IBPNa
[M+Na]+ 425.0101, found 425.0096; Anal calcd for C18H17IBP: C, 53.78; H, 4.26; found: C, 53.97; H,
4.36.
(2-Iodophenyl)-dicyclohexylphosphine borane (10l). The same general procedure as above was
used, but using the diiodobenzene 9c, except that after adding nꢀBuLi at ꢀ78°C, the resulting solution
was stirred 30 minutes at this temperature then 30 minutes at room temperature. Purification: column
chromatography (elution with 2:1 petroleum ether/methylene chloride). Colourless solid; Yield 56%
(0.19 g); mp 144ꢀ146°C; Rf 0.33 (petroleum ether/methylene chloride 2:1); IR (neat) 2919, 2851, 2397,
2352, 1573, 1556, 1447, 1414, 1345, 1064, 1040, 1004, 918, 887, 852, 818, 762, 734, 714, 639 cmꢀ1; 1H
NMR (300 MHz, CDCl3) δ 1.00ꢀ1.17 (m, 10H), 1.44ꢀ1.56 (m, 6H), 1.63ꢀ1.67 (m, 2H), 1.76ꢀ1.80 (m,
2H), 2.73ꢀ2.85 (m, 2H), 6.92 (tt, J = 1.5, 7.5 Hz, 1H), 7.22 (tt, J = 1.3, 7.5 Hz, 1H), 7.77 (dt, J = 1.5, 7.9
Hz, 1H), 7.86 (ddd, J = 0.9, 7.7, 12.9 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) δ 25.7 (d, J = 1.2 Hz), 26.9
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(d, J = 3.5 Hz), 27.1 (d, J = 2.7 Hz), 27.8, 28.7 (d, J = 1.2 Hz), 32.5 (d, J = 31.8 Hz), 99.8 (d, J = 2.3
Hz), 127.9 (d, J = 11.2 Hz), 131.2 (d, J = 47.2 Hz), 132.2 (d, J = 2.2 Hz), 140.8 (d, J = 16.0 Hz), 141.7
(d, J = 5.2 Hz); 31P NMR (121 MHz, CDCl3) δ 41.6 (br.s); HRMS (ESIꢀQꢀTOF) calcd for C18H29PIBNa
[M+Na]+ 437.1030, found 437.1012; Anal calcd for C18H29PIB: C, 52.21; H, 7.06; found: C, 52.19; H,
6.98.
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(R)-(2-Bromophenyl)-(2-methoxyphenyl)-phenylphosphine borane (10n). Purification: column
chromatography (elution with 3:1 petroleum ether/ethyl acetate). Colourless solid; Yield 53% (0.17 g);
mp 152ꢀ154°C; Enantiomeric excess: 95% by HPLC analysis (chiralpak AD, 0.2 mL.minꢀ1, hexane/2ꢀ
propanol 99:1, tR (R) = 29.4 min, tR (S) = 32.2 min); Rf 0.18 (petroleum ether/ethyl acetate 3:1); [α]D ꢀ
1.3 (c 1.6, CHCl3); IR (neat) 3054, 2940, 2838, 2384, 1589, 1575, 1559, 1478, 1454, 1431, 1277, 1265,
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1252, 1164, 1134, 1103, 1059, 1021, 854, 802, 733 cmꢀ1; H NMR (300 MHz, CDCl3) δ 3.56 (s, 3H),
6.94 (dd, J = 3.8, 8.3 Hz, 1H), 7.08 (tdd, J = 0.8, 2.1, 7.5 Hz, 1H), 7.28ꢀ7.33 (m, 3H), 7.44ꢀ7.54 (m,
4H), 7.60ꢀ7.64 (m, 1H), 7.80ꢀ7.87 (m, 3H); 13C NMR (75.5 MHz, CDCl3) δ 55.4, 111.5 (d, J = 4.6 Hz),
116.5 (d, J = 57.8 Hz), 121.5 (d, J = 12.2 Hz), 126.7 (d, J = 6.4 Hz), 127.0 (d, J = 9.2 Hz), 128.3 (d, J =
59.9 Hz), 128.4 (d, J = 10.5 Hz), 131.0 (d, J = 61.4 Hz), 131.1, (d, J = 2.4 Hz), 131.7 (d, J = 2.1 Hz),
133.8 (d, J = 1.9 Hz), 133.9 (d, J = 9.8 Hz), 134.5, (d, J = 6.0 Hz), 135.0 (d, J = 9.8 Hz), 135.6 (d, J =
9.8 Hz), 161.2; 31P NMR (121 MHz, CDCl3) δ 23.7 (br.s); HRMS (ESIꢀQꢀTOF) calcd for
C19H19BBrOPNa [M+Na]+ 407.0346, found 407.0333; Anal calcd for C19H19BBrOP: C, 59.27; H, 4.97;
found: C, 58.89; H, 5.25.
