1,2-ferrocenediylazaphosphinines: An unusual coordination behavior and application to allylic alkylation

Article abstract of DOI:10.1021/om020929n

The reaction of 1,2-ferrocenediylazaphosphinines (1a, R¹ = H; 1b, R¹ = Me; 1c, R¹ = Ph) with M(CO)₆ (M = Mo, W), MX(CO)₅ (M = Mn, Re; X = Br, Cl), and [Pd(η³-C₃H₅)Cl]₂ shows a strong tendency to adopt an unusual chelating bidentate coordination through nitrogen and the carbonyl oxygen, yielding M(η²-N,O)(CO)₄ (2, M = Mo; 3, M = W), M(η²-N,O)(X)-(CO)₃ (6, M = Mn, X = Br; 7, M = Re, X = Cl), and [Pd(η²-N,O)(η³-C₃H₅)]BF ₄ (after treatment with AgBF₄) (8), respectively. X-ray crystallographic structure determinations of 3a (R¹ = H) and 8a (R¹ = H) show the formation of a five-membered metallacycle with the distance of the metal - carbonyl oxygen bond being shorter than that of the metal - nitrogen bond in both compounds. The complexes 2 and 3 further undergo oxidative addition with allyl iodide to yield the corresponding M(II) complexes of the type [M(η²-N,O)(η³-C₃H₅)(I)CO) ₂] (4, M = Mo; 5, M = W). Complexes 2-5 and 8 were employed as catalysts for nucleophilic allylic substitution of allyl acetates as a probe for both regio- and enantioselectivities of the reaction. All reactions involving unsymmetrical allyl acetates (E)-RCH=CHCH₂OAc (R = Pr, Ph) led exclusively to the formation of achiral linear product (E)-RCH=CHCH₂Nu regardless of the type of catalysts, the ligand, or the allyl substrate employed. One exception to the above statement is the observation that Mo- and W-based catalysts (2-5) are totally inactive toward the allylic substitution of cinnamyl acetate (R = Ph). Asymmetric allylic alkylation of a symmetrically 1,3-disubstituted substrate, PhCH=CHCH(OAc)Ph, is accomplished only by Pd-catalysts (8) with enantiomeric excesses up to 50% ee.

Full text of DOI:10.1021/om020929n

Organometallics 2003, 22, 1475-1482
1475
1,2-F er r ocen ed iyla za p h osp h in in es: An Un u su a l
Coor d in a tion Beh a vior a n d Ap p lica tion to Allylic
Alk yla tion
Thanh Thien Co, Seung Whan Paek, Sang Chul Shim, Chan Sik Cho, and
Tae-J eong Kim*
Department of Industrial Chemistry, Kyungpook National University, Taegu, Korea 702-701
Dong Woong Choi and Sang Ook Kang
Department of Chemistry, Korea University, 208 Seochang, Chochiwon,
Chung-nam, Korea 339-700
J ong Hwa J eong
Department of Chemistry, Kyungpook National University, Taegu, Korea 701-702
Received November 7, 2002
The reaction of 1,2-ferrocenediylazaphosphinines (1a , R1 ) H; 1b, R1 ) Me; 1c, R1 ) Ph)
with M(CO)6 (M ) Mo, W), MX(CO)5 (M ) Mn, Re; X ) Br, Cl), and [Pd(η3-C3H5)Cl]2 shows
a strong tendency to adopt an unusual chelating bidentate coordination through nitrogen
and the carbonyl oxygen, yielding M(η2-N,O)(CO)4 (2, M ) Mo; 3, M ) W), M(η2-N,O)(X)-
(CO)3 (6, M ) Mn, X ) Br; 7, M ) Re, X ) Cl), and [Pd(η2-N,O)(η3-C3H5)]BF4 (after treatment
with AgBF4) (8), respectively. X-ray crystallographic structure determinations of 3a (R1 )
H) and 8a (R1 ) H) show the formation of a five-membered metallacycle with the distance
of the metal-carbonyl oxygen bond being shorter than that of the metal-nitrogen bond in
both compounds. The complexes 2 and 3 further undergo oxidative addition with allyl iodide
to yield the corresponding M(II) complexes of the type [M(η2-N,O)( η3-C3H5)(I)(CO)2] (4, M )
Mo; 5, M ) W). Complexes 2-5 and 8 were employed as catalysts for nucleophilic allylic
substitution of allyl acetates as a probe for both regio- and enantioselectivities of the reaction.
All reactions involving unsymmetrical allyl acetates (E)-RCHdCHCH2OAc (R ) Pr, Ph) led
exclusively to the formation of achiral linear product (E)-RCHdCHCH2Nu regardless of the
type of catalysts, the ligand, or the allyl substrate employed. One exception to the above
statement is the observation that Mo- and W-based catalysts (2-5) are totally inactive toward
the allylic substitution of cinnamyl acetate (R ) Ph). Asymmetric allylic alkylation of a
symmetrically 1,3-disubstituted substrate, PhCHdCHCH(OAc)Ph, is accomplished only by
Pd-catalysts (8) with enantiomeric excesses up to 50% ee.
