Tunable phosphinite, phosphite and phosphoramidite ligands for the asymmetric hydrovinylation reactions

Article abstract of DOI:10.1016/j.tet.2005.03.120

Only a limited number of ligands have been successfully employed for the Ni-catalyzed asymmetric hydrovinylation reaction. Diarylphosphinites, carrying β-acylamino groups prepared from readily available carbohydrates, in conjunction with highly dissociated counteranions {[(3,5-(CF₃) ₂C₆H₃]₄B^- or SbF ₆^-}, effect the hydrovinylation of vinylarenes under ambient pressure of ethylene with high enantioselectivity. Nitrogen substituents such as -COCF₃ and COPh groups lead to isomerization of the primary products (3-arylbutenes) to Z- and E-2-aryl-2-butenes. In a prototypical synthesis of a 2-arylproionic acid, (S)-3-(4-bromophenyl)-1-butene (89% ee) has be transformed into (R)-ibuprofen by Ni-catalyzed cross-coupling with i-BuMgBr, followed by oxidation of the double bond with NaIO₄ and KMnO ₄. Asymmetric codimerization of norbonene and ethylene using binaphthol-derived phosphoramidites as ligands gives 1:1, 2:1 or polymeric adducts depending on the relative configurations and nature of the BINAP and amine moieties. With one of the phosphoramidite-Ni complexes, counteranions BAr₄^- [Ar=3,5-(CF₃)₂C ₆H₃] and SbF₆^-, which had been used interchangeably in other reactions, give either a 1:1 adduct or a 2:1 adduct, respectively.

Full text of DOI:10.1016/j.tet.2005.03.120

Tetrahedron 61 (2005) 6352–6367
Tunable phosphinite, phosphite and phosphoramidite ligands for
the asymmetric hydrovinylation reactions
*
Haengsoon Park, Ramaiah Kumareswaran and T. V. RajanBabu
Department of Chemistry, The Ohio State University, 100 W. 18th Avenue, Columbus, OH 43210, USA
Received 3 November 2004; revised 21 February 2005; accepted 4 March 2005
Available online 10 May 2005
Abstract—Only a limited number of ligands have been successfully employed for the Ni-catalyzed asymmetric hydrovinylation reaction.
Diarylphosphinites, carrying b-acylamino groups prepared from readily available carbohydrates, in conjunction with highly dissociated
counteranions {[(3,5-(CF3)2C6H3]4BK or SbF6K}, effect the hydrovinylation of vinylarenes under ambient pressure of ethylene with high
enantioselectivity. Nitrogen substituents such as –COCF3 and COPh groups lead to isomerization of the primary products (3-arylbutenes) to
Z- and E-2-aryl-2-butenes. In a prototypical synthesis of a 2-arylproionic acid, (S)-3-(4-bromophenyl)-1-butene (89% ee) has be transformed
into (R)-ibuprofen by Ni-catalyzed cross-coupling with i-BuMgBr, followed by oxidation of the double bond with NaIO4 and KMnO4.
Asymmetric codimerization of norbonene and ethylene using binaphthol-derived phosphoramidites as ligands gives 1:1, 2:1 or polymeric
adducts depending on the relative configurations and nature of the BINAP and amine moieties. With one of the phosphoramidite–Ni
complexes, counteranions BArK4 [ArZ3,5-(CF3)2C6H3] and SbFK6 , which had been used interchangeably in other reactions, give either a 1:1
adduct or a 2:1 adduct, respectively.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
Development of new asymmetric catalytic processes
depends on the availability of enantiomerically pure ligand
precursors that are amenable to fine-tuning for optimum
performance.1 Once the essential features of the ligand
system are identified, substantial modifications in the
scaffolding and in the steric and electronic environments
around the chelating atoms are often necessary to achieve
acceptable levels of catalytic efficiency and enantio-
selectivity. Nowhere is such a strategy more important
than in the discovery of new catalytic processes that involve
the use of relatively stable carbon feedstocks such as HCN,
CO or olefins for selective C–C bond-forming reactions. At
the appropriate stages in the catalytic cycle, the ligand
should promote activation of the substrate(s) and induce
high selectivity in the bond-forming process. Following the
pioneering works of Cullen2 and Selke,3 we have invested
considerable effort in the design and use of readily available
carbohydrates as precursors4 for variety diarylphosphinite
and phospholane5 ligands. Thus electronically tuned
glucose- and fructose-derived phosphinites (e.g., Fig. 1)
were found to be excellent ligands for Ni(0)-catalyzed
asymmetric hydrocyanation of vinylarenes6 and Rh(I)-
Figure 1. Diarylphosphinite ligands for hydrogenation and hydrocyanation
reactions.
catalyzed hydrogenation of dehydroamino acids.7 These
studies also provided some of the first demonstrable
examples8 of electronic tuning of asymmetric catalysts for
not only hydrocyanation and hydrogenation but also
hydroformylation9 and Pd-catalyzed asymmetric allylation
reactions.10
(1)
Keywords: Asymmetric catalysis; Hydrovinylation; Phosphinite; Phos-
phite; Phosphoramidite ligands; Salt effects; Ibuprofen.
As early as 1991, during the initial studies of asymmetric
hydrocyanation we also recognized that the hydroxyl groups
*
Corresponding author. Tel.: C1 614 688 3543; fax: C1 614 292 1685;
e-mail: rajanbabu.1@osu.edu
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.03.120

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
6353
on carbohydrates can be readily converted into phosphite
esters (Eq. 1), and depending on the source of the
(RO)P(OR0)-Cl,11 additional elements of chirality can be
introduced into the ligand.12 As can be expected from such
modular ligands, which combine two chiral fragments, the
sense and extent of asymmetric induction will depend on
whether the two elements are matching or mismatching
(Eq. 2).13 Mono- and bis-phosphites of this structural type
have since been found to have wide applications in
enantioselective Rh-catalyzed hydrogenation reactions.14
phosphite ligands for the asymmetric hydrovinylation
reaction.21 Phosphoramidite ligands are suitable also for
hydrovinylation of norbornene.21b In this instance, dramatic
changes on the course of the reaction with minor changes in
the structure of the ligand and nature of the counteranion
were noticed. The details of this study are also reported
here.22
(3)
(2)
2. Results
2.1. Hydrovinylation of vinylarenes
2.1.1. Ligands from monosaccharides. In our initial
survey of ligands prepared from several monosaccharide
derivatives it became apparent that simple monodentate
diarylphosphinites like 4 and 5 (Fig. 2) were viable ligands
for the hydrovinylation of styrene under our standard
conditions (Eq. 3), where as bidentate bisphosphinites23 like
6, or b-amino-phosphinites like 7 were not.24
Diol for ligand
backbone
(Eq. 1)
(S)
(SS)
(RR)
(R)
%ee (Eq. 2)
49 (S)
13(R) 60(S)
26 (S)
In related developments, Feringa et al. have reported the
synthesis and applications of highly versatile phosphorami-
dite ligands derived from binaphthol and various chiral
amines.15 Mono- and bi-dentate analogs of Feringa’s
ligands have been used in a number of reactions including
hydrogenations,16 conjugate addition reactions,17 and
Ir-catalyzed allylation reactions.18
Among the various ligands we examined, the b-acetamido-
diarylphosphinites (e.g., 5) showed the most promise, and
thus were chosen for further development. The syntheses of
this type of ligands were carried out as follows: inside a
drybox, to a solution of 1 equiv each of the alcohol and
triethylamine in CH2Cl2 is added 1 equiv of the chlorodiar-
ylphosphine6a in CH2Cl2 (Eq. 4). The resulting mixture is
stirred overnight at rt and is subsequently concentrated in
vacuo. The residue is then dissolved in a small amount of
toluene, filtered through a pad of celite to remove the amine
hydrochloride. Further concentration and recrystallization
from cyclohexane or hexane gives the pure ligand.
In a study that is especially relevant to this report, Leitner et
al. found that the Feringa’s phosphoramidites are excellent
ligands for the asymmetric hydrovinylation of vinylarenes.19
Ni-catalyzed asymmetric hydrovinylation is a very demand-
ing reaction with only a limited number of ligands giving
acceptable selectivity for the desired 3-arylbutenes.20 In this
paper, we disclose the full details of our own studies on the
application of carbohydrate-derived phosphinite and
(4)
(5)
Syntheses of the phosphite ligands were accomplished by
adding a solution of the chlorodioxophospholane11a (from
(R/S) binaphthol or (RR/SS)-hydrobenzoin) in CH2Cl2 to an
equimolar mixture of the sugar and 4-dimethylamino-
pyridine (Eq. 5). The mixture is stirred overnight and
subsequently worked up as described before. The pure
Figure 2. Diarylphosphinite ligands for hydrovinylation (yield of
product/ee for hydrovinylation of styrene (Eq. 3) are shown in brackets).