(S)-Ferrocenyl-(2-bromophenyl)-phenylphosphine borane (10p). Purification: recrystallization in
methylene chloride/hexane. Orange solid; Yield 47% (0.18 g); mp 208ꢀ210°C; Enantiomeric excess:
99% by HPLC analysis (chiralcel ODꢀH, 0.5 mL.minꢀ1, hexane/2ꢀpropanol 98:2, tR (R) = 19.6 min, tR (S)
= 23.2 min); Rf 0.39 (petroleum ether/ethyl acetate 3:1); [α]D +162.9 (c 0.5, CHCl3); IR (neat) 3092,
3074, 3054, 2408, 2382, 2350, 1571, 1555, 1483, 1450, 1437, 1417, 1387, 1334, 1308, 1271, 1249,
1169, 1130, 1105, 1060, 1053, 1022, 998, 844, 765, 753, 739, 721 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ
4.09 (sl, 5H), 4.14ꢀ4.16 (m, 1H), 4.51ꢀ4.53 (m, 1H), 4.61ꢀ4.62 (m, 1H), 4.84ꢀ4.87 (m, 1H), 7.22ꢀ7.31
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(m, 3H), 7.48ꢀ7.59 (m, 4H), 7.73ꢀ7.80 (m, 2H); C NMR (75.5 MHz, CDCl3) δ 69.2 (d, J = 70.1 Hz),
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69.9, 72.0, 72.1 (d, J = 5.0 Hz), 72.2 (d, J = 6.7 Hz), 74.7 (d, J = 14.5 Hz), 126.9 (d, J = 8.6 Hz), 127.0
(d, J = 7.2 Hz), 128.5 (d, J = 10.5 Hz), 129.7 (d, J = 61.4 Hz), 131.1 (d, J = 2.4 Hz), 132.1 (d, J = 2.0
Hz), 132.6 (d, J = 9.8 Hz), 132.9 (d, J = 58.1 Hz), 134.7 (d, J = 5.7 Hz), 135.6 (d, J = 8.8 Hz); 31P NMR
(121 MHz, CDCl3) δ 23.3 (br.s); HRMS (ESIꢀQꢀTOF) calcd for C22H21PBrBFeNa [M+Na]+ 484.9905,
found 484.9912; Anal calcd for C22H21PBrBFe: C, 57.08; H, 4.57; found: C, 56.78; H, 4.61.
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(S)-Ferrocenyl-(2-iodophenyl)-phenylphosphine borane (10q). Purification: Recrystallization in
methylene chloride/hexane. Orange solid; Yield 55% (0.23 g); mp 218ꢀ220°C; Enantiomeric excess:
99% by HPLC analysis (chiralcel ODꢀH, 0.5 mL.minꢀ1, hexane/2ꢀpropanol 98:2, tR (R) = 19.2 min, tR (S)
= 25.2 min); Rf 0.54 (petroleum ether/ethyl acetate 3:1); [α]D +207.1 (c 0.6, CHCl3); IR (neat) 3124,
3086, 3052, 2407, 2380, 2350, 1553, 1483, 1426, 1387, 1368, 1335, 1100, 1059, 1027, 1010, 821, 739,
716, 693 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 4.07ꢀ4.08 (m, 1H), 4.09 (sl, 5H), 4.51ꢀ4.52 (m, 1H), 4.62ꢀ
4.63 (m, 1H), 7.07 (tt, J = 1.6, 7.5 Hz), 7.14 (ddd, J = 1.7, 7.8, 11.0 Hz, 1H), 7.28ꢀ7.33 (m, 2H), 7.50ꢀ
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7.63 (m, 3H), 7.77ꢀ7.83 (m, 2H), 7.91 (ddd, J = 1.0, 3.1, 7.8 Hz, 1H); C NMR (75.5 MHz, CDCl3) δ
69.8 (d, J = 70.0 Hz), 70.0, 71.7 (d, J = 3.7 Hz), 72.1 (d, J = 8.4 Hz), 72.3 (d, J = 6.5 Hz), 74.9 (d, J =
14.9 Hz), 100.2 (d, J = 9.8 Hz), 127.6 (d, J = 8.3 Hz), 128.6 (d, J = 10.5 Hz), 129.2 (d, J = 60.8 Hz),
131.3 (d, J = 2.4 Hz), 131.7 (d, J = 2.1 Hz), 133.4 (d, J = 9.5 Hz), 135.4 (d, J = 9.0 Hz), 136.0 (d, J =
58.3 Hz), 142.2 (d, J = 7.1 Hz); 31P NMR (121 MHz, CDCl3) δ 27.5 (br.s); HRMS (ESIꢀQꢀTOF) calcd
for C22H21PIBFeNa [M+Na]+ 532.9764, found 532.9747; Anal calcd for C22H21PIBFe: C, 51.82; H,
4.15; found: C, 52.03; H, 4.12.
(S)-(2-Bromophenyl)-phenylisopropylphosphine
borane
(10r).
Purification:
column
chromatography (elution with 3:1 petroleum ether/ethyl acetate). Colourless oil; Yield 48% (0.13 g);
Enantiomeric excess: 95% by HPLC analysis (lux 5u cellulose 2, 0.2 mL.minꢀ1, hexane/2ꢀpropanol 98:2,
tR (S) = 35.2 min, tR (R) = 37.7 min); Rf 0.52 (petroleum ether/ethyl acetate 3:1); [α]D ꢀ45.0 (c 0.3,
CHCl3); IR (neat) 2971, 2932, 2872, 2381, 1576, 1453, 1436, 1417, 1271, 1254, 1108, 1065, 1039,
1024, 739, 696 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 1.02 (dd, J = 7.1, 17.1 Hz, 3H), 1.32 (dd, J = 7.0,
16.4 Hz, 3H), 3.31ꢀ3.45 (m, 1H), 7.23ꢀ7.40 (m, 5H), 7.48 (ddd, J = 1.3, 2.5, 7.9 Hz, 1H), 7.55ꢀ7.61 (m,
2H), 8.08 (ddd, J = 1.6, 7.7, 12.5 Hz, 1H); 13C NMR (75.5 MHz, CDCl3) δ 17.3 (d, J = 2.3 Hz), 18.0 (d,
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J = 2.1 Hz), 21.3 (d, J = 35.7 Hz), 127.4 (d, J = 10.8 Hz), 127.7, 128.3 (d, J = 55.2 Hz), 128.4, 128.5,
129.6 (d, J = 50.6 Hz), 130.6 (d, J = 2.3 Hz), 132.4, 132.6, 132.8 (d, J = 2.2 Hz), 134.6 (d, J = 4.8 Hz),
138.1 (d, J = 14.6 Hz); 31P NMR (121 MHz, CDCl3) δ 35.0ꢀ35.6 (m); HRMS (ESIꢀQꢀTOF) calcd for
C15H19PBBrNa [M+Na]+ 343.0396, found 343.0407; Anal calcd for C15H19PBBr: C, 56.12; H, 5.97;
found: C, 56.50; H, 6.16.