In tr od u ction
(1a -c) are not only powerful ligands in a Cu-catalyzed
cyclopropanation of styrene to achieve a complete dias-
tereoselectivity1,4 but also nucleophilic catalysts for
highly regio- and enantioselective ring opening of ep-
oxides.5 Intrigued by these observations and motivated
by our continuing effort in the design and application
of new ferrocene derivatives for use in asymmetric
catalysis,6 we have extended our investigation with 1
to their reaction and coordination chemistry with vari-
ous transition metal compounds that may find even
wider application as catalysts in this area.
We have recently shown that the reaction of 1-(R-
aminoalkyl)-2-diphenylphosphinoferrocene with glyox-
als results in, via an unusual cyclization, 1,2-ferrocene-
diylazaphosphinines (1a -c, Scheme 1) rather than the
expected condensation product of bisferrocenyldiimines.1
These compounds constitute a completely new family
of planar chiral ferrocenes that are of intense current
research interest in the field of asymmetric catalysis.2,3
We have further demonstrated that our new compounds
(1) Hwang, G.-H.; Ryu, E.-S.; Park, D.-K.; Shim, S. C.; Cho, C. S.;
Kim, T.-J .; J eong, J . H.; Cheong, M. Organometallics 2001, 20, 5784.
(2) For recent reviews on the synthesis and the use of planar chiral
ferrocenes in asymmetric catalysis, see: (a) Richards, C. J .; Locke, A.
J . Tetrahedron: Asymmetry 1998, 9, 2377. (b) Kagan, H. B.; Riant, O.
In Advances in Asymmetric Synthesis; Hassner, A., Ed.; J AI Press
Inc.: Greenwich, CT, 1997; Vol. 2, p 189. (c) Togni, A. In Ferrocenes:
Homogeneous Catalysis, Organic Synthesis, Materials Science; Togni,
A., Hayashi, T., Eds.; VCH: Weinheim, Germany, 1995; Chapters 2-4.
(3) For recent reviews on heterocyclic analogues of planar chiral
ferrocenes such as aza- and phosphaferrocenes, see: (a) Ganter, C. J .
Chem. Soc., Dalton Trans. 2001, 3541. (b) Fu, G. C. Acc. Chem. Res.
2000, 33, 412, and references therein.
(4) Paek, S. H.; Co, T.-T.; Lee, D. H.; Park, Y. C.; Kim, T.-J . Bull.
Korean Chem. Soc. 2002, 23, 1702.
(5) Unpublished results in this laboratory.
(6) (a) Song, J .-H.; Cho, D.-J .; J eon, S.-J .; Kim, Y.-H.; Kim, T.-J .
Inorg. Chem. 1999, 38, 893. (b) Cho, D.-J .; J eon, S.-J .; Kim, H.-S.; Cho,
C. S.; Shim, S. C.; Kim, T.-J . Tetrahedron: Asymmetry 1999, 10, 3833.
(c) Cho, D.-J .; J eon, S.-J .; Kim, H.-S.; Kim, T.-J . Synlett 1998, 617. (e)
Kim, T.-J .; Lee, H.-Y.; Ryu, E.-S.; Park, D.-K.; Cho, C. S.; Shim, S. C.;
J eong, J . H. J . Organomet. Chem. 2002, 649, 258. (f) Park, D.-K.; Ryu,
E.-S.; Paek, S. H.; Shim, S. C.; Cho, C. S.; Kim, T.-J . Bull. Korean
Chem. 2002, 23, 721.
10.1021/om020929n CCC: $25.00 © 2003 American Chemical Society
Publication on Web 02/14/2003

1476 Organometallics, Vol. 22, No. 7, 2003
Co et al.
Sch em e 1
Sch em e 2
isomer is attained regardless of the reaction parameters
such as metal, ligand, or allyl substrate employed. In
contrast, all complexes but 8 in their enantiomerically
pure forms show total inactivity toward asymmetric
allylic alkylation of a symmetrically 1,3-disubstituted
substrate, 1,3-diphenyl-2-propenyl acetate. These ob-
servations along with the reaction and coordination
chemistry of 1 with a series of transition metal com-
plexes will be presented in this paper.