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H. Park et al. / Tetrahedron 61 (2005) 6352–6367
phosphite ligands were obtained by column chromato-
graphy inside the drybox.
were examined, the allo-series (entries 1, 4 and 5) and
gluco-series (entries 2 and 3). In general, outstanding
selectivity for the primary product, 3-aryl-1-butene (2) is
observed with the diarylphosphinite ligands as long as the
N-substituent is an acetyl group (vide infra for other acyl
groups). In overall yield and selectivity, in the phosphinite
series, the allo-derivatives (entry 1) are better than the
gluco-derivatives (entry 2). Whether a 3,5-bis-CH3-C6H3-
substituent or a 3,5-bis-CF3-C6H3-substituent on phos-
phorus is better depends on the configuration of the
carbon to which is attached the diarylphosphinite moiety.
In the gluco-series (entry 2), for both styrene and
4-bromostyrene, the CF3-aromatic substituent is better,
whereas in the allo-series (entry 1) the CH3-aromatic
substituent is clearly superior. In the hybrid ligands carrying
the sugar and the BINAPO moieties, the combination of
the (R)-BINAP and D-gluco appear to give the best yield
and selectivity for styrene hydrovinylation (entries 3 and 4).
The hydrobenzoin-derived phosphite generally gave poor
selectivity, the best result coming from a combination
of (SS)-hydrobenzoin and the D-allopyranoside (entry 5,
ligand 11D).
Typically, the catalyst precursor is prepared by mixing
stoichiometric amounts of allyl nickel bromide dimer and
the ligand (1:1 Ni/L) in CH2Cl2, followed by exchanging
the bromide ion by addition of NaC Ar4BK (ArZ3,5-
(CF3)2-C6H3) or another appropriate Ag salt (Eq. 3). The
precipitated salts are removed by filtration through celite.
Oxygen-free ethylene is then introduced into the flask after
cooling the Ni-complex to the appropriate temperature
(K70 to K55 8C), followed by the substrate dissolved in
CH2Cl2. After w2 h, the reaction is quenched with
ammonium chloride, the product is isolated by evaporation
of the solvent. Selectivity factors are determined by NMR
spectroscopy, GC and HPLC.
2.1.2. Asymmetric hydrovinylation of prototypical vinyl-
arenes. Table 1 shows the yields and ee’s obtained when
various b-acetamidophosphinites are used as ligands for the
Ni(II)-catalyzed asymmetric hydrovinylation of various
vinylarenes (Eq. 3). In this study, two series of sugars
Table 1. Asymmetric hydrovinylation of vinylarenes using phosphinite and phosphite ligandsa
Entry
Ligand
Styrene
%ee
4-Br-styrene
%ee
4-i-Bu-styrene
Yieldb
Yield
Yield
%ee
1.
8A RZCH3
8B RZCF3
89c
95
81 (S)
62 (S)
94
19
89 (S)
43 (S)
99
99
74(S)
59 (S)
2.
9A RZCH3
9B RZCF3
93
93
9 (S)
45(S)
88
13 (S)
47(S)
—
36
—
61(S)
3.
4.
10A Z(R)-BINAPO2
10B Z(S)-BINAPO2
95
26
62(S)
2 (R)
—
—
—
—
—
—
—
—
11A Z(R)-BINAPO2
11B Z(S)-BINAPO2
84
83d
44 (S)
19 (S)
—
—
—
—
99
—
38 (S)
—
5.
11CZ(RR)
11DZ(SS)
53
83
5 (R)
30 (S)
—
—
—
—
—
—
—
—
a For typical reaction conditions see Eq. 3. Yield of 3-arylbutene (2). Selectivity for 2 O99% unless otherwise mentioned.
b Some of the variable yields of 3-phenylbutene reflect the volatility of the product.
c Selectivity 89%; rest 3a.
d Selectivity 83%; rest 3a.

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
6355
Table 2. Asymmetric hydrovinylation of vinylarenes. Effect of N-substituent
Entry Ligand, L Conver. (%)
Selectivity
% 2a
w40
% c/t-3a
% ee (2a)
O99a
w60
87 (S)
12
1.
O99b
O99c
w66
w23
34
77
80 (S)
82 (S)
13
2.
a Conditions: see Eq. 3. 2 mol% [(h3-allyl)NiL]BARF/2 h.
b 3 mol% [(h3-allyl)NiL/BARF]/0.5 h.
c 3 mol% [(h3-allyl)NiL/BARF]/2.0 h.
2.1.3. Effect of N-acyl substituent: isomerization of the
primary product. Having identified 8A (entry1, Table 2) as
the best ligand for hydrovinylation of styrene, 4-bromo-
styrene and 4-isobutylstyrene, we decided to examine the
effect of nitrogen substituents on the course of the reaction.
We find that a seemingly minor change in the N-substituent
has a profound effect on the overall utility of the reaction.
The results obtained upon substituting the –COCH3 group
with –COCF3 and –COPh groups are shown in Table 2.
Even though the N-C(O)CF3 ligand 12 gave 3-phenyl-1-
butene (2a) with one of the highest enantioselectivities we
have observed (87%, entry 1), isomerization of this product
to 2-phenyl-2-butene (3a) significantly erodes the overall
selectivity for the reaction. Ligand 13 with an N-C(O)Ph
group also behaves in a similar fashion. Quenching the
reaction at various times (30 or 120 min) seems to indicate
that both enantiomers of 3-phenylbutenes undergo the
isomerization with nearly equal facility (entry 2).
The results are shown in Table 3. These results confirm the
marginally superior effect of SbF6 as a counteranion in the
hydrovinylation of 4-bromostyrene. Thus the use of Ar4B
resulted in up to 6% formation of the isomerized product 3b,
while SbF6 gave an exquisite reaction with O99%
selectivity for the desired 3-(4-bromophenyl)butene in
89% ee (entry 2). Both BF4 and OTf gave lower conversions
and selectivities under identical conditions (entries 3 and 4).
2.1.5. Asymmetric hydrovinylation of 4-bromostyrene
and identification of the major product. The enantiomeric
excess of 3-(4-bromophenyl)-but-1-ene (2b), a key com-
pound {([a]2D5 C9.9G1 (c 7.02, CHCl3)}, from which
several 2-arylpropionic acids could be prepared by cross-
coupling chemistry (vide infra), was determined by three
independent methods, all agreeing within experimental
error. The ee’s for compound 2b and the corresponding
debrominated derivative, 3-phenyl-1-butene (2a prepared
by treatment of 2b with Mg in MeOH, O99% yield) were
determined by HPLC on chiralcel OJ column. Kumada
coupling of 2b and i-BuMgBr in the presence of 1.6 mol%
of (dppe)NiCl2 gave 2c25 (89%ee, HPLC). Subsequent
ozonolysis and oxidation of the resulting aldehyde26 gave
ibuprofen (Scheme 1), whose configuration and enantio-
meric excess were established by conversion to the known
(K)-menthyl esters.27 Gas chromatographic analysis of
2.1.4. Effect of counteranion. We have previously shown
that counteranions play a very significant role in the
efficiency and selectivity of the hydrovinylation reaction
and there is a synergistic relation between the nature of the
ligand and the counteranion.23,24 The effect of the counter-
anion was examined in the context of hydrovinylation of
4-bromostyrene using the best ligand, 8A.
Table 3. Asymmetric hydrovinylation of vinylarenes. Effect of counteranionsa
Entry
Ligand
Counteranion X
4-Bromostyrene
Conversion (%)
Selectivity (% 3a)
% ee
1
2
3
4
BARF
SbF6
BF4
O99
98
24
94
89 (S)
89 (S)
86 (S)
74 (S)
O99
O99
O99
OTf
70
8A
a Conditions: see Scheme 1, step 1. 1 mol% [(h3-allyl)NiLX]2/CH2Cl2, K55 8C/2 h.

6356
H. Park et al. / Tetrahedron 61 (2005) 6352–6367
Scheme 1. Asymmetric hydrovinylation of 4-bromostyrene.
(K)-menthyl esters of ibuprofen using chiralsil-L-val
column revealed baseline separation, with a diastereomeric
excess of 89% for the (R)-ibuprofen ester. This confirms the
overall selectivity and the absolute configuration of the
primary product of hydrovinylation.
2-(3-bromophenyl)-propionic acid. The diastereomeric
(K)-menthyl esters were analyzed by gas chromatography
(Scheme 2).28 For comparison, authentic samples of
racemic 17 and the corresponding (K)-methyl esters were
prepared from racemic 16.
Hydrovinylation of 3-bromostyrene under these conditions
gave 88% yield of 3-(3-bromophenyl)-but-1-ene (16) with
O99% selectivity for the 3-arylbut-1-ene. The enantio-
selectivity of the product (87% ee, S) was ascertained
by first converting this into (K)-menthyl esters of the
2.1.6. Hydrovinylation of norbornene. In 2003 we
reported that hydrovinylation of norborne is an excellent
reaction giving either a 1:1 (norbornene/ethylene) adduct or
a 2:1 adduct depending on the size of the phosphine that is
employed (Scheme 3).22,29,30 As shown in Scheme 3, a
bulky phosphine, Cy3P (cone angle 1808), gives a 1:1 adduct
whereas a smaller phosphine, Ph3P (cone angle 1458), gave
2:1 adduct. We also reported that 2-benzyloxy-20-diphenyl-
phosphino-1,10-binaphthyl gave w50% ee for the hydro-
vinylation product (K)1831,32(Table 4, entry 1).
In view of the excellent results obtained by Leitner19 on the
use of binaphthol-derived phosphoramidites for the asym-
metric hydrovinylation of styrene derivatives, we decided to
examine these and related ligands for the hydrovinylation of
norbornene under our reaction conditions (Scheme 4). The
results are shown in Table 4.
The selectivities of these reactions under catalysis by
phosphoramidite–Ni complexes (entries 2–7, Table 4) show
remarkable dependence on the counteranion and the nature
of the P–N appendages. Whereas the phosphoramidite 21
Scheme 2. Asymmetric hydrovinylation of 3-bromostyrene.
Scheme 3. Ligand dependence of hydrovinylation of norbornene.