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(S)-(2-Bromophenyl)-cyclohexylphenylphosphine
borane
(10s).
Purification:
column
chromatography with a mixture 4:1 petroleum ether/ethyl acetate, as eluent. Colourless oil; Yield 47%
(0.14 g); Enantiomeric excess: 95% by HPLC analysis (chiralcel ODꢀH, 0.2 mL.minꢀ1, hexane/2ꢀ
propanol 98:2, tR (S) = 26.1 min, tR (R) = 28.1 min); Rf 0.46 (petroleum ether/ethyl acetate 4:1); [α]D ꢀ
21.6 (c 0.2, CHCl3); IR (neat) 2936, 2853, 2385, 2348, 1577, 1559, 1489, 1453, 1439, 1421, 1133, 1110,
1057, 1021, 1003, 762, 737 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 1.29ꢀ1.50 (m, 5H), 1.74ꢀ1.83 (m, 3H),
1.90ꢀ1.92 (m, 1H), 2.03ꢀ2.05 (m, 1H), 3.18ꢀ3.24 (m, 1H), 7.35 (t, J = 7.5 Hz, 1H), 7.41ꢀ7.48 (m, 4H),
7.58 (d, J = 7.8 Hz, 1H), 7.65ꢀ7.68 (m, 2H), 8.17ꢀ8.20 (m, 1H); 13C NMR (75.5 MHz, CDCl3) δ 25.8 (d,
J = 1.5 Hz), 26.7, 26.8, 27.0 (d, J = 12.6 Hz), 28.1, 31.3 (d, J = 34.7 Hz), 127.4 (d, J = 11.0 Hz), 128.0
(d, J = 12.6 Hz), 128.4 (d, J = 67.3 Hz), 128.5 (d, J = 9.9 Hz), 129.1 (d, J = 51.1 Hz), 130.6 (d, J = 2.4
Hz), 132.4 (d, J = 8.7 Hz), 132.8 (d, J = 2.2 Hz), 134.5 (d, J = 4.7 Hz), 138.3 (d, J = 15.1 Hz); 31P NMR
(121 MHz, CDCl3) δ 31.3ꢀ31.6 (m); HRMS (ESIꢀQꢀTOF) calcd for C18H23PBBrNa [M+Na]+ 383.0709,
found 383.0723; Anal calcd for C18H23PBBr: C, 59.88; H, 6.42; found: C, 60.10; H, 6.16.
Borane decomplexation in free o-halogenoarylphosphine (11). General procedure. A solution of
oꢀhalogenoaryl phosphine borane 10 (0.5 mmol) and DABCO® (1.5 mmol) in 3 mL of dry toluene was
stirred under argon at room temperature overnight. The solvent was evaporated under vacuum and the
residue was purified by flash chromatography on silica gel and/or recrystallization.
(2-Bromophenyl)-diphenylphosphine (11a)21a. Purification: column chromatography (elution with
3:1 petroleum ether/ethyl acetate). White solid; Yield 79% (0.13 g); mp 112ꢀ114°C (Litt21a: 112ꢀ
114°C); Rf 0.48 (petroleum ether/ethyl acetate 3:1); IR (neat) 3056, 2925, 2854, 1586, 1572, 1555,
1479, 1448, 1436, 1420, 1312, 1249, 1181, 1161, 1121, 1093, 1073, 1017, 851, 756, 743, 696 cmꢀ1;
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1H NMR (300 MHz, CDCl3) δ 6.66ꢀ6.70 (m, 1H), 7.10ꢀ7.13 (m, 2H), 7.18ꢀ7.30 (m, 10H), 7.50ꢀ7.54
(m, 1H); 13C NMR (75.5 MHz, CDCl3) δ 127.4, 128.6 (d, J = 7.2 Hz), 129.0, 129.5 (d, J = 50.3 Hz),
130.2, 133.0 (d, J = 2.3 Hz), 134.1 (d, J = 20.2 Hz), 135.5, 135.8 (d, J = 10.5 Hz), 138.9 (d, J = 11.5
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Hz); P NMR (121 MHz, CDCl3) δ ꢀ5.1 (s); HRMS (ESIꢀQꢀTOF) calcd for C18H14PBrNa [M+Na]+
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362.9909, found 362.9910.
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(2-Bromo-4,5-dimethylphenyl)-diphenylphosphine (11c). Purification: column chromatography
(elution with 3:1 petroleum ether/ethyl acetate). White solid; Yield 84% (0.155 g); mp 148ꢀ150°C; Rf
0.63 (petroleum ether/ethyl acetate 3:1); IR (neat) 3054, 2938, 2918, 1586, 1477, 1457, 1449, 1433,
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1383, 1345, 1152, 1117, 1093, 1070, 1022, 996, 911, 880, 747, 740, 693 cmꢀ1; H NMR (300 MHz,
13
CDCl3) δ 2.06 (s, 3H), 2.25 (s, 3H), 6.52 (d, J = 3.0 Hz, 1H), 7.28ꢀ7.41 (m, 11H); C NMR (75.5
MHz, CDCl3) δ 19.3, 19.4, 126.9 (d, J = 30.8 Hz), 128.5 (d, J = 7.1 Hz), 128.9, 133.7, 133.9 (d, J =
31
20.2 Hz), 135.0 (d, J = 9.3 Hz), 135.4, 136.0, 136.2 (d, J = 10.3 Hz), 139.5; P NMR (121 MHz,
CDCl3) δ ꢀ6.1 (s); HRMS (ESIꢀQꢀTOF) calcd for C20H18PBrNa [M+Na]+ 391.0222, found 391.0240;
Anal calcd for C20H18PBr: C, 65.06; H, 4.91; found: C, 65.07; H, 5.15.