Resu lts a n d Discu ssion
Syn th esis. Scheme 1 demonstrates that all reactions
lead to η2-N,O chelation, forming a five-membered
metallacyclic ring as confirmed by various spectroscopic,
analytical, and X-ray crystallographic techniques. These
observations are rather unusual considering the fact
that a simple carbonyl oxygen is a poor ligand for an
organometallic fragment, although it is quite common
for an amide carbonyl to be involved in coordination as
a hemilabile chelating η2-N,O or η2-P,O ligand (vide
infra). Thus, to the best of our knowledge, they consti-
tute the first isolated and fully characterized represen-
tative of the complexes where a simple ketonic (or
aldehydic) oxygen participates in chelation. It is tempt-
ing to propose that the extended resonance leading to
an enolate such as shown in Scheme 2, in addition to
the chelate effect, may partially be responsible for such
a unique coordination behavior. For comparison, it is
worth noting that a structurally related mode of η2-N,O
or η2-P,O chelation involving a carbonyl oxygen can be
found with some donors incorporating a carboxylic
amide group. Recent examples for the former case
include (1) a neutral bimetallic Mo(I) complex, {MoCl-
(η3-C3H5)(CO)2}2-µ-trans-1,2-bis(2-pyridinecarboxamide-
)cyclohexane, where the bridge bis(chelate) ligand in-
volves coordination of an amide carbonyl oxygen and a
pyridine nitrogen,10 and (2) a neutral Mo(0) complex,
Mo(CO)3[η3-1,2-bis(dih ydr ooxa zoleca r boxa m ide)-
cyclohexane], where the ligand binds to Mo with the two
dihydrooxazole rings and one of the amide carbonyl
oxygens.9e The examples for the latter case are ubiqui-
tous and can be found mostly in connection with Pd-
complexes.11 These include (1) a cationic Pd(II) complex
of an acetamide-derived η2-P,O ligand, [PdMe{η2-PPh2-
NHC(O)Me}{PPh2NHC(O)Me}],11d and (2) a cationic
bimetallic Pd(II) complex incorporating the Trost ligand,
{Pd(η3-C3H5)}2-µ-trans-1,2-diaminocyclohexane-N,N′-
Our initial finding is an unusual chelating bidentate
mode of 1 through nitrogen and carbonyl oxygen, an η2-
N,O chelation, toward a range of transition metals such
as M(CO)6 (M ) Mo, W), MX(CO)5 (M ) Mn, Re; X )
Cl, Br), and [Pd(η3-C3H5)Cl]2, leading to the formation
of M(η2-N,O)(CO)4, [M(η2-N,O)(η3-C3H5)(I)(CO)2] (after
oxidative addition of C3H5I), M(η2-N,O)(X)(CO)3, and
[Pd(η2-N,O)(η3-C3H5)]BF4 (after treatment with AgBF4),
respectively. The attractiveness of these compounds
derives from their potential attributes of chemo-, regio-,
or stereoselectivity in catalytic allylic alkylation of
various allylic acetates. For instance, unsymmetrically
1,3-disubstituted allyl derivatives such as RCHdCHCH2-
OAc (R ) Pr, Ph) are particularly demanding sub-
strates, because, in addition to the requirement of
enantiocontrol, the problem of regioselectivity has to be
resolved.7 With most palladium catalysts, such sub-
strates react with soft carbon nucleophiles preferentially
at the less substituted terminus, giving rise to an achiral
linear product.8 With certain molybdenum and tungsten
catalysts incorporating phosphinodihydrooxazoles or
bis(pyridine), on the other hand, such propensity is
generally reversed to yield chiral, branched regioiso-
mers.9 However, our own investigation on the same
reaction by employing 2-5 and 8 as catalyst argues
against the rule of thumb stated above, demonstrating
that near perfect regioselectivity in favor of a linear
(7) For comprehensive recent reviews on the issue of regioselectivity
of unsymmetrically substituted 1,3-allyl derivatives, see: (a) Trost, B.
M.; Lee, C. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley-
VCH: New York, NY, 2000; pp 593-650. (b) Pfaltz, A.; Lautens, M.
In Comprehensive Asymmetric Catalysis; J acobsen, E. N., Pfaltz, A.,
Yamamoto, H., Eds.; Springer: Berlin, Germany, 1999; Vol. II, pp 833-
884.
(8) Godleski, S. A. In Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon Press: Oxford,
U.K., 1991; Vol. 4, pp 585-662. (b) However, for recent interesting
exceptions with Pd catalysis, see: Hayashi, T.; Kawatsura, M.; Uozumi,
Y. Chem. Commun. 1997, 561. Pre´toˆt, R.; Pfaltz, A. Angew. Chem.,
Int. Ed. 1998, 37, 323.
(10) Morales, D.; Pe´rez, J .; Riera, L.; Corzo-Sua´rez, R.; Garc´ıa-
Granda, S.; Miguel, D. Organometallics 2002, 21, 1540.
(9) (a) Lloyd-J ones, G. C.; Pfaltz, A. Angew. Chem., Int. Ed. Engl.
1995, 34, 462. (b) Trost, A. M.; Hachiya, I. J . Am. Chem. Soc. 1998,
120, 1104. (c) Glorius, F.; Pfaltz, A. Org. Lett. 1999, 1, 142. (d) Belda,
O.; Kaiser, N.-F.; Bremberg, U.; Larhed, M.; Hallberg, A.; Moberg, C.
J . Org. Chem. 2000, 65, 5868. (e) Glorius, F.; Neuburger, M.; Pfaltz,
A. Helv. Chim. Acta 2001, 84, 3178. (f) Trost, M.; Dogra, K.; Hayachi,
I.; Emura, T.; Hughes, D. L.; Krska, S.; Reamer, R. A.; Palucki, M.;
Yasuda, N.; Reider, P. J . Angew. Chem., Int. Ed. 2002, 41, 1929.