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
Table 4. Asymmetric hydrovinylation of norbornenea
6357
Entry
Ligand, L
Additive
T 8C/t (h)
18 (%)b
19 (%)b
% eec
Comments
Ref. 22
1(a)
1(b)
1(c)
NaBARF
AgSbF6
AgNTf2
K50/2.5
K50/2.0
K50/2.0
69d
O99
O99
0
0
0
44
50
50
20
2(a)
2(b)
2(c)
NaBARF
AgOTf
AgSbF6
K50/2.5
K50/2.5
K50/2.5
O99
20d
0
0
0
O99
80
—
34
—
—
—
21 (RaScSc)
22 (RaRcRc)
23 (RaScSc)
3.
NaBARF
K50/2.5
!2%
0
—
—
4(a)
4(b)
AgSbF6 or
NaBARF
K50/3
K50/3
0
0
0
0
—
—
Polymer
(100%)
Polymer
(100%)
Polymer
(100%)
5
AgSbF6
K50/3
0
0
—
24 (SaScSc)
6(a)
6(b)
AgSbF6 or
NaBARF
K50/2.5
K50/2.5
30
1
35
—
—
—
—
—
25
7(a)
7(b)
AgSbF6 or
NaBARF
K50/2.5
K50/2.5
3
2
28
—
—
—
26
a See Scheme 4 for typical procedure. Results of at least two experiments in each case.
b GC and NMR, isolated yield vary because of volatility of 18.
c By NMR (see text).
d Rest starting material.
(RaScSc) is a good ligand (entry 2a and 2c), the correspond-
ing (RaRcRc)-diastereomer 22 gives less than 2% of the
product (entry 3). For the ligand 21, the counteranion
determines whether 1:1 or 1:2 adduct is produced
(Scheme 3). With NaBARF as the additive, only 1:1 adduct
18 is produced (entry 2a), whereas with AgSbF6, which we
have successfully used in place of NaBARF in some of the
early hydrovinylation experiments (Table 3, entries 1 and
2), the only product is the 2:1 adduct 19, formed in nearly
quantitative yield (entry 2c). Perhaps the most striking result
is the effect of the amine component of the phosphorami-
dites (entries 4 and 5). Thus phosphoramidites derived
from (2S,4S)-diethylpyrrolidine and either (R)-binaphthol
or (S)-binaphthol (23 and 24) give none of the simple
adducts 18 or 19. Nearly quantitative yield of polymeric
Scheme 4. Counteranion dependence of hydrovinylation of norbornene.

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H. Park et al. / Tetrahedron 61 (2005) 6352–6367
Scheme 5. Abbreviated mechanism of asymmetric hydrovinylation and olefin isomerization.
materials were formed under the standard conditions
(entries 6 and 7).33
synergistic relationship between a possible hemilabile
coordination of one of the Ph groups to Ni and each of the
anions could be quite different. In the absence of such a
phenyl group (for example, in ligands, 23 and 24) a more
active catalyst, not unlike the naked nickel catalyst
popularized by Goodall et al. for polymerization of
norbornene, is generated, and polymerization ensues
(Table 4, entries 4, 5).33b Traditionally, these cationic Ni-
complexes have only olefinic ligands and/or Ni–C s-bonds,
and the reaction is done in the presence of highly dissociated
counter anions. Cationic Ni-complexes containing bulky
phosphine ligands have recently been reported to be
effective for non-living polymerization of styrene.36 With-
out additional work, including a full characterization of
the phosphoramide-derived catalyst precursor(s) and the
norbornene polymers they produce, a discussion of the
unusual ligand-dependent selectivity of the Ni(II)-com-
plexes will be highly speculative. Further studies along
these lines will be forthcoming.
Phosphoramidites 25 and 26 are poor ligands and showed no
selectivity in the formation of either the 1:1 or the 2:1
adduct (entry 4). Clearly, AgSbF6 appears to give better
yields.
3. Discussion
While it is premature to propose models23,34 for the
asymmetric induction in any of the studies reported in this
paper, some observations are worthy of note. The diaryl-
phosphinite ligands derived from b-acylaminoalcohols are
useful ligands for hydrovinylation of vinylarenes. The two
asymmetric centers in the backbone, likely variations of the
acyl group and the P-aryl-substituents provide myriad
possibilities for further tuning of these ligands. We have not
conclusively shown that the N-acyl group is the hemilabile
group involved in the reaction. Yet, the complete lack of
`
reactivity of a ligand with a b-amino group vis-a-vis a
4. Conclusions
b-amido (e.g., 7 vs 5, Fig. 2) group and the effect of the
N-acyl groups (Table 2) are highly suggestive of a crucial
role for this functionality.35 It is conceivable that the
[LNi–H]C species, 27 (Scheme 4), which is the presumed
catalyst is more reactive with olefins when an N-C(O)CF3 or
N-C(O)Ph group is present at the b-position of the ligand,
leading to indiscriminate addition–elimination reactions
which results in isomerization of the primary product 2a
(Scheme 5).
Diarylphosphinites, carrying a b-acylamino groups pre-
pared from readily available carbohydrates, in conjunction
with highly dissociated counterions {[(3,5-(CF3)2C6H3]4BK
or SbFK6 }, effect the hydrovinylation of vinylarenes
under ambient pressure of ethylene with the high
enantioselectivity. Nitrogen substituents such as –COCF3
and COPh groups lead to isomerization of the primary
products (3-arylbutenes) to Z- and E-2-aryl-2-butenes. The
intermediate 3-arylbutenes are useful for the synthesis
of anti-inflammatory 2-arylpropionic acids. Asymmetric
codimerization of norbonene and ethylene using binaphthol-
derived phosphoramidites as ligands gives 1:1, 2:1 or
polymeric adducts depending on the relative configurations
and nature of the BINAP and amine moieties. With one of
Another notable observation is the counteranion effect
seen in the hydrovinylation of norbornene using ligand 21
(Table 4, entry 2). At present we have no explanation for the
fact that BARF anion gives a 1:1 adduct, 18, and SbF6 a 2:1
adduct, 19 (Scheme 3). However, one can speculate that the

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
6359
the phosphoramidite–Ni complexes, counteranions BAr4K
[ArZ3,5-(CF3)2C6H3] and SbFK6 , which had been used
interchangeably in other reactions, give either a 1:1 adduct
or a 2:1 adduct, respectively.
precursors benzyl 2-acetamido-2-deoxy-4,6-O-phenyl-
methyl-a-D-glucopyranoside,38 2-amino-2-deoxy-4,6-O-
phenylmethyl-a-D-glucopyranoside,38 benzyl 2-acetamido-
2-deoxy-4,6-O-phenylmethyl-a-D-allopyranoside,39 diaryl-
phosphinite ligand 6,6a phosphoramidites ligands40 21 and
22, 4-i-butylstyrene,41 NaBAr4 (ArZ3,5-(CF)3–C6H3).42
5. Experimental
5.2. Synthesis of phosphinite and phosphite ligands
5.1. General procedures
The preparations of all air-sensitive trivalent phosphorus
compounds were carried out under an inert atmosphere of
nitrogen in a Vacuum Atmospheres drybox. Since air-
sensitive phosphorus compounds result in poor C, H-analy-
Reactions requiring air-sensitive manipulations were con-
ducted under an inert atmosphere of nitrogen in a Vacuum
Atmospheres drybox or by using Schlenk techniques.
Methylene chloride and toluene were distilled from calcium
hydride under nitrogen and stored over molecular sieves.
Tetrahydrofuran, diethyl ether, and hexane were distilled
under nitrogen from sodium/benzophenone ketyl. Ethylene
(99.5%) was purchased from Matheson Inc., and passed
through Drierite before use. Styrene was purchased from
Aldrich, vacuum-transferred, and stored at K30 8C. For
ozonolysis, ozone gas was delivered using a Welsbach
ozone generator. Analytical TLC was performed on E.
Merck precoated (0.25 mm) silica gel 60 F254 plates. Flash
column chromatography was carried out on silica gel 40
(Scientific Adsorbents Incorporated, Microns Flash). Gas
chromatographic analyses were performed on a Hewlett-
Packard 5890 equipped with an HP-ultra-1 crosslinked
methyl silicone capillary column (25 m length!0.2 mm
i.d.) and a FID detector connected to a HP 3396 integrator.
Helium was used as the carrier gas. Chiral gas chromato-
graphic separations of the (K)-menthol esters 2-aryl-
propionic acids were accomplished using Chirasil-L-Val
on WCOT fused silica (25 m!0.25 mm, 0.12 mm film
thickness) capillary GC column purchased from Chrompack
(1130 Route 202 South Raritan, New Jersey 08869). The
absolute configuration of 3-phenyl-1-butene was deter-
mined by GC analysis using a 50 m Lipodex C capillary
column (conditions: 1.5 mL helium/min, 35 oC (50 min),
0.1 8C/min (60 min), 41 8C (30 min); retention times:
R-isomer 95.8 min, S-isomer 97.2 min). Determination of
the configuration of other compounds is described under the
appropriate experiments. Enantiomeric excesses of 3-aryl-
1-butenes were determined by HPLC using a Daicel
Chiralcel OJ column using hexane as the solvent where
base-line separation was obtained. Optical rotations were
recorded on a Perkin–Elmer Model 241 polarimeter at the
sis, the purities of the ligands were confirmed by 1H and 31
P
NMR, and in most instances the ligands are O95% pure.
The phosphinite ligands were synthesized according to one
of the following procedures unless stated otherwise.6a
Procedure A. To a solution of 1.0 equiv of a chlorodi-
arylphosphine and 1.0 equiv of 4-dimethylaminopyridine
(DMAP) in toluene (5 mL) was added dropwise 1.0 equiv of
the alcohol in toluene (2 mL). The mixture was stirred for
6–10 h at rt and filtered through a short pad of Celite to
remove the precipitated DMAP$HCl. The filtrate was
concentrated to dryness in vacuo, and the crude product
was recrystallized from cyclohexane and/or hexane inside
the drybox to afford the corresponding phosphinite as a
white crystalline solid.
Procedure B. To a solution of 1 equiv of an alcohol and
1 equiv of triethylamine (TEA) or DMAP in dichloro-
methane (5 mL) was added dropwise 1 equiv of a
chlorodiarylphosphine in dichloromethane (2 mL). The
resulting mixture was stirred overnight at rt and was
concentrated in vacuo. The residue was suspended in a small
amount of toluene, filtered through a short pad of Celite to
remove TEA hydrochloride or DMAP hydrochloride, and
then was concentrated to dryness in vacuo. The crude
product was purified by recrystallization inside the drybox
from cyclohexane and/or hexane to afford the corresponding
phosphinite as a white crystalline solid.
Procedure C. To a solution of 1 equiv of an alcohol and
1 equiv of DMAP in dichloromethane (5 mL) was added,
dropwise, 1 equiv of chlorodiarylphosphonite in dichloro-
methane (2 mL). The resulting mixture was stirred
overnight at rt and concentrated in vacuo. The residue
was suspended in a small amount of toluene, filtered
through a short pad of Celite to remove DMAP hydro-
chloride, and then concentrated to dryness in vacuo. The
crude product was chromatographed (inside drybox) to
afford the corresponding phosphite as a white crystalline
solid.
˚
sodium D line in chloroform treated with 4 A molecular
sieves. Compounds for which an exact mass is reported
exhibited no significant peaks at m/z greater than that of the
parent. Elemental analyses were done by Atlantic Microlab,
Inc., Norcross, GA.
Starting materials diphenylchlorophosphine, 2-acetamido-
2-deoxy-a-D-glucopyranose, 1,2:5,6-O-diisopropylidene-D-
glucofuranose, (S,S)-(K)-hydrobenzoin and (R,R)-(C)-
hydrobenzoin, 4-bromostyrene, 3-bromostyrene, 2-vinyl-
naphthalene, norbornene and (K)-menthol and various
silver salts were purchased from commercial sources. The
following compounds were prepared by the procedures from
the references cited: chloro-bis-[3,5-di-(trifluoromethyl)-
phenyl]phosphine,4a chloro-bis-(3,5-dimethylphenyl)phos-
phine,4a chloro-dioxophospholanes11a from binaphthol and
hydroxybenzoin, (R)- and (S)-binaphthols,37 sugar
5.2.1. 3-O-[bis-(a,a,a,a0,a0,a0-Hexafluoro-3,5-xylyl)phos-
phino]-1,2:5,6-di-O-isopropylidene-a-D-glucofuranose
1
[4, ArZ3,5-(CF3)2C6H3)]. Procedure B. 73% Yield; H
NMR (300 MHz, CDCl3) d 8.00–7.90 (m, 6H, aromatic),
5.92 (d, JZ3.6 Hz, 1H), 4.63 (dd, JZ3.6, 1.8 Hz, 1H), 4.54
(dd, JZ9.1, 2.7 Hz, 1H), 4.25–4.20 (m, 1H), 4.14–4.02
(m, 3H), 1.51 (s, 3H, Me), 1.40 (s, 3H, Me), 1.30 (s, 3H, Me)
1.17 (s, 3H, Me); 31P NMR (101 MHz, CDCl3) d 105.8
(s, 1P).