(2-Iodophenyl)-diphenylphosphine (11d).21a Purification: column chromatography (elution with 3:1
petroleum ether/ethyl acetate). White solid; Yield 83% (0.16 g); mp 120ꢀ122°C (Litt21a: 119ꢀ120°C);
Rf 0.64 (petroleum ether/ethyl acetate 3:1); IR (neat) 3052, 1568, 1549, 1477, 1434, 1414, 1327,
1
1265, 1179, 1158, 1118, 1090, 1070, 1027, 971, 947, 740, 693 cmꢀ1; H NMR (300 MHz, CDCl3) δ
6.71 (dt, J = 2.0, 7.7 Hz, 1H), 6.94 (td, J = 1.7, 7.6 Hz, 1H), 7.15ꢀ7.21 (m, 5H), 7.24ꢀ7.31 (m, 6H),
13
7.82 (ddd, J = 1.1, 3.1, 7.8 Hz, 1H); C NMR (75.5 MHz, CDCl3) δ 107.0 (d, J = 39.7 Hz), 128.3,
128.7 (d, J = 7.1 Hz), 129.0, 130.1, 134.0 (d, J = 20.0 Hz), 134.2 (d, J = 1.0 Hz), 136.3 (d, J = 10.9
Hz), 139.8 (d, J = 3.8 Hz), 142.3 (d, J = 9.3 Hz); 31P NMR (121 MHz, CDCl3) δ 8.0 (s); HRMS (ESIꢀ
QꢀTOF) calcd for C18H14PINa [M+Na]+ 410.9770, found 410.9771.
(R
)-(2-bromophenyl)-(2-methoxyphenyl)-phenylphosphine
(11e).
Purification:
column
chromatography (elution with 3:1 petroleum ether/ethyl acetate). Analytical pure sample can be
obtained by recrystallization in methylene chloride/methyl alcohol. Colourless solid; Yield 90% (0.17
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The Journal of Organic Chemistry
g); mp 128ꢀ130°C; Enantiomeric excess: 99% by HPLC analysis (chiralpak AD, 0.2 mL.minꢀ1,
hexane/2ꢀpropanol 99:1, tR (R) = 30.8 min, tR (S) = 35.0 min). Rf 0.41 (petroleum ether/ethyl acetate
3:1); [α]D ꢀ20.6 (c 0.5, CHCl3); IR (neat) 3063, 2930, 2833, 1581, 1571, 1553, 1458, 1428, 1298,
1271, 1239, 1162, 1128, 1093, 1069, 1041, 1017, 864, 793, 752 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ
3.77 (s, 3H), 6.78ꢀ6.82 (m, 1H), 6.65ꢀ6.70 (m, 1H), 6.87ꢀ6.96 (m, 2H), 7.18ꢀ7.24 (m, 2H), 7.28ꢀ7.43
(m, 6H), 7.58ꢀ7.63 (m, 1H); 13C NMR (75.5 MHz, CDCl3) δ 55.7, 110.3 (d, J = 1.5 Hz), 121.2, 124.5
(d, J = 12.4 Hz), 127.3, 128.5 (d, J = 7.4 Hz), 129.0, 130.0, 130.1 (d, J = 32.0 Hz), 130.6, 132.8 (d, J
= 2.4 Hz), 133.9, 134.1, 134.4, 135.4 (d, J = 10.5 Hz), 138.5 (d, J = 11.4 Hz), 161.3 (d, J = 15.8 Hz);
31P NMR (121 MHz, CDCl3) δ ꢀ15.3 (s); HRMS (ESIꢀQꢀTOF) calcd for C19H16PBrONa [M+Na]+
393.0014, found 393.0006; Anal calcd for C19H16PBrO: C, 61.48; H, 4.34; found: C, 61.37; H, 4.59.
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(S)-Ferrocenyl-(2-bromophenyl)-phenylphosphine (11g). Purification: column chromatography
(elution with 3:1 petroleum ether/ethyl acetate). Orange solid; Yield 75% (0.17 g); Enantiomeric
excess: 99% by HPLC analysis after complexation with borane (chiralcel ODꢀH, 0.5 mL.minꢀ1,
hexane/2ꢀpropanol 98:2, tR (R) = 19.6 min, tR (S) = 23.2 min). Rf 0.50 (petroleum ether/ethyl acetate
3:1); [α]D +207.0 (c 0.6, CHCl3); IR (neat) 3104, 3045, 2926, 2855, 1741, 1552, 1481, 1446, 1436,
1420, 1308, 1270, 1248, 1192, 1163, 1108, 1098, 1016, 1003, 890, 821, 749, 698 cmꢀ1; 1H NMR (300
MHz, CDCl3) δ 3.60ꢀ3.61 (m, 1H), 3.98 (sl, 5H), 4.21ꢀ4.23 (m, 1H), 4.29ꢀ4.31 (m, 1H), 4.36ꢀ4.39 (m,
13
1H), 6.84 (dt, J = 2.1, 7.4 Hz, 1H), 7.06ꢀ7.19 (m, 2H), 7.28ꢀ7.32 (m, 3H), 7.34ꢀ7.42 (m, 3H); C
NMR (75.5 MHz, CDCl3) δ 69.9, 71.7, 72.3, 72.4 (d, J = 7.1 Hz), 75.3 (d, J = 31.8 Hz), 76.5 (d, J =
7.6 Hz), 128.1, 129.0 (d, J = 8.0 Hz), 129.4 (d, J = 30.3 Hz), 129.9, 130.9, 133.6 (d, J = 1.7 Hz),
134.8 (d, J = 1.5 Hz), 135.2 (d, J = 20.6 Hz), 137.3 (d, J = 8.6 Hz), 142.6 (d, J = 14.8 Hz); 31P NMR
(121 MHz, CDCl3) δ ꢀ16.6 (s); HRMS (ESIꢀQꢀTOF) calcd for C22H18PFeBr [M]+ 447.9675, found
447.9686; Anal calcd for C22H18PFeBr: C, 58.84; H, 4.04; found: C, 59.19; H, 4.05.