(11) For some examples of X-ray crystallographically characterized
complexes of this type, see: (a) Braunstein, P.; Douce, L.; Fischer, J .;
Graig, N. C.; Goetz-Grandmont, G.; Matt, D. Inorg. Chim. Acta 1992,
194, 151. (b) Andrieu, J .; Braunstein, P.; Drillon, M.; Ingold, F.; Rabu,
P.; Tiripicchio, A.; Ugozzoli, F. Inorg. Chem. 1996, 35, 5986. (c) Leung,
P. H.; Loh, S. K.; Vittal, J . J .; White, A. J . P.; Williams, D. J . Chem.
Commun. 1997, 1987. (d) Braunstein, P.; Frison, C.; Morise, X.; Adams,
R. D. J . Chem. Soc., Dalton Trans. 2000, 2205.

1,2-Ferrocenediylazaphosphinines
Organometallics, Vol. 22, No. 7, 2003 1477
Ta ble 1. Su m m a r y of Cr ysta llogr a p h ic Da ta for 3a
a n d 8a
3a
8a
empirical formula
fw
C
30H22FeNO5PW
C29H27BF4FeNOPPd
685.55
747.16
cryst size (mm)
space group
a (Å)
b (Å)
c (Å)
V (Å3)
0.35 × 0.40 × 0.40 0.40 × 0.40 × 0.45
P212121
Pna21
11.3160(8)
13.8693(10)
19.9330(16)
3128.4(4)
4
14.4365(12)
11.2483(6)
16.9363(11)
2750.2(3)
4
Z
T (K)
293(2)
293(2)
radiation, λ (Å)
θ range (deg)
data collected: h; k; l 0, 13; 0, 17; 0, 24
Mo KR 0.71070
1.79-25.97
Mo KR 0.71070
2.17-25.47
0, 17; -13, 0; 0, 20
2785
1.291
1376
FMLS on F2
1.069
no. of unique reflns
3431
4.225
1456
FMLS on F2
1.222
µ (mm-1
F(000)
)
refinement
GOF
R indices (I > 2σ(I))a R1 ) 0.0594;
wR2 ) 0.1675
R1 ) 0.0494;
wR2 ) 0.1346
F igu r e 1. Crystal structure of 3a . Thermal ellipsoids are
drawn at 50% probability.
largest diff peak and 2.361 and -1.754 0.822 and -0.479
hole (e/Å3)
bis(2′-diphenylphosphinobenzoyl), where the bridge bis-
(chelate) ligand involves coordination of an amide car-
bonyl oxygen and a phosphine to each metal.12
R1 ) ∑||Fo| - |Fo||/∑|Fc|. wR2 ) [∑wi(Fo - Fc2)/wi(Fo2)]1/2
.
a
2
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 3a a n d 8a
The syntheses of our new compounds (2-8) are quite
straightforward. Gentle reflux of an equimolar mixture
of 1 and M(CO)6 (M ) Mo, W) in THF/toluene afforded
2 (M ) Mo) and 3 (M ) W) as dark red crystals after
purification by column chromatography on silica gel.13
Analytical, spectroscopic, and X-ray crystal structure
data in the case of 3a are all consistent with their
formulations. For example, three strong ν(CO) bands
from 2a and 3a are indicative of (cis-chelate)M(CO)4
(1882, 1855, 1803 cm-1 for 2a ; 1868, 1845, 1800 cm-1
for 3a ). Yet, due to the C1-symmetric nature of the
ligand (1), all four carbonyls become nonequivalent in
the given structure and thus give rise to four singlets
in their 13C NMR spectra (205.6, 206.2, 224.3, 225.2 ppm
for 2a ; 204.0, 204.5, 216.5, 217.3 ppm for 3a ). An
additional NMR spectral feature to be noted is a
significant coordination shift (∆δ ≈ 10 ppm)) found for
the ylidic phosphorus signal, although this atom is not
directly involved in the coordination with metal. A
detailed NMR assignment for the complexes was made
by comparison and by analogy with the NMR data for
the ligand itself.14 A more conclusive structural confir-
mation comes from the X-ray crystal structure of 3a
shown in Figure 1. A summary of crystallographic data
and selected bond lengths and angles are listed in
Tables 1 and 2, respectively. The structure shows the
geometry around tungsten to be a slightly distorted
octahedron with cis-chelation of nitrogen and oxygen.
Near perfect coplanarity encompassing the fused het-
eroaromatic ring of the ligand is further extended, on
complexation, to the W-containing metallacyclic ring.