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H. Park et al. / Tetrahedron 61 (2005) 6352–6367
5.2.5. Benzyl0 2-acetamido-4,6-O-benzylidene-3-O-[bis-
(a,a,a,a0,a0,a -hexafluoro-3,5-xylyl)phosphino]-2-deoxy-
a-D-allopyranoside (8B). Procedure B. 75% Yield; 1H
NMR (300 MHz, CDCl3) d 8.45–6.94 (m, 16H, aromatic),
5.62 (d, JZ8.5 Hz, 1H, NH), 5.46 (s, 1H, benzylic), 4.89 (d,
JZ4.8 Hz, 1H, H-1), 4.88 and 4.70 (AB, JZ12.0 Hz, 2H,
OCH2Ph), 4.75 (m, 1H, H-3), 4.39–4.17 (m, 3H, H-2, H-5,
H-6eq), 3.75 (dd, JZ9.5, 2.6 Hz, 1H, H-4), 3.67 (t, JZ
10.2 Hz, 1H, H-6ax), 1.56 (s, 3H, CH3CO); 31P NMR
(101 MHz, CDCl3) d 106.9 (s, 1P).
5.2.2. Methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-
O-(di-3,5-xylylphosphino)-b-D-glucopyranoside [5, ArZ
3,5-(CH3)2C6H3)]. Procedure B. 92% Yield; 1H NMR
(300 MHz, CDCl3) d 7.51–6.82 (m, 11H, aromatic), 5.46 (s,
1H, benzylic), 5.24 (br d, JZ8.0 Hz, 1H, NH), 4.91 (d, JZ
8.3 Hz, 1H, H-1), 4.66 (td, JZ9.4, 9.1 Hz, 1H, H-3), 4.36
(dd, JZ10.4, 4.9 Hz, 1H, H-6eq), 3.77 (t, JZ10.2 Hz, 1H,
H-6ax), 3.75 (t, JZ9.2 Hz, 1H, H-4), 3.59–3.44 (m, 2H,
H-2, H-5), 3.49 (s, 3H, OMe), 2.29 (s, 6H, 2Me), 2.06 (s, 6H,
2Me), 1.59 (s, 3H, CH3CO); 31P NMR (101 MHz, CDCl3) d
120.9 (s, 1P).
5.2.6. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-
O-(di-3,5-xylylphosphino)-a-D-glucopyranoside (9A).
Procedure B. 92% Yield; H NMR (300 MHz, CDCl3) d
1
7.37–6.82 (m, 16H, aromatic), 5.53 (br d, JZ9.2 Hz, 1H,
NH), 5.44 (s, 1H, benzylic), 4.95 (d, JZ3.6 Hz, 1H, H-1),
4.71 and 4.45 (AB, JZ11.8 Hz, 2H, OCH2Ph), 4.48 (td, JZ
10.1, 3.6 Hz, 1H, H-2), 4.35 (td, JZ9.5, 9.2 Hz, 1H, H-3),
4.23 (dd, JZ10.1, 4.6 Hz, 1H, H-6eq), 3.93 (td, JZ9.8,
4.6 Hz, 1H, H-5), 3.78 (t, JZ9.1 Hz, 1H, H-4), 3.76 (t, JZ
10.1 Hz, 1H, H-6ax), 2.30 (s, 6H, 2Me), 2.07 (s, 6H, 2Me),
1.50 (s, 3H, CH3CO); 31P NMR (101 MHz, CDCl3) d 120.8
(s, 1P)
5.2.3. Methyl 4,6-O-benzylidene-3-O-[bis(a,a,a,a0,a0,a0-
hexafluoro-3,5-xylyl)phosphino]-2-deoxy-2-(ethyl-
amino)-b-D-glucopyranoside (7, ArZ3,5-(CF3)2C6H3).
1
Procedure B. 90% Yield; H NMR (300 MHz, CDCl3) d
7.97–7.05 (m, 11H, aromatic), 5.30 (s, 1H, benzylic), 5.10
(d, 8 Hz), 4.38–4.31 (m, 2H), 4.13 (m, 1H), 3.81–3.71 (m,
2H), 3.56 (s, 3H, OMe), 3.43 (m, 1H), 2.87–2.78 (m, 2H),
2.45 (m, 1H), 0.82 (t, 3H, CH3); 31P NMR (101 MHz,
CDCl3) d 106.2 (s, 1P).
5.2.7. Benzyl0 2-acetamido-4,6-O-benzylidene-3-O-[bis-
(a,a,a,a0,a0,a -hexafluoro-3,5-xylyl)phosphino)-2-deoxy-
a-D-glucopyranoside (9B). Procedure B. 89% Yield;
1H NMR (300 MHz, C6D6) d 8.40–6.84 (m, 16H, aromatic),
5.10 (s, 1H, benzylic), 5.00 (br d, JZ10.0 Hz, 1H, NH), 4.71
(td, JZ10.2, 3.8 Hz, 1H, H-2), 4.61 (d, JZ3.8 Hz, 1H, H-1),
4.31 and 3.98 (AB, JZ11.6 Hz, 2H, OCH2Ph), 4.26 (m, 1H,
H-3), 4.00 (m, 1H, H-6eq), 3.86 (td, JZ9.8, 4.9 Hz, 1H,
H-5), 3.40 (t, JZ10.2 Hz, 1H, H-4), 3.34 (t, JZ9.3 Hz, 1H,
H-6ax), 1.13 (s, 3H, CH3CO); 31P NMR (101 MHz, C6D6) d
105.8 (s, 1P).
5.2.4. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-
O-(di-3,5-xylylphosphino)-a-D-allopyranoside (8A).
Procedure B. 90% Yield; H NMR (300 MHz, CDCl3) d
7.51–6.97 (m, 16H, aromatic), 5.59 (d, JZ8.5 Hz, 1H, NH),
5.56 (s, 1H, benzylic), 4.85 and 4.53 (AB, JZ12.0 Hz, 2H,
OCH2Ph), 4.84 (d, JZ3.9 Hz, 1H, H-1), 4.60–4.42 (m, 2H,
H-2, H-3), 4.39–4.23 (m, 2H, H-5, H-6eq), 3.77–3.69 (m,
2H, H-4, H-6ax), 2.18 (s, 6H, 2Me), 2.16 (s, 6H, 2Me), 1.34
(s, 3H, CH3CO);31PNMR (101 MHz, CDCl3) d 123.6(s, 1P).
1
5.2.8. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-a-
D-glucopyrano-side cyclic (R)-[1,10-binaphthalene]-2,20-
diyl Phosphite (10A). Procedure C. 70% Yield; H NMR
1
(300 MHz, CDCl3) d 7.99–7.20 (m, 22H, aromatic), 5.80
(d, JZ9.4 Hz, 1H, NH), 5.56 (s, 1H, benzylic), 4.98 (d, JZ
3.5 Hz, 1H, H-1), 4.72 and 4.48 (AB, JZ11.7 Hz, 2H,
OCH2Ph), 4.61–4.44 (m, 2H, H-2, H-3), 4.27 (dd, JZ10.1,
4.7 Hz, 1H, H-6eq), 3.91 (td, JZ9.9, 4.7 Hz, 1H, H-5), 3.74
(t, JZ10.2, 1H, H-6ax), 3.71 (t, JZ9.2 Hz, 1H, H-4), 2.09
(s, 3H, CH3CO); 31P NMR (101 MHz, CDCl3) d 148.2
(s, 1P).