(S)-(2-bromophenyl)-phenylisopropylphosphine (11h). Purification: column chromatography
(elution with 3:1 petroleum ether/ethyl acetate). Colourless oil; Yield 82% (0.125 g); Enantiomeric
excess: 95% by HPLC analysis after complexation with borane (lux 5u Celluloseꢀ2, 0.2 mL.minꢀ1,
hexane/2ꢀpropanol 98:2, tR (S) 39.6 min, tR (R) 42.3 min); Rf 0.59 (petroleum ether/ethyl acetate 3:1);
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20
D
[
α]
ꢀ52.9 (c 0.4; CHCl3); IR (neat) 3054, 2952, 2865, 1556, 1449, 1421, 1384, 1365, 1250, 1228,
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7
1
1155, 1124, 1096, 1018, 878, 746, 697 cmꢀ1; H NMR (300 MHz, CDCl3) δ 1.06 (dd, J = 6.8, 15.5
Hz, 3H), 1.20 (dd, J = 6.9, 16.0 Hz, 3H), 2.41ꢀ2.47 (m, 1H), 7.19ꢀ7.22 (m, 1H), 7.32ꢀ7.35 (m, 3H),
7.37 (td, J = 1.3, 7.6 Hz, 1H), 7.46ꢀ7.50 (m, 3H), 7.59 (ddd, J = 1.2, 3.4, 8.0 Hz, 1H); 13C NMR (75.5
8
9
MHz, CDCl3)
δ 19.3 (d, J = 19.6 Hz), 19.8 (d, J = 19.6 Hz), 25.3 (d, J = 9.1 Hz), 127.3, 128.3 (2s),
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128.9, 130.0, 131.4 (d, J = 30.2 Hz), 132.8, 133.3 (d, J = 2.6 Hz), 133.7, 133.8, 136.6 (d, J = 13.0
31
Hz), 138.6 (d, J = 14.8 Hz); P NMR (121 MHz, CDCl3)
δ ꢀ1.4 (s); HRMS (ESIꢀQꢀTOF) calcd for
C15H16PBrNa [M+Na]+ 329.0065, found 329.0057.
Synthesis of
a two steps reaction sequence.
(2-bromophenyl)-di(
-tolyl)phosphine (11b)50. To a solution of secondary phosphine borane 8g
o-halogenoaryl phosphine (11) starting from secondary phosphine borane (8), using
o
(0.19 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon at ꢀ78°C nꢀBuLi (0.83
mmol). The resulting solution was stirred at this temperature during one hour and 1,2ꢀ
dibromobenzene (0.15 mL, 1.16 mmol) was then added dropwise followed by nꢀBuLi (0.17 mmol).
After one hour at ꢀ78°C, the reaction mixture was quenched with water (10 mL) and extracted with
methylene chloride (3x10 mL). The organic phases were dried over MgSO4, filtered and the solvent
evaporated giving a residue which was diluted with dry toluene (5 mL) under argon atmosphere.
DABCO® (0.28 g, 2.49 mmol) was added and the resulting solution was stirred at room temperature
overnight. The solvent was evaporated under vacuum and the crude product was purified by column
chromatography on silica gel using petroleum ether/ethyl acetate 3:1 as eluent. White solid; Overall
yield 40% (0.12 g); Rf 0.59 (petroleum ether/ethyl acetate 3:1); IR (neat) 3055, 3002, 2973, 1588,
1
1554, 1466, 1445, 1422, 1377, 1271, 1250, 1201, 1161, 1130, 1099, 1017, 867, 746, 715 cmꢀ1; H
NMR (300 MHz, CDCl3) δ 2.46 (2s, 6H), 6.76ꢀ6.78 (m, 3H), 7.12ꢀ7.14 (m, 2H), 7.22ꢀ7.24 (m, 2H),
7.27ꢀ7.29 (m, 2H), 7.32 (td, J = 1.3, 7.4 Hz, 2H), 7.64ꢀ7.66 (m, 1H); 13C NMR (75.5 MHz, CDCl3) δ
21.1, 21.3, 126.3, 127.6, 129.0, 130.1, 130.2 (d, J = 4.6 Hz), 130.6 (d, J = 32.5 Hz), 133.1 (d, J = 2.9
31
Hz), 133.2, 134.0 (d, J = 11.4 Hz), 134.7, 137.7 (d, J = 10.8 Hz), 142.8 (d, J = 27.4 Hz); P NMR
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(121 MHz, CDCl3) δ ꢀ19.7 (s); HRMS (ESIꢀQꢀTOF) calcd for C20H18PBrNa [M+Na]+ 391.0222,
found 391.0210; Anal calcd for C20H18PBr: C, 65.06; H, 4.91; found: C, 65.14; H, 5.00.