The four W-CO bonds are of similar length and fall in
the range 1.91(2)-2.04(2) Å. The W-O bond (2.19(1) Å)
3a
W-C(29)
W-C(28)
1.91(3) W-C(27)
2.04(2) W-O(1)
C(1)-O(1) 1.28(2) C(1)-C(2) 1.39(3) N-C(2)
N-C(3) 1.32(3) P-C(2) 1.77(2) P-C(6)
C(3)-C(5) 1.41(3) C(5)-C(6) 1.47(3)
1.94(2) W-C(30) 1.98(3)
2.19(1) W-N
2.32(2)
1.38(2)
1.72(2)
C(28)-W-C(30)
C(27)-W-C(28)
C(27)-W-O(1)
N-W-O(1)
169(1)
85(1)
177.7(8)
74.0(5)
115(1)
C(29)-W-C(27)
C(28)-W-C(29)
N-W-C(29)
C(15)-P-C(21)
C(2)-N-W
88(1)
88.1(9)
166.9(8)
106.3(9)
110(1)
W-O(1)-C(1)
8a
Pd-O
P-C(2)
N-C(3)
2.082(9) Pd-N
1.774(8) P-C(15)
1.28(1) N-C(2)
2.137(8) P-C(6)
1.792(6) P-C(21)
1.43(1) O-C(1)
1.762(5)
1.804(5)
1.30(1)
C(1)-C(2) 1.35(2) C(3)-C(5) 1.47(1) C(3)-C(4) 1.51(1)
O-Pd-N
81.8(3)
122.9(8)
105.9(6)
124.2(9)
124.5(7)
C(6)-P-C(2)
C(3)-N-Pd
C(1)-O-Pd
C(1)-C(2)-N
N-C(3)-C(5)
102.6(4)
131.1(7)
109.3(7)
118.4(8)
125.2(8)
C(3)-N-C(2)
C(2)-N-Pd
O-C(1)-C(2)
N-C(2)-P
is shorter than the W-N bond (2.32(2) Å). Parallel
observations are found with Mo(CO)3[η3-1,2-bis(dihy-
drooxazolecarboxamide)cyclohexane], where the bond
distances of Mo-O and Mo-N are 2.2685(5) and 2.347-
(5) Å, respectively.9e The C(1)-C(2) distance (1.39(2) Å)
carries a partial multiple-bond character, supporting our
proposal concerning the resonance structure in Scheme
2. Numerical parameters for the ligand remain almost
the same upon complexation.
The complexes 2 and 3 readily undergo oxidative
addition by allyl iodide to give the corresponding M(II)
complexes [M(η2-N,O)(η3-C3H5)(I)(CO)2] (4, M ) Mo; 5,
M ) W), respectively.15,16 Their synthesis may be
justified in that they may not only serve as catalyst
precursors for the allylic alkylation but also exist as
(12) Butts, C. P.; Crosby, J .; Lloyd-J ones, G. C.; Stephen, S. C. Chem.
Commun. 1999, 1707.
(13) For an unknown reason, the reaction of Cr(CO)6 with 1 did not
lead to the formation of the expected product (η2-N,O)Cr(CO)4 even
under harsh reaction conditions during an extended period of time.
(14) Complete NMR data for 1 are provided in the Suppporting
Information, ref 1.
(15) Dieck, H. T.; Friedel, H. J . Organomet. Chem. 1968, 14, 375.
(16) Hull, C. G.; Stiddard, M. H. B. J . Organomet. Chem. 1967, 9,
519.

1478 Organometallics, Vol. 22, No. 7, 2003
Co et al.
reactive intermediates in the catalytic cycle as a result
of oxidative addition to an electron-rich zerovalent
species. Subsequent alkylation either directly to the allyl
or to the metal followed by an alkyl-to-allyl migration
with concomitant reductive elimination of the resulting
olefin would complete the cycle.7,17 With soft nucleo-
philes [M(L-L)(η3-C3H5)(X)(CO)2] (L-L ) bipy, phen;
X ) halide) complexes are known to react to afford
olefins.18 Yet with hard nucleophiles such as alkyl and
acetylide anions alkylation takes place selectively at the
metal, and neither acyl complexes nor allylic alkylation
products are formed.19
The structural identifications for 4 and 5 were per-
formed without difficulty. Thus, for example, the per-
sistence of a cis-M(CO)2 unit is confirmed by infrared
and 13C NMR spectra showing, respectively, two strong
ν(CO) bands (1923 and 1831 cm-1 for 4a ; 1912 and 1814
cm-1 for 5a ) and two carbonyl singlets (227.4 and 227.9
for 4a ). In addition, the pattern of three multiplets
arising from anti- and syn-protons (H29/H31) and the
F igu r e 2. Crystal structure of 8a . Thermal ellipsoids are
drawn at 50% probability.