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
6361
1H), 4.19–4.09 (m, 2H), 3.66–3.36 (m, 2H), 1.71 (s, 3H,
CH3CO); 13C NMR (101 MHz, CDCl3) d 170.1, 137.6,
137.5, 137.3, 136.7, 136.7, 129.5, 129.1, 129.0, 128.8,
128.8, 128.6, 128.3, 127.0, 102.5, 96.8, 87.4, 82.8, 77.6,
70.8, 70.0, 69.8, 69.5, 58.5, 49.5; 31P NMR (101 MHz,
CDCl3) d 144.0 (s, 1P).
5.2.9. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-a-
D-glucopyranoside cyclic (S)-[1,10-binaphthalene]-2,20-
diyl phosphite (10B). Procedure C. Quantitative yield; H
1
NMR (300 MHz, CDCl3) d 7.94–7.14 (m, 22H, aromatic),
5.67 (s, 1H, benzylic), 5.55 (d, JZ9.1 Hz, 1H, NH), 4.97 (d,
JZ3.7 Hz, 1H, H-1), 4.73 and 4.48 (AB, JZ11.7 Hz, 2H,
OCH2Ph), 4.52 (q, JZ9.7 Hz, 1H, H-3), 4.38–4.25 (m, 2H,
H-2, H-6eq), 3.99 (td, JZ9.9, 4.7 Hz, 1H, H-5), 3.85 (t, JZ
10.2 Hz, 1H, H-6ax), 3.77 (t, JZ9.3 Hz, 1H, H-4), 1.78 (s,
3H, CH3CO); 31P NMR (101 MHz, CDCl3) d 150.9 (s, 1P).
5.2.13. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-
a-D-allopyranoside cyclic (S,S)-1,2-diphenylethylene
phosphite (11D). Procedure C. 83% Yield; 1H NMR
(250 MHz, CDCl3) d 7.45–6.83 (m, 20H, aromatic), 6.06 (d,
JZ9.5 Hz, 1H, NH), 5.54 (s, 1H, benzylic), 4.93 (d, JZ
9.2 Hz, 1H), 4.80–4.68 (m, 3H), 4.52 and 4.27 (AB, JZ
11.7 Hz, 2H, OCH2Ph), 4.37–4.15 (m, 3H), 3.72–3.64 (m,
2H), 1.82 (s, 3H, CH3CO); 13C NMR (101 MHz, CDCl3) d
170.2, 138.1, 137.6, 137.5, 137.0, 136.9, 129.6, 129.0,
128.9, 128.9, 128.7, 128.6, 128.5, 128.3, 127.4, 127.3,
126.9, 102.7, 97.7, 87.3, 83.7, 71.5, 71.1, 70.9, 69.7, 66.3,
58.8, 49.7; 31P NMR (101 MHz, CDCl3) d 144.9 (s, 1P).
5.2.10. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-
a-D-allopyranoside cyclic (R)-[1,10-binaphthalene]-2,20-
diyl phosphite (11A). Procedure C. 80% Yield; H NMR
1
(300 MHz, CDCl3) d 7.98–6.86 (m, 22H, aromatic), 5.78 (d,
JZ9.5 Hz, 1H, NH), 5.71 (s, 1H, benzylic), 4.86 (dt, JZ9.5,
3.0 Hz, 1H, H-2), 4.78 (d, JZ4.5 Hz, 1H, H-1), 4.58 and
4.30 (AB, JZ12.2 Hz, 2H, OCH2Ph), 4.45–4.27 (m, 3H,
H-3, H-5, H-6eq), 3.84–3.75 (m, 2H, H-4, H-6ax), 1.67 (s,
3H, CH3CO); 31P NMR (101 MHz, CDCl3) d 156.0 (s, 1P).
5.2.14. Benzyl 4,6-O-benzylidene-2-deoxy-3-O-(di-3,5-
xylylphosphino)-2-(2,2,2-trifluoroacetamido)-a-D-allo-
pyranoside (12). Procedure B. 81% Yield; 1H NMR
(400 MHz, CDCl3) d 7.29–6.90 (m, 16H, aromatic), 6.46
(d, JZ9.4 Hz, 1H, NH), 5.47 (s, 1H, benzylic), 4.82 (d, JZ
4.3 Hz, 1H, H-1), 4.80 and 4.51 (AB, JZ12.0 Hz, 2H,
OCH2Ph), 4.53 (m, 1H, H-3), 4.41 (td, JZ10.2, 5.1 Hz, 1H,
H-5), 4.26 (dt, JZ9.5, 3.9 Hz, 1H, H-2), 4.19 (dd, JZ10.3,
5.2 Hz, 1H, H-6eq), 3.68–3.64 (m, 2H, H-4, H-6ax), 2.12 (s,
6H, 2Me), 2.08 (s, 6H, 2Me); 13C NMR (101 MHz, CDCl3)
d 145.1, 144.6, 141.0, 140.1, 139.8, 139.6, 134.4, 133.3,
131.5, 131.3, 130.9, 130.8, 130.7, 130.6, 130.4, 130.1,
129.9, 129.0, 104.7, 98.2, 80.8, 72.9, 71.8, 68.5, 61.0, 52.3,
23.9, 23.8; 31P NMR (162 MHz, CDCl3) d 126.1 (s, 1P).
5.2.11. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-
a-D-allopyranoside cyclic (S)-[1,10-binaphthalene]-2,20-
diyl phosphite (11B). Procedure C. 88% Yield; H NMR
1
(250 MHz, CDCl3) d 7.82–6.88 (m, 22H, aromatic), 6.09 (d,
JZ9.4 Hz, 1H, NH), 5.54 (s, 1H, benzylic), 4.79 (dt, JZ8.7,
2.9 Hz, 1H, H-2), 4.72 (d, JZ4.4 Hz, 1H, H-1), 4.43 and
4.24 (AB, JZ12.5 Hz, 2H, OCH2Ph), 4.34 (m, 1H, H-3),
4.08–3.98 (m, 2H, H-5, H-6eq), 3.64–3.57 (m, 2H, H-4,
H-6ax), 1.97 (s, 3H, CH3CO); 13C NMR (71.6 MHz,
CDCl3) d 169.3, 148.1, 147.4, 137.4, 137.3, 132.8, 131.5,
130.9, 130.3, 129.3, 129.2, 128.4, 128.3, 128.3, 128.2,
127.5, 127.2, 127.1, 127.0, 126.6, 126.3, 126.2, 126.0,
125.0, 124.9, 121.9, 121.9, 121.5, 101.6, 96.4, 77.2, 71.6,
71.4, 69.8, 68.9, 57.7, 48.9, 48.9; 31P NMR (101 MHz,
CDCl3) d 150.6 (s, 1P).
5.2.15. Benzyl 2-benzamido-4,6-O-benzylidene-2-deoxy-
3-O-(di-3,5-xylylphosphino)-a-D-allopyranoside (13).
Procedure B. 77% Yield; H NMR (250 MHz, CDCl3) d
1
7.34–6.82 (m, 21H, aromatic), 6.35 (d, JZ9.2 Hz, 1H, NH),
5.45 (s, 1H, benzylic), 4.89 (d, JZ4.2 Hz, 1H, H-1), 4.70
and 4.48 (AB, JZ12.0 Hz, 2H, OCH2Ph), 4.61–4.41 (m,
3H, H-2, H-3, H-5), 4.17 (dd, JZ10.2, 5.2 Hz, 1H, H-6eq),
3.72–3.61 (m, 2H, H-4, H-6ax), 2.07 (s, 6H, 2Me), 1.99 (s,
6H, 2Me); 13C NMR (101 MHz, CDCl3) d 166.8, 144.0,
142.9, 138.8, 138.1, 138.9, 137.6, 133.7, 131.9, 131.8,
130.9, 129.1, 128.9, 128.7, 128.6, 128.4, 128.3, 128.2,
128.1, 127.8, 127.5, 127.2, 126.8, 102.5, 97.3, 78.8, 70.7,
70.7, 66.3, 58.9, 50.3, 21.7, 21.6; 31P NMR (101 MHz,
5.2.12. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-
a-D-allopyranoside cyclic (R,R)-1,2-diphenylethylene
phosphite (11C). Procedure C. 84% Yield; 1H NMR
(250 MHz, CDCl3) d 7.36–7.03 (m, 20H, aromatic), 5.99 (d,
JZ9.45 Hz, 1H, NH), 5.47 (s, 1H, benzylic), 5.19 (d, JZ
9.6 Hz, 1H), 4.82 (d, JZ4.5 Hz, 1H), 4.76 and 4.54 (AB,
JZ12.2 Hz, 2H, OCH2Ph), 4.68–4.63 (m, 2H), 4.35 (m,