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(R)-(2-bromophenyl)-(2-methoxyphenyl)-phenylphosphine (11e). To a solution of secondary
7
8
9
phosphine borane (S)ꢀ8i (0.19 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon
at ꢀ78°C nꢀBuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour
and 1,2ꢀdibromobenzene (0.15 mL, 1.16 mmol) was then added dropwise followed by nꢀBuLi (0.17
mmol). After one hour at ꢀ78°C, the reaction mixture was quenched with water (10 mL) and extracted
with methylene chloride (3x10 mL). The organic phases were dried over MgSO4, filtered and the
solvent evaporated giving a residue which was diluted with dry toluene (5 mL) under argon
atmosphere. DABCO (0.28 g, 2.49 mmol) was added and the resulting solution was stirred at room
temperature overnight. The solvent was evaporated under vacuum and the crude product was purified
by column chromatography on silica gel using petroleum ether/ethyl acetate 3:1 as eluent. Analytical
pure sample can be obtained by recrystallization in methylene chloride/methyl alcohol. Colorless
solid; Overall yield 45% (0.14 g); Enantiomeric excess: 99% by HPLC analysis (chiralpak AD, 0.2
mL.minꢀ1, hexane/2ꢀpropanol 99:1, tR (R) = 30.8 min, tR (S) = 35.0 min); Rf 0.41 (petroleum
ether/ethyl acetate 3:1). All of the analyses were similar to that already described above.
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(R)-(2-iodophenyl)-(2-methoxyphenyl)-phenylphosphine (11f). To a solution of secondary
phosphine borane (S)ꢀ8i (0.19 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon at ꢀ
78°C nꢀBuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour and
1,2ꢀdiiodobenzene (0.15 mL, 1.16 mmol) was then added dropwise followed by nꢀBuLi (0.17 mmol).
After one hour at ꢀ78°C, the reaction mixture was quenched with water (10 mL) and extracted with
methylene chloride (3x10 mL). The organic phases were dried over MgSO4, filtered and the solvent
evaporated giving a residue which was diluted with dry toluene (5 mL) under argon atmosphere.
DABCO® (0.28 g, 2.49 mmol) was added and the resulting solution was stirred at room temperature
overnight. The solvent was evaporated under vacuum and the crude product was purified by column
chromatography on silica gel using petroleum ether/ethyl acetate 3:1 as eluent. White solid; Overall
1
31
yield 42% (0.145 g); mp 110ꢀ112°C; Enantiomeric excess: 95% by H NMR and/or P NMR of the
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corresponding phosphine oxide with (R)ꢀ3,5ꢀdinitroꢀNꢀ(1ꢀphenylꢀethyl)ꢀbenzamide as chiral reagent;
Rf 0.45 (petroleum ether/ethyl acetate 3:1); [α]D ꢀ24.2 (c 0.4, CHCl3); IR (neat) 3050, 2933, 2835,
1584, 1573, 1554, 1472, 1462, 1431, 1300, 1274, 1241, 1183, 1163, 1130, 1094, 1071, 1043, 1024,
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796, 753, 698 cmꢀ1; H NMR (300 MHz, CDCl3) δ 3.67 (s, 3H), 6.56 (ddd, J = 1.7, 4.4, 7.4 Hz, 1H),
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9
6.72 (dt, J = 1.9, 7.7 Hz, 1H), 6.77ꢀ6.86 (m, 2H), 6.92 (td, J = 1.7, 7.6 Hz, 1H), 7.13ꢀ7.32 (m, 7H),
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13
7.81 (ddd, J = 1.1, 3.1, 7.8 Hz, 1H); C NMR (75.5 MHz, CDCl3) δ 55.8, 107.2 (d, J = 41.4 Hz),
110.4 (d, J = 1.5 Hz), 121.2, 125.0 (d, J = 12.7 Hz), 128.1, 128.5, 128.6, 128.9, 130.0, 130.6, 133.9,
134.1, 134.2, 134.5, 135.8 (d, J = 10.9 Hz), 139.6 (d, J = 3.8 Hz), 141.9 (d, J = 9.0 Hz), 161.2 (d, J =
15.6 Hz); 31P NMR (121 MHz, CDCl3) δ 1.8 (s); HRMS (ESIꢀQꢀTOF) calcd for C19H16PIONa
[M+Na]+ 440.9876, found 440.9891; Anal calcd for C19H16PIO: C, 54.57; H, 3.86; found: C, 54.55; H,
3.90.