Ta ble 3. Allylic Alk yla tion a s a F u n ction of Meta l,
Liga n d , a n d Allyl Su bstr a tea
1
central proton (H30) in H NMR is diagnostic of a static
(without fast equilibrium to η1) η3-C3H5 group like the
one present in related [Mo(N-N)(X)(η3-C3H5)(CO)2]
complexes.19b Attempted crystallization for the purpose
of clarifying the disposition of the allyl group has so far
been frustrating. Yet it is common to most known [Mo-
(L-L)(X)(η3-allyl)(CO)2] compounds that the allyl group
and the two CO ligands define one face of the octahedron
with the open face of the allyl pointing toward the
carbonyls.9e,10,19,20
conditions
ratioc
yield
t/h T/°C (%)b 10:11
entry
catalyst
R
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Mo(1a )(CO)4, 2a
Mo(1a )(CO)4, 2a
Mo(1a )(CO)2(π-C3H5)(I), 4a Pr
Pr 24
Ph 24
80
80
80
80
80
80
80
80
80
80
RT
70
70
70
33 100:0
0
90 100:0
66 100:0
72 100:0
0
12 100:0
0
23 100:0
0
5
Mo(1b)(CO)2(π-C3H5)(I), 4b Pr 24
Mo(1c)(CO)2(π-C3H5)(I), 4c Pr 24
Mo(1a )(CO)2(π-C3H5)(I), 4a Ph 24
In an analogous manner, the group 7 complexes 6 and
7 were also prepared in high yields as red crystalline
solids by reacting 1 with MX(CO)5 (M ) Mn, Re; X )
Br, Cl). Both compounds show three characteristic ν-
(CO) bands (2018, 1917, 1897 cm-1 for 6a ; 2013, 1917,
1877 cm-1 for 7a ) and three 13C NMR signals in the
carbonyl region (222.8, 224.7, 225.4 ppm for 6a ; 192.6,
198.2, 199.3 ppm for 7a ). Again the failure in obtaining
single crystals from these complexes precluded us from
locating the position of the halide ligand.
W(1a )(CO)4, 3a
W(1a )(CO)4, 3a
Pr 24
Ph 24
W(1a )(CO)2(π-C3H5)(I), 5a Pr 24
W(1a )(CO)2(π-C3H5)(I), 5a Ph 24
[Pd(1a )(π-C3H5)]BF4, 8a
[Pd(1c)(π-C3H5)]BF4, 8c
[Pd(1a )(π-C3H5)]BF4, 8a
[Pd(1c)(π-C3H5)]BF4, 8c
Pr
5
90 100:0
90 100:0
Pr 24
Ph 24
Ph 24
93
88
93:7
92:8
a
Detailed procedure provided in Experimental Section: Nu )
dimethyl malonate. Isolated yield. c Determined by GC.
b
center.11,12 The steric repulsion between the allyl ligand
and the methyl group at C(3) may be a contributing
factor in lengthening the Pd-N bond distance. One of
the most striking differences in the nature of chelation
between 1 and most P,O chelates lies in the fact that
the former, in contrast to the latter, shows no sign of
hemilabile properties, as confirmed by their NMR (1H
and 31P) spectra. The room-temperature 31P NMR
spectrum of 8a , for example, reveals only a sharp singlet
at δ 4.80. The same NMR spectra allow us to confirm
the static nature of the allyl group as well as the their
presence.21 Yet, the three bond distances of Pd-C(27),
Pd-C(28), and Pd-C(29) could not be determined
without ambiguity due to the disorder of the allyl group
at palladium. The C(1)-C(2) distance (1.35(2) Å) also
carries a partial multiple-bond character.
The cationic Pd(II) complexes (8a ,c) were obtained as
dark red crystals from the reaction of 1 with [Pd(η3-
C3H5)Cl]2 followed by treatment with AgBF4. Analytical
and spectroscopic including HRMS data are fully con-
sistent with the formulation of [Pd(η2-N,O)(η3-C3H5)]-
BF4. A definitive evidence for the η2-N,O chelation
comes from the X-ray crystal structure of 8a shown in
Figure 2. A summary of crystallographic data and
selected bond lengths and angles are listed in Tables 1
and 2, respectively. The geometry around palladium
adopts a slightly distorted square plane, and the fused
heterocyclic ring comprising the Pd-metallacycle and the
ferrocenediylazaphosphinine ring forms an almost co-
planar structure, as observed with 3a . The Pd-O bond
of 2.082(9) Å is slightly shorter than the Pd-N bond
(2.137(8) Å) and also shorter than those found for the
carbonyl group of a P,O chelate coordinated to a Pd
Ca ta lytic Allylic Alk yla tion . Table 3 shows the
results on the catalytic allylic alkylation of unsymmetri-
cally 1,3-disubstituted allyl derivatives as a function of
metal, ligand, and allyl substrate. The most character-
istic feature of the table is that all reactions involving
hexenyl acetate (9a , R ) Pr) exhibit a perfect regiocon-
(17) Sjo¨gren, M. P. T.; Frisell, H.; Åkermark, B.; Norrby, P. O.;
Eriksson, L.; Vitagliano, A. Organometallics 1997, 16, 942.
(18) Trost, B. M.; Lautens, M. J . Am. Chem. Soc. 1982, 104, 5543.
(19) (a) Pe´rez, J .; Riera, L.; Riera, V.; Garc´ıa-Granda, S.; Garc´ıa-
Rodr´ıguez, E. J . Am. Chem. Soc. 2001, 123, 7469. (b) Pe´rez, J .; Riera,
L.; Riera, V.; Garc´ıa-Granda, S.; Garc´ıa-Rodr´ıguez, E. Organometallics
2002, 21, 1622.
(21) Åkermark, B.; Krakenberger, B.; Hansson, S.; Vitagliano, A.
(20) Curtis, M. D.; Eisenstein, O. Organometallics 1984, 3, 887.