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H. Park et al. / Tetrahedron 61 (2005) 6352–6367
CDCl3) d 123.6 (s, 1P).
over magnesium sulfate, analyzed by GC to determine the
conversion of the substrate. 1H NMR spectra was also used
to determine the isomeric rations. The organic extract was
concentrated under reduced pressure to afford the corre-
sponding hydrovinylation product. Enantiomeric excesses
were determined by HPLC using a Daicel Chiralcel OJ
column eluting with hexane (0.3–0.6 mL/min) for styrene
derivatives.
Procedure C. Use of AgSbF6 and AgBF4 in Ni-catalyzed
hydrovinylations of 4-bromostyrene (Table 3). A solution of
0.0050 equiv of [Ni(allyl)Br]2 and 0.010 equiv of ligand 8A
in dichloromethane (3 mL) was stirred for 30 min at rt and
then added to a suspension of 0.011 equiv of a silver salt in
dichloromethane (2 mL). The resulting brown suspension
was stirred for 5 min, filtered through a short pad of celite
into a Schlenk flask, and then taken out of the drybox.
Oxygen-free ethylene (z1 atm) was introduced into the
yellow-brown catalyst solution at K55 8C, and 1.0 mmol of
4-bromostyrene was added dropwise via a syringe. The
resulting reaction mixture was stirred for 2 h at K55 8C
under an ethylene atmosphere (z1 atm), quenched with
half-saturated aqueous ammonium chloride (5 mL), and
extracted with dichloromethane (50 mL). The concentrated
solution was analyzed as described before.
5.3. Hydrovinylation reactions
The preparations of all hydrovinylation catalysts were
carried out under a nitrogen atmosphere in a Vacuum
Atmospheres drybox. The hydrovinylation reactions were
conducted under an inert atmosphere of nitrogen using
Schlenk techniques.
Procedure A. Use of triphenylphosphine and AgOTf23. The
following is a typical procedure for the Ni(II)-catalyzed
hydrovinylation reactions. To a red solution of 0.0035 equiv
of [Ni(allyl)Br]2 in dichloromethane (1.5 mL) was added a
solution of 0.0070 equiv of triphenylphosphine in dichloro-
methane (1.5 mL). Then, the resulting yellow solution was
added to a suspension of 0.0080 equiv of silver triflate in
dichloromethane (2 mL). After 1.5 h of stirring at rt, the
brown suspension was filtered through a short pad of Celite
into a Schlenk flask, removed from the drybox, and cooled
to K55 8C. Oxygen-free ethylene (z1 atm) was then
introduced into the yellow catalyst solution, and 1.0 mmol
of a hydrovinylation substrate was added dropwise through
a rubber septum with a syringe. The resulting reaction
mixture was stirred for 2 h at K55 8C under an ethylene
atmosphere (z1 atm), quenched with half-saturated
aqueous ammonium chloride solution (5 mL), and product
was extracted with diethyl ether or dichloromethane
(50 mL). The organic phase was dried over magnesium
sulfate, analyzed by GC to determine the conversion of the
substrate, and concentrated under reduced pressure to afford
the corresponding hydrovinylation product.
5.3.1. [(S)-1-Methylallyl]benzene. Procedure B (LZ8A).
0.030 equiv of catalyst used; reaction temperature: K70 oC;
quantitative yield (89% of 3-phenylbut-1-ene), eeZ81%
1
(S); H NMR (300 MHz, CDCl3) of 3-phenylbut-1-ene: d
7.37–7.21 (m, 5H, aromatic), 6.06 (ddd, JtransZ17.0 Hz,
JcisZ10.3 Hz, JZ6.5 Hz, 1H), 5.10 (dt, JtransZ17.1 Hz,
JZ1.6 Hz, 1H), 5.07 (dt, JcisZ10.3 Hz, JZ1.5 Hz, 1H),
3.51 (m, 1H), 1.41 (d, JZ7.0 Hz, 3H); NMR spectra of
minor impurities useful for determining selectivity: (E)-2-
phenylbut-2-ene: d 7.41–7.20 (m, 5H, aromatic), 5.89 (qq,
JZ6.9, 1.4 Hz, 1H), 2.07 (m, 3H), 1.82 (dq, JZ6.8, 1.2 Hz,
3H); (Z)-2-phenylbut-2-ene: d 7.41–7.20 (m, 5H, aromatic),
5.58 (qq, JZ6.9, 1.4 Hz, 1H), 2.07 (m, 3H), 1.62 (dq, JZ
6.8, 1.5 Hz, 3H).
The absolute configuration of 3-phenyl-1-butene was
determined by GC analysis using a 50 m Lipodex C
capillary column25 [conditions: 1.5 mL helium/min, 35 8C
(50 min), 0.1 8C/min (60 min), 41 8C (30 min); retention
times: R-isomer 95.8 min, S-isomer 97.2 min].
Procedure B. Typical for asymmetric hydrovinylation
reactions. The following is a typical procedure for the
Ni(II)-catalyzed asymmetric hydrovinylation reactions of
norbornene and 4-bromostyrene using NaBARF as the
additive. To a red solution of 0.01 equiv of [Ni(allyl)Br]2 in
dichloromethane (1.5 mL) was added a solution of
0.021 equiv of a chiral phosphorus ligand (L) in dichloro-
methane (1.5 mL). Then, the resulting orange solution was
added to a suspension of 0.029 equiv of the additive in
dichloromethane (2 mL). The mixture was stirred for 1.5 h
at rt, filtered through a short pad of celite into a Schlenk
flask, and taken out of the drybox. Oxygen-free ethylene
(z1 atm) was then introduced to the orange catalyst
solution at the appropriate temperatures shown in Tables 3
and 4. The hydrovinylation substrate (1 mmol) was added
dropwise via a syringe. The resulting reaction mixture was
stirred for the indicated times at low temperature under an
ethylene atmosphere (z1 atm). The reaction was quenched
with half-saturated aqueous ammonium chloride (5 mL),
and the product was extracted with diethyl ether or
dichloromethane (50 mL). The organic layer was dried
5.4. Reactions using ligands 12 and 13 with b-
NHC(O)CF3 and b-NHC(O)Ph groups (Table 2)
Procedure B (LZ12). 0.020 equiv of catalyst used; O99%
yield (40% of (S)-3-phenylbut-1-ene, 60% of (E)- and (Z)-2-
phenylbut-2-ene); eeZ87% (S).
Procedure B (LZ13, 30 min.): 0.030 equiv of catalyst used;
O99% yield (66% of (S)-3-phenylbut-1-ene, 34% of (E)-
and (Z)-2-phenylbut-2-ene); eeZ80% (S).
Procedure B (LZ13, 120 min): 0.030 equiv of catalyst
used; O99% yield (23% of (S)-3-phenylbut-1-ene, 77% of
(E)- and (Z)-2-phenylbut-2-ene); eeZ82% (S).
5.4.1. 1-Bromo-4-[(S)-1-methylallyl]benzene (2b).