(S)-(2-bromophenyl)-(2-methylphenyl)-phenylphosphine (11i). To a solution of secondary
phosphine borane (R)ꢀ8m (0.18 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon at
ꢀ78°C nꢀBuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour and
1,2ꢀdibromobenzene (0.15 mL, 1.16 mmol) was then added dropwise followed by nꢀBuLi (0.17
mmol). After one hour at ꢀ78°C, the reaction mixture was quenched with water (10 mL) and extracted
with methylene chloride (3x10 mL). The organic phases were dried over MgSO4, filtered and the
solvent evaporated giving a residue which was diluted with dry toluene (5 mL) under argon
atmosphere. DABCO® (0.28 g, 2.49 mmol) was added and the resulting solution was stirred at room
temperature overnight. The solvent was evaporated under vacuum and the crude product was purified
by column chromatography on silica gel using petroleum ether/ethyl acetate 4:1 as eluent. White
solid; Overall yield 66% (0.195 g); mp 90ꢀ92°C; Enantiomeric excess: 73% by 31P NMR of the
corresponding phosphine oxide with (R)ꢀ3,5ꢀdinitroꢀNꢀ(1ꢀphenylꢀethyl)ꢀbenzamide as chiral reagent;
Rf 0.58 (petroleum ether/ethyl acetate 4:1); [α]D +14.5 (c 0.4, CHCl3); IR (neat) 3054, 1554, 1445,
1436, 1421, 1271, 1250, 1101, 1093, 1018, 744, 716, 696 cmꢀ1; H NMR (300 MHz, CDCl3) δ 2.44
1
(d, J = 1.2 Hz, 3H), 6.74ꢀ6.79 (m, 2H), 7.12 (td, J = 1.2, 7.0 Hz, 1H), 7.19ꢀ7.24 (m, 2H), 7.25ꢀ7.33
(m, 4H), 7.35ꢀ7.42 (m, 3H), 7.61ꢀ7.65 (m, 1H); 13C NMR (75.5 MHz, CDCl3) δ 21.3 (d, J = 21.8 Hz),
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126.2, 127.5, 128.7 (d, J = 7.3 Hz), 129.1 (d, J = 7.2 Hz), 130.2, 130.2 (d, J = 31.3 Hz), 130.3 (d, J =
4.9 Hz), 133.0, 133.1, 134.2, 134.5, 134.6, 134.7 (d, J = 11.4 Hz), 135.0 (d, J = 10.3 Hz), 138.3 (d, J
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2
3
4
5
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= 10.8 Hz), 142.5 (d, J = 26.6 Hz); P NMR (121 MHz, CDCl3) δ ꢀ12.2 (s); HRMS (ESIꢀQꢀTOF)
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9
calcd for C19H17PBrNa [M+H]+ 355.0246, found 355.0248; Anal calcd for C19H16PBr: C, 64.24; H,
4.54; found: C, 64.60; H, 4.66.
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Synthesis of (R)-(2-Bromophenyl)-(2-methoxyphenyl)-phenylphosphine oxide (13). To a solution
of (R)ꢀ(2ꢀmethoxyphenyl)ꢀphenylphosphine oxide 12 (0.19 g, 0.83 mmol) in dry THF (2 mL) was
added dropwise under argon at ꢀ78°C nꢀBuLi (0.83 mmol). The resulting solution was stirred at this
temperature during one hour and 1,2ꢀdibromobenzene 9a (0.28 g, 1.16 mmol) was then added
followed by nꢀBuLi (0.17 mmol). After stirring to room temperature over one hour, the reaction
mixture was quenched with water (10 mL) and extracted with methylene chloride (3x10 mL). The
organic phases were dried over MgSO4, filtered and the solvent evaporated giving a residue which
was purified by column chromatography on silica gel using ethyl acetate as eluent. Analytical pure
sample can be obtained by recrystallization in methylene chloride/hexane. White solid; Yield 65%
(0.21 g); Enantiomeric excess: 99% by HPLC analysis (chiralpak IB, 1.5 mL.minꢀ1, hexane/2ꢀ
propanol 90:10, tR (R) = 21.6 min, tR (S) = 25.1 min); Rf 0.28 (ethyl acetate ); [α]D +18.6 (c 0, 8
CHCl3); IR (neat) 3242, 3092, 3062, 2993, 2946, 2847, 1728, 1585, 1476, 1461, 1427, 1276, 1244,
1178, 1132, 1167, 1074, 1010, 883, 865, 800, 772, 737, 695 cmꢀ1; 1H NMR (500 MHz, CDCl3) δ 3.55
(s, 3H), 6.94 (ddd, J = 0.8, 3.8, 8.3 Hz, 1H), 7.11 (tdd, J = 0.8, 2.1, 7.5 Hz, 1H), 7.29ꢀ7.36 (m, 2H),
7.40ꢀ7.49 (m, 3H), 7.58ꢀ7.61 (m, 2H), 7.62ꢀ7.66 (m, 1H) 7.76ꢀ7.95 (m, 3H); 13C NMR (126 MHz,
CDCl3) δ 55.4, 111.1 (d, J = 7.0 Hz), 120.1 (d, J = 107.2 Hz), 121.3 (d, J = 11.9 Hz), 126.2 (d, J = 4.6
Hz), 126.7 (d, J = 11.6 Hz), 128.1 (d, J = 12.7 Hz), 131.6 (d, J = 2.7 Hz), 132.2 (d, J = 10.6 Hz),
132.3 (d, J = 110.3 Hz), 132.6 (d, J = 2.4 Hz), 133.8 (d, J = 109.0 Hz), 134.3 (d, J = 2.0 Hz), 134,4
31
(d, J = 7.7 Hz), 135.0 (d, J = 7.3 Hz), 135.2 (d, J = 11.0 Hz), 160.6 (d, J = 3.4 Hz); P NMR (202
MHz, CDCl3) δ 28.3 (s); HRMS (ESIꢀOrbitrap) calcd for C19H16PO2BrNa [M+Na]+ 409.0071, found
409.0076.
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ACKNOWLEDGMENT
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The authors are grateful for the financial support provided by CNRS (Centre National de la
Recherche Scientifique), the “Ministère de l’Education Nationale et de la Recherche”, the "Conseil
Regional de Bourgogne", and the Agence Nationale pour la Recherche (grant 07BLAN292ꢀ01
MetChirPhos). It is a pleasure for us to acknowledge the skilled technical assistance of M. J. Ondelꢀ
Eymin, F. Chaux and M. J. Penouilh for mass spectrometry analyses.
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SUPPORTING INFORMATION PARAGRAPH
1H, 13C, 31P of all compounds. Structure and crystallographic data of 2ꢀbromophenylꢀ
dicyclohexylphosphine borane 10b, 2ꢀbromoꢀ4,5ꢀdimethylphenylꢀdiphenylphosphine borane 10i.