Organometallics 1987, 6, 620.

1,2-Ferrocenediylazaphosphinines
Organometallics, Vol. 22, No. 7, 2003 1479
trol in favor of a linear achiral isomer (10a ) in high
yields regardless of the metal or the ligand employed
(entries 1, 3-5, 7, and 11-12). In particular, it is
noteworthy to observe such a complete reversal of
regioselectivity with our Mo- and W-based catalysts (2-
5). As mentioned earlier, these results are quite contrary
to those found with other Mo- and W-complexes incor-
porating such ligands as phosphinooxazolines or bis(2-
pyridinecarboxamide)cyclohexane derivatives.9 Further-
more, the perfect regioselectivity as well as the high
reactivity accomplished by catalysts 2-5 may well
deserve comparison with those attainable by related Mo-
and W-based catalysts. For instance, Mo(0) and Mo(II)
complexes of the types Mo(N-N)(CO)4 and [M(N-N)-
(π-allyl)(OTf)(CO)2], where N-N represents various
phenanthroline ligands, have been reported to exhibit
much lower degrees of reactivity and regioselectivity for
the same reaction, consequently giving rise to a distri-
bution of various products.17 Of three types of catalysts
we have employed, M(η2-N,O)(CO)4 (2 and 3), [M(η2-
N,O)(η3-C3H5)(I)(CO)2] (4 and 5), and [Pd(η2-N,O)(η3-
C3H5)]BF4 (8), the first type has proved the least
effective in that the reaction requires longer reaction
time as well as higher reaction temperature only to give
the lowest overall yields (<33%) (entries 1 and 7). When
the comparison is made between molybdenum and
tungsten, the former works more efficiently (entries 1
vs 7 and 3 vs 9). The structural variation in the ligand
from 1a to 1c has little effect on the regioselectivity of
the reaction (entries 3-5 and 11-12). An additionally
striking feature of Table 3 is that for an unknown
reason, Mo- and W-based catalysts (2-5) are totally
ineffective for the conversion of cinnamyl acetate (9b,
R ) Ph) toward the formation of either 10b or 11b
(entries 2, 6, 8, and 10). This was evidenced by near
quantitative recovery of the starting compound in the
form of cinnamyl alcohol (PhCHdCHCH2OH) that
might have been formed as a result of simple hydrolysis
of the reactant acetate under the basic workup condi-
tions. On the other hand, the Pd-catalysts (8), the most
efficient of all, catalyze the allylation of both hexenyl
acetate (9a ) and cinnamyl acetate (9b) alike, producing
the linear isomer (10) with near perfect regioselectivity
(entries 11-14).
diphenyl-2-propenyl acetate (12). Quite disappointingly,
however, all of Mo- and W-based complexes (2-5)
exhibit near zero catalytic activity under the standard
set of reaction conditions, as were the cases with the
reaction of cinnamyl acetate (cf. entries 2, 6, 8, 10, Table
3). Only Pd-complexes (8a ,c) catalyze the reaction to
give 13 with high chemical yields and a certain degree
of enantiomeric excess reaching 50% ee. Studies on fine-
tuning of the catalysts to improve their enantioselection
are currently underway and will be the subject of our
future communication.
Exp er im en ta l Section
Gen er a l Rem a r k s. All reactions were carried out under
an atmosphere of nitrogen using standard Schlenk techniques.
Solvents were dried using standard procedures. The 1H and
13C NMR experiments were performed on a Bruker Advance
400 or 500 spectrometer. The 31P NMR spectra were recorded
on a Varian Unity Invova 300 WB spectrometer. Chemical
shifts are given as δ values with reference to tetramethylsilane
(TMS) as internal standard. Coupling constants are in Hz.
GC-mass spectra were obtained by using a Micromass QUAT-
TRO II GC8000 series model with electron energy of 20 or 70
eV. IR spectra were run on a Mattson FT-IR Galaxy 6030E
spectrophotometer. All commercial reagents were purchased
from Aldrich and used as received. 1,2-Ferrocenediylazaphos-
phinines (1a -c) were prepared according to the methods
described earlier by us.1
Syn th esis of 2a . A 50 mL, two-necked round-bottom flask
equipped with a condenser was charged with 1a (0.50 g, 1.10
mmol) and Mo(CO)6 (0.33 g, 1.23 mmol) in a mixture of THF
(10 mL) and toluene (25 mL). The mixture was stirred at 90
°C for 3 h, during which time the solution turned deep red.