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
6363
Procedure B (LZ8A, SbF6 counteranion). 0.010 equiv of
catalyst used; quantitative yield (w98% yield of 3-(4-
bromophenyl)but-1-ene, eeZ89% (S)); 1H NMR
(300 MHz, CDCl3) of 3-(4-bromophenyl)but-1-ene d
7.48–7.40 (m, 2H, aromatic), 7.12–7.06 (m, 2H, aromatic),
5.97 (ddd, JtransZ17.7 Hz, JcisZ9.8 Hz, JZ6.4 Hz, 1H),
5.05 (dt, JtransZ17.6 Hz, JZ1.5 Hz, 1H), 5.05 (dt, JcisZ
9.9 Hz, JZ1.5 Hz, 1H), 3.44 (quin, JZ6.9 Hz, 1H), 1.35 (d,
JZ7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) d 152.2,
150.3, 139.1, 136.7, 127.5, 121.3, 50.3, 28.3; Purity by GC
and NMR O98%; Anal. Found (calcd) C 57.00 (56.90), H
5.30 (5.25), Br 37.72 (37.85); [a]1D8 C9.9G0.1 (c 7.02,
CHCl3).
stirring was continued for 1 h at 0 8C and for another hour at
rt. It was concentrated under reduced pressure, diluted with
water, and extracted with petroleum ether (bp 40–60 8C).
The organic extract was washed with saturated aqueous
sodium bicarbonate, dried over magnesium sulfate, and
concentrated to dryness in vacuo to afford 153 mg (96%) of
the intermediate aldehyde as a colorless oil. The crude
product was used for the next step without further
purification.
To a suspension of aldehyde from the above step (100 mg,
0.67 mmol) and magnesium sulfate (123 mg, 0.5 mmol) in
acetone (15 mL) was added dropwise a solution of
potassium permanganate (116 mg, 0.734 mmol) in acetone
(10 mL) for 30 min. The resulting mixture was stirred for
2 h at rt, and the solvent was removed under reduced
pressure. The residue was extracted with hot water (3!
20 mL) and filtered. The filtrate was washed with chloro-
form (10 mL), acidified with 1 N aqueous hydrochloric acid
to pH 2, and then extracted with chloroform (3!30 mL).
The combined organic extracts were dried over magnesium
sulfate and concentrated to dryness in vacuo to afford 70 mg
(66%) of 14 as an off white solid. To ascertain the absolute
configuration and the enantioselectivity, the crude product
14 (0.5 mg in 100 mL of dichloromethane) was converted to
the corresponding ibuprofen (K)-menthyl esters by mixing
with 100 mL of an esterification solution, prepared as
described below, and then stirring the resulting mixture
for 30 min. The esterification solution was prepared by
dissolving 3.5 g of (K)-menthol, 0.12 g of dicyclohexyl-
carbodiimide, 6 mg of 4-dimethylaminopyridine, and 25 mL
of 1 M HCl in 1 mL of dichloromethane. The diastereo-
meric menthyl esters were analyzed by GC on a Chirasil-L-
Val column (conditions: 150 8C; retention times: R-acid
ester 29.9 min, S-acid ester 30.9 min). The major acid
isomer was identified as R-ibuprofen (89% ee) by
comparison of retention times with that of authentic
samples. Correspondingly, the olefin product, 2c (3-(4-
isobutylphenyl)-but-1-ene), was established as having the S
configuration.
5.4.2. 1-Isobutyl-4-[(S)-1-methylallyl]benzene (2c).
Procedure B (LZ8A). 0.020 equiv of catalyst used;
quantitative yield; eeZ74% (S); 1H NMR (300 MHz,
CDCl3) d 7.14–7.05 (m, 4H, aromatic), 6.01 (ddd, Jtrans
17.0 Hz, JcisZ10.3 Hz, JZ6.5 Hz, 1H), 5.05 (dt, Jtrans
Z
Z
17.2 Hz, JZ1.6 Hz, 1H), 5.02 (dt, JcisZ10.3 Hz, JZ
1.5 Hz, 1H), 3.45 (m, 1H), 2.44 (d, JZ7.2 Hz, 2H), 1.85
(sept, JZ6.8 Hz, 1H), 1.35 (d, JZ7.0 Hz, 3H), 0.91 (d, JZ
6.0 Hz, 6H); 13C NMR (101 MHz, CDCl3) d 144.0, 143.2,
139.8, 129.5, 127.3, 113.2, 45.5, 43.2, 30.6, 22.8, 21.2);
Purity by GC and NMR: O99%; [a]1D8 C6.8G0.1(c 2.1,
CHCl3).
5.4.3. Conversion to 2b to 2a [(S)-1-methylallyl]benzene.
In a Schlenk flask was charged compound 2b (45 mg,
0.21 mmol) in methanol (6 mL) and attached a vigreux
column with a balloon of nitrogen. Mg turnings (350 mg)
were added in small portion, and stirring was continued for
1 d at rt. The reaction mixture was diluted with diethyl ether
(30 mL) and water (5 mL). The organic layer was dried
over magnesium sulfate, and concentrated under reduced
pressure to afford 25 mg (89%) of 3-phenyl-1-butene as a
colorless oil. The product was analyzed by GC (O99%
yield) and HPLC (eeZ89% (S).
5.4.4. Conversion of 2b to 2c (S)-(1-isobutyl-4-[1-
methylallyl]benzene). A solution of isobutyl bromide
(400 mg, 2.92 mmol) in diethyl ether (5 mL) was added to
Mg turnings (100 mg, 4.11 mmol) in diethyl ether (5 mL).
The mixture was stirred overnight at rt and added dropwise
to a mixture of compound 2b (360 mg, 1.7 mmol) and
(dppp) NiCl2 (15 mg, 0.028 mmol) in diethyl ether (10 mL).
The resulting reaction mixture was heated at reflux over-
night, quenched with half-saturated aqueous ammonium
chloride, and extracted with diethyl ether (50 mL). The
organic phase was dried over magnesium sulfate and
concentrated under reduced pressure. The crude product
and chromatographed on silica with hexane as solvent to
afford 300 mg (95% yield) of (S)-2c as a colorless oil,
ascertained by HPLC of having ee of 89% (S).
5.4.6. 2-(3-Bromophenyl)-1-butene (16, racemic). To a
solution of allylnickel bromide (2.2 mg, 0.0061 mmol) in
CH2Cl2 (1.0 mL), was added a solution of triphenylphos-
phine (3.2 mg, 0.0122 mmol) in CH2Cl2 (2.0 mL). The
resulting orange solution was added to a suspension of silver
triflate (3.8 mg, 0.015 mmol) in CH2Cl2 (1.0 mL), and the
resulting mixture was stirred at rt for 1.5 h. The mixture was
filtered through celite to get a clear yellow solution which
was subsequently cooled to K52 8C. Ethylene was intro-
duced to the reaction followed by addition of 3-bromo-
styrene (1, 148 mg, 0.86 mmol) in 0.5 mL of CH2Cl2. The
reaction was stirred at K52 8C for 3 h and was quenched by
adding saturated aqueous NH4Cl solution (5 mL). The
mixture was extracted twice with ether. GC showed O99%
conversion and O99% selectivity. The dried organic layer
was evaporated to afford crude product (16, 170 mg, 99%).
1H NMR (400 MHz, CDCl3): 1.35 (d, JZ7.0, 3H); 3.45
(q, JZ6.8, 1H); 5.03–5.13 (m, 2H); 7.10–7.21 (m, 2H);
7.31–7.42 (m, 2H). 13C NMR (100 MHz, CDCl3): 20.80;
43.10; 114.03; 112.72; 126.18; 129.44; 130.18; 130.60;
142.57; 148.15.
5.4.5. (R)-2-(4-Isobutylphenyl)propionic acid (14).21
A
solution of compound 2c (170 mg, 1.06 mmol) in dichloro-
methane–methanol (2:1, 30 mL) was cooled to K78 8C, and
ozone was passed through the solution until the blue color
persisted. It was stirred for 30 min at K78 8C, nitrogen was
purged for few minutes to remove excess ozone, and
dimethylsulfide (0.5 mL) was added to the mixture. The
resulting mixture was permitted to warm to 0 8C, and

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H. Park et al. / Tetrahedron 61 (2005) 6352–6367
5.4.7. 2-(3-Bromophenyl)-propionic acid (17, racemic).
To a solution of 2-(3-bromophenyl)-1-butene (racemic 16,
47 mg, 0.22 mmol) in 1:2 t-butanol/H2O (18 mL), was
added KMnO4 (108 mg, 0.68 mmol), NaIO4 (880 mg,
4.1 mmol) and K2CO3 (223 mg, 1.6 mmol). The pH of the
reaction solution was adjusted to 8 with 3 M NaOH aqueous
solution. The reaction was stirred for 3 h at rt. Concentrated
HCl was added to adjust the pH of the solution to 1, and
NaHSO3 was added to reduce KMnO4 until the reaction
mixture turned yellow greenish. The mixture was extracted
with ether and the ether layer was extracted with 3 M NaOH
aqueous solution. The aqueous layer was acidified with
concentrated HCl and then extracted with ether. The dried
organic layer was evaporated and the product was subjected
to chromatography (10:1 CH2Cl2/MeOH) to get 2-(3-
bromophenyl)-propionic acid (36 mg, 72%). 1H NMR
(400 MHz, CDCl3): 1.40 (d, 3H); 3.58 (q, 1H); 7.03–7.21
(m, 2H); 7.23–7.44 (m, 2H).
CDCl3): 20.80; 43.10; 114.03; 122.72; 126.18; 129.44;
130.18; 130.60; 142.57; 148.15.
5.4.10. (K)-Menthyl (R)-2-(3-bromophenyl)-propionate
(18). The optically enriched (S)-2-(3-bromophenyl)-1-
butene (16) was also oxidized and esterified with (K)-
menthol to the (K)-menthyl ester as described for the
racemic counterpart. Gas chromatography on chirasil S-Val
column showed this material to be of 87% ee.
5.5. Synthesis of phosphoramidite ligands
5.5.1. Synthesis of 2,5-diethylpyrrolidine$HCl. (K)-(2S,
5S)-2,5-Diethylpyrrolidine$HCl was synthesized from (3R,
6R)-octane-3,6-diol by following the literature procedure43
described for (C)-(2R, 5R)-2, 5-dimethylpyrrolidine. HCl,
via mesylation of the diol, reaction of the dimesylate with
benzyl amine to get N-benzyl-(2S, 5S)-2, 5-diethylpyrro-
lidine followed by debenzylation and salt formation.
5.4.8. (K)-Menthyl (RCS) 2-(3-bromophenyl)-propio-
nate (18). To a mixture of 2-(3-bromophenyl)-propionic
acid from the previous step (36 mg, 0.16 mmol), (K)-
menthol (62 mg, 0.40 mmol), DCC (1,3-dicyclohexyl-
carbodiimide, 49 mg, 0.24 mmol) and a few crystals of
DMAP, was added anhydrous CH2Cl2 (2.0 mL). The
resulting mixture was stirred for 15 h at rt. The reaction
mixture was filtered to remove the urea. The filtrate was
evaporated and the residue was dissolved in ether. After
filtration to remove the insoluble materials, the filtrate was
washed with 0.5 M HCl twice and then with saturated
NaHCO3. The dried organic layer was evaporated and
chromatography (10:1 hexanes/ether) of the residue
afforded the desired product as a 1:1 mixture of dia-
stereomers (55 mg, 95%). The two isomers were cleanly
separated on chirasil-S-val- column (RT ester from (R)-acid
20.41 min.; ester from (S)-acid 21.86 min). 1H NMR
(250 MHz, CDCl3): 0.57 (d, 3H); 0.71–2.16 (m, 16H),
3.68 (quint, 1H), 4.66 (dq, 1H), 7.12–7.28 (m, 2H); 7.37–
7.52 (m, 2H). 13C NMR (100 MHz, CDCl3): 16.04; 16.40;
18.23; 18.59; 20.85; 20.94; 22.17; 22.21; 23.38; 23.58;
25.99; 26.43; 31.54; 31.60; 34.42; 34.44; 40.65; 41.62;
45.73; 45.79; 47.15; 47.34; 74.96; 75.04; 122.70; 126.39;
130.20; 130.31; 130.86; 131.90; 143.21; 143.32; 173.58;
173.67.
5.5.2. Dimesylate of (RR)-octane-3,6-diol. The crude
1
product was found to be pure by NMR. Yield w100%. H
NMR (400 MHz, CDCl3) d 4.72–4.69 (m, 2H), 3.01 (s, 6H),
1.75 (dd, JZ3, 2.7 Hz, 4H), 1.72–1.65 (m, 4H), 0.93
(s, 6H); 13C NMR (100 MHz, CDCl3) d 84.2, 39, 29.5, 27.8,
9.7.
5.5.3. (C)-N-Benzyl-(2S, 5S)-2,5-diethylpyrrolidine. The
product was isolated in 72% yield as an oil by flash column
1
chromatography (SiO2, 3% EtOAc in hexanes). H NMR
(400 MHz, CDCl3) d 7.28 (d, JZ7.2 Hz, 2H), 7.19 (t, JZ
7.2 Hz, 2H), 7.1 (t, JZ7.2 Hz, 1H), 3.73 (d, JZ14 Hz, 1H),
3.58 (d, JZ14 Hz, 1H), 2.71 (br s, 2H), 1.83–1.72 (m, 2H),
1.56–1.47 (m, 2H), 1.42–1.36 (m, 2H), 1.13–1.02 (m, 2H),
0.7 (t, JZ7.6 Hz, 6H); 13C NMR (100 MHz, CDCl3) d
140.8, 128.7, 128.4, 126.7, 62.2, 51.6, 28, 23.5, 10.8. [a]D22
C111.9 (c 3, CH2Cl2).
5.4.9. (S)-2-(3-Bromophenyl)-1-butene (16). To a solution
of allylnickel bromide (1.8 mg, 0.0050 mmol) in CH2Cl2
(1.0 mL), was added a solution of 8A ligand in CH2Cl2
(1.5 mL) at rt. The resulting solution was stirred for 30 min.
before it was added to a suspension of AgSbF6 (3.8 mg,
0.011 mmol) in CH2Cl2 (1.0 mL). The mixture was stirred
for 5 min before it was filtered through celite into a Schlenk
tube. The celite pad was washed with CH2Cl2 (1.5 mL). The
solution was cooled down to K52 8C and ethylene was
introduced. 3-Bromostyene (138 mg, 0.75 mmol) in CH2Cl2
(0.5 mL) was added slowly. The reaction was stirred for
2.2 h before it was quenched with saturated NH4Cl (5 mL)
and extracted twice with ether. The dried ether layer was
evaporated to get crude product (157 mg, 99%), GC of
5.5.4. (K)-(2S, 5S)-2,5-Diethylpyrrolidine$HCl. The
product was obtained as a pale yellowish solid in 82%
yield after crystallization from a 4:1 solvent mixture of
CH2Cl2, hexanes. 1H NMR (400 MHz, CDCl3) d 9.38 (br s,
2H), 3.55 (br s, 2H), 2.15–2 (m, 4H), 1.72–1.6 (m, 4H), 0.99
(t, JZ7 Hz, 6H); 13C NMR (100, CDCl3) d 61.4, 30.3, 26.1,
11.4. [a]2D2 K2.87 (c 3, CH2Cl2); mp 222–226 8C.
1
which showed 88% conversion with O99% selectivity. H
1
and 13C NMR are consistent with the structure. H NMR
(400 MHz, CDCl3): 1.36 (d, 3H); 3.45 (quint, 1H), 5.02–
5.12 (m, 2H), 5.93–6.08 (m, 1H). 13C NMR (100 MHz,