Crystallographic data of (S)ꢀFerrocenylꢀ(2ꢀbromophenyl)ꢀphenylphosphine borane 10p, (S)ꢀFerrocenylꢀ
(2ꢀiodophenyl)ꢀphenylphosphine
borane
10q
and
(R)ꢀ(2ꢀbromophenyl)ꢀ(2ꢀmethoxyphenyl)ꢀ
phenylphosphine 11e. This material is available free of charge via the internet at http://pubs.acs.org.
REFERENCES
(1) (a) Tang, W.; Zang, X. Chem. Rev. 2003, 103, 3029. (b) Shimidzu, H.; Nagasaki, I.; Saito, T.
Tetrahedron 2005, 61, 5405. (c) Arrayas, R. G.; Adrio, J.; Carretero, J. C. Angew. Chem. Int. Ed., 2006,
45, 7674. (d) Jäkel, C.; Paciello, R. Chem. Rev. 2006, 106, 2912. (e) Zhang, W.; Chi, Y.; Zhang, X. Acc.
Chem. Res. 2007, 40, 1278. (f) Hargaden, G. C.; Guiry, P. J. Chem. Rev. 2009, 109, 2505.
(2) Phosphorous Ligands in Asymmetric Catalysis, Börner, A. (Ed.), WileyꢀVCH, Weinheim,
2008, Vol. 3.
(3) (a) Ouchi, Y.; Morisaki, Y.; Ogoshi, T.; Chujo, Y. Chem. Asian. J. 2007, 2, 397. (b) Salomon, C.;
Fortin, D.; Khiri, N.; Jugé, S.; Harvey, P. D. Eur. J. Inorg. Chem. 2011, 16, 2597.
(4) (a) Horner, L.; Winkler, H.; Rapp, A.; Mentrup, A.; Hoffmann, H.; Beck, P. Tetrahedron Lett.
1961, 161. (b) Luckenbach, R. Phosphorus 1972, 1, 223. (c) Leglaye, P.; Donadieu, B.; Brunet, J.ꢀJ.,
28
ACS Paragon Plus Environment

Page 29 of 35
The Journal of Organic Chemistry
Chauvin, R. Tetrahedron Lett. 1998, 39, 9179ꢀ9182.
Bayardon, J.; Jugé, S. Org. Lett. 2010, 12, 1568.
(d) Rémond, E.; Tessier, A.; Leroux, F. R.;
1
2
3
4
5
6
7
8
(5) (a) Rein, T.; Reiser, O. Acta Chem. Scand. 1996, 50, 369. (b) Rein, T.; Pedersen, T. M. Synthesis
2002, 5, 579.
9
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
(6) (a) Dalko, P. I.; Moisan, L. Angew. Chem. Int. Ed. 2001, 40, 3726. (b) Shi, M.; Chen, L.ꢀH.; Li,
C. ꢀQ. J. Am. Chem. Soc. 2005, 127, 3790. (c) R.; Wang, X.; Hashimoto, T.; Maruoka, K. Angew. Chem.
Int. Ed. 2008, 47, 9466. (d) He, R.; Maruoka, K. Synthesis 2009, 13, 2289. (e) He, R.; Ding, C.;
Maruoka, K. Angew. Chem. Int. Ed. 2009, 48, 4559.
(7) (a) Kagan, H. B.; Sasaki, M. in The Chemistry of Organophosphorus Compounds, Hartley, F. R.
(Ed.), J. Wiley, 1990, Vol. 1. (b) Pietrusiewicz, K.; Zablocka, M. Chem. Rev. 1994, 94, 1375. (c)
Kolodiazhnyi, O. I. Tetrahedron: Asymmetry 1998, 9, 1279. (d) Berthod, M.; Mignani, G.; Woodward,
G.; Lemaire, M. Chem. Rev. 2005, 105, 1801. (e) Grabulosa, A.; Granell, J.; Muller, G. Coord. Chem.
Rev. 2007, 251, 25.
(8) Ohff, M.; Holz, J.; Quirmbach, M.; Börner, A. Synthesis 1998, 1391.
(9) (a) Trost, B.M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921. (b) Breit, B.; Laungani A. C.
Tetrahedron: Asymmetry 2003, 14, 3823. (c) Hird, A. W.; Hoveyda, A. H. Angew. Chem. Int. Ed. 2003,
42, 1276. (d) Johannesen, S. A.; Glegola, K.; Sinou, D.; Framery, E.; Skrydstrup, T. Tetrahedron Lett.
2007, 48, 3569. (e) Marhino, V. R.; Rodrigues A. I.; Burke, A. J. Tetrahedron: Asymmetry 2008, 19,
454.
(10) (a) Brunner, H.; Ittner, K. ꢀP.; Lunz, D.; Schmatloch, S.; Schmidt, T.; Zabel, M. Eur J. Org.
Chem. 2003, 855. (b) Schenkel, L. B.; Ellman, J. A. J. Org. Chem. 2004, 69, 1800. (c) FloresꢀLopez, C.
Z.; FloresꢀLopez, L. Z.; Aguirre, G.; Hellberg, L. H.; ParraꢀHake, M. ; Somanathan, R. J. Mol. Catal. A
: Chem. 2004, 215, 73. (d) Birabar, D. B.; Gau, H. –M. Tetrahedron: Asymmetry 2008, 19, 733. (e)
Wencel, J.; Rix, D.; Jennequin, T.; Labat, S.; Crévisy, C.; Mauduit, M. Tetrahedron: Asymmetry 2008,
19, 1804.
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