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
6365
5.6. Preparation of binaphthyl-O, O0-dioxo-N-[(2S, 5S)-
diethylpyrrolidino]phospholidines
septum was quickly replaced by a glass stopper while
flushing N2 and the reaction flask was taken inside a glove
box. Toluene was removed under vacuum and the residue
was added 3!3 mL of 3:1 hexanes, ether and filtered
through cotton. The filtrate was concentrated to dryness.
The residue was dissolved in 3 mL of toluene and cooled
to approximately K20 8C. Triethylamine (0.3 mL) and
(R)-bis(a-methylbenzyl) amine (0.7 mmol, 158 mg) in
2 mL of toluene were added successively and the resultant
mixture was stirred at rt overnight. Toluene was removed
under reduced pressure and to the residue was added 3!
3 mL of 3:1 hexanes, ether mixture. Filtration through
cotton and concentration of the filtrate gave a crude product
which was purified by flash column chromatography (SiO2,
100% hexanes) to afford 82 mg (57%) of pure 25 as a
colorless solid. 1H NMR (250 MHz, CDCl3) d 7.1 (s, 10H),
4.62–4.45 (m, 3H), 4.15–4.13 (m, 1H), 2.04–1.6 (m, 10H),
1.72 (d, JZ7.25 Hz, 6H), 1.43–1.36 (m, 2H); 13C NMR
(63 MHz, CDCl3) d 144.3, 128.2, 128, 126.5, 81.9 and 81.8,
53.6 and 53.4, 37.6 and 36.8, 34.9 and 34.8, 33.4 and 33.3,
23.9 and 22.9, 22.7 and 22.5; 31P NMR (101 MHz, CDCl3)
d 130.
In a flame dried two necked flask equipped with a stirring
bar, long reflux condenser attached to a guard tube filled
with NaOH pellets, were placed binaphthol (286 mg,
1 mmol) and 5 mL of freshly purified PCl3. The mixture
was refluxed at 82 8C for 4 h. After cooling to rt, the reaction
flask was tightly closed and taken inside a glove box.
Removal of PCl3 under high vacuum afforded 355 mg of
colorless solid (31P NMR: d 176, s) which was redissolved
in dry toluene (6 mL) and cooled to approximately K20 8C
in the freezer. To this cold solution 164 mg (1 mmol) of (2S,
5S)-2, 5-diethylpyrrolidine. HCl and triethylamine (3 mL)
were added successively, and stirred at rt for 20 h. Toluene
was removed under reduced pressure. To the residue 3!
3 mL portions of a mixture of hexanes, ether (3:1) was
added to dissolve the product leaving most of the Et3N$HCl.
Filtration, concentration of the filtrate followed by
flash column chromatographic purification (SiO2, 100%
hexanes)
afforded
phosphoramidite
23
(R)-binaphthol] or 24 [from (S)-binaphthol] as a colorless
[from
solid in 40–45% yield.
5.6.1. (R)-2,20-O, O-(1, 10-Binaphthyl)-O, O0-dioxo-N-
[(2S, 5S)-2,5-diethylpyrrolidino]phospholidine (23). 1H
NMR (250 MHz, CDCl3) d 7.94–7.84 (m, 4H), 7.47–7.2 (m,
8H), 3.52–3.45 (m, 2H), 1.9–1.72 (m, 2H), 1.55–1.41 (m,
4H), 1.3–1.18 (m, 2H), 0.65 (t, JZ7.5 Hz, 6H); 31P NMR
(101 MHz, CDCl3) d 149.9.
5.6.4. 1,6-O, O-(1S, 5S, 6S)-cis, cis-spiro[4.4]nonyl-O, O0-
dioxo-N, N-bis[(1R)-phenylethyl]aminophospholidine
(26). Following the above procedure 26 (172 mg, 61%)
was obtained as a colorless solid starting from PCl3
(0.76 mmol, 66 mL), triethylamine (1.52 mmol, 0.21 mL),
(1S, 5S, 6S)-spiro[4.4]nonane-1,6-diol (0.69 mmol,
108 mg) and then triethylamine (0.5 mL), (S)-bis(a-
methylbenzyl) amine (1.4 mmol, 315 mg).1H NMR
(250 MHz CDCl3) d 7.19–7.05 (m, 10H), 4.75–4.62 (m,
2H), 4.35 (dd, JZ4.75, 2.75 Hz, 1H), 4.12 (dd, JZ3.5,
1.75 Hz, 1H), 2.06–1.88 (m, 6H), 1.9–1.62 (m, 4H), 1.72
(d, JZ7.25 Hz, 6H), 1.5–1.35 (m, 2H); 13C NMR
(63 MHz, CDCl3) d 142, 128.3, 128, 126.6, 82.3 and
81.2, 57, 52.4 and 52.3, 37.8 and 37, 34.7 and 33.8, 24.1
and 23.1, 22.5 and 22.3; 31P NMR (101 MHz, CDCl3) d
126.1.
5.6.2. (S)-2,20-O, O-(1, 10-Binaphthyl)-O, O0-dioxo-N-
[(2S, 5S)-2,5-diethylpyrrolidino]-phospholidine (24). H
NMR (250 MHz, CDCl3) d 7.87–7.76 (m, 4H), 7.32–7.09
(m, 8H), 3.16 (br s, 2H), 1.71–1.64 (m, 4H), 1.5–1.22 (m,
4H), 0.55 (t, JZ7.5 Hz, 6H); 31P NMR (101 MHz, CDCl3) d
155.9.
1
5.6.3. 1,6-O, O-(1S, 5S, 6S)-cis,cis-spiro[4.4]nonyl-O, O0-
Dioxo-N, N-bis[(1S)-phenylethyl]-aminophospholidine
(25). In a Schlenk flask equipped with a stirring bar and a
rubber septum was placed PCl3 (0.39 mmol, 34 mL) in
toluene (2 mL) at K60 8C under N2. Triethylamine
(0.77 mmol, 107 mL) in neat was introduced through a
syringe followed by a toluene (2 mL) solution of (1S, 5S,
6S)-spiro[4.4]nonane-1,6-diol (0.35 mmol, 55 mg).44 The
resultant mixture was stirred at K60 8C for 2 h. The rubber
Acknowledgements
Financial assistance for this research by US National
Science Foundation (CHE-0308378) and the Petroleum

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H. Park et al. / Tetrahedron 61 (2005) 6352–6367
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metal-catalyzed C–C bond-forming reactions reported. See:

H. Park et al. / Tetrahedron 61 (2005) 6352–6367
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