Chromatographic separation on silica gel with a mixture of
MeOH and diethyl ether (9:1) as an eluent followed by removal
of solvents gave red solids. Recrystallization from CH2Cl2/
diethyl ether yielded 0.55 g of 2a (76%) in two crops as red
crystals. 31P NMR (121 MHz, CDCl3, H3PO4): δ 4.99 (s). 1H
NMR (400 MHz, CDCl3): δ 2.78 (s, H4), 3.91 (s, H10-H14),
4.78 (m, H7), 4.88 (m, H8), 5.02 (m, H9), 7.22-7.27 (m, H22/
H26), 7.34-7.41 (m, H23/H25), 7.49-7.60 (m, H24), 7.67-7.70
(m, H16/H20), 7.70-7.78 (m, H18), 7.84-7.88 (m, H17/H19),
8.16 (d, J ) 1.0, H1). 13C NMR (100.6 MHz, CDCl3): δ 28.4 (s,
C4), 60.4 (d, J ) 101.6, C6), 71.9 (d, J ) 6.7, C9), 72.3 (d, J )
8.2, C7), 72.4 (s, C10-C14), 76.3 (d, J ) 11.6, C8), 81.2 (d, J
) 7.0, C5), 94.2 (d, J ) 101.6, C2), 125.4 (d, J ) 94.1, C15),
128.2 (d, J ) 89.1, C21), 130.1 (d, J ) 12.6, C22/C26), 130.3
(d, J ) 13.2, C17/C19), 133.6 (d, J ) 10.9, C16/C20), 133.7 (d,
J ) 11.0, C23/C25), 133.9 (d, J ) 2.8, C24), 134.9 (d, J ) 3.3,
C18), 154.8 (d, J ) 7.7, C3), 179.9 (d, J ) 33.0, C1), 205.6 (s),
206.2 (s), 224.3 (s), 225.2 (s) (C27-C30). IR ν(CO): 1882 (vs),
Although much has yet to be known concerning the
origin of such unique regioselectivity demonstrated by
our catalytic systems, it may be safe to state that the
unsymmetric bonding nature of the ligand (1) should
exhibit an electronic and/or steric bias for the disposition
of the unsymmetrically substituted ally derivatives in
the coordination sphere and the subsequent attack of
the nucleophile as well. Finally, according to the results
in Table 3, our catalysts (2-5, 8) are not suitable as a
probe for enantioselectivity of unsymmetric 1,3-disub-
stituted allyl substrates. However, they bear some
synthetic advantages in that they negate the prepara-
tion and employment of (C7H8)M(CO)3 or (EtCN)3M-
(CO)3 as the precatalyst, which requires laborious
preparative work and careful handling.
1855 (vs), 1803 (vs) cm-1. HRMS (EI, m/z): calcd for C30H22
NPO5FeMo 661.9717 (M+), found 632.9708 (M+ - CO). Anal.
Calcd for 30H22NPO5FeMo: C, 54.66; H, 4.36; N, 2.12.
Found: C, 54.35; H, 4.19; N, 1.64.
-
C
In this regard the way may be open for these
complexes in their enantiomerically pure forms to be
employed in the asymmetric allylic alkylation of sym-
metrically 1,3-disubstituted ally derivatives such as 1,3-

1480 Organometallics, Vol. 22, No. 7, 2003
Co et al.
Syn th esis of 3a . This compound was prepared in the same
manner as described above replacing Mo(CO)6 with W(CO)6
as a reagent. Yield: 0.76 g, 92%. Red single crystals suitable
for X-ray structural determination were grown by slow diffu-
sion of diethyl ether into a solution of 3a in CH2Cl2. 31P NMR
(121 MHz, CDCl3, H3PO4): δ 5.72 (s). 1H NMR (400 MHz,
CDCl3): δ 2.83 (s, H4), 3.94 (s, H10-H14), 4.80 (m, H7), 4.91
(m, H8), 5.04 (m, H9), 7.25-7.29 (m, H22/H26), 7.40-7.43 (m,
H23/H25), 7.52-7.55 (m, H24), 7.68-7.72 (m, H16/H20), 7.76-
7.80 (m, H18), 7.84-7.89 (m, H17/H19), 8.26 (d, J ) 2.0, H1).
13C NMR (100.6 MHz, CDCl3): δ 29.4 (s, C4), 60.3 (d, J )
102.8, C6), 72.4 (d, J ) 6.3, C9), 72.5 (d, J ) 7.2, C7), 72.6 (s,
C10-C14), 76.6 (d, J ) 12.1, C8), 81.1 (d, J ) 7.6, C5), 97.4
(d, J ) 104.4, C2), 124.9 (d, J ) 94.5, C15), 127.7 (d, J ) 89.6,
C21), 130.2 (d, J ) 13.2, C22/C26), 130.4 (d, J ) 13.2, C17/
C19), 132.6 (d, J ) 11.6, C16/C20), 133.6 (d, J ) 10.9, C23/
C25), 134.2 (d, J ) 2.8, C24), 135.2 (d, J ) 2.8, C18), 156.7 (d,
J ) 7.6, C3), 181.3 (d, J ) 31.5, C1), 204.0 (s), 204.5 (s), 216.5
(s), 217.3 (s) (C27-C30). IR ν(CO): 1868 (vs), 1845 (vs), 1800
(vs) cm-1. HRMS (EI, m/z): calcd for C30H22NPO5FeW 747.0095
(M+), found 747.0115. Anal. Calcd for C30H22NPO5FeW: C,
48.19; H, 2.95; N, 1.87. Found: C, 48.32; H, 2.69; N, 1.74.
Syn th esis of 4b. Yield: 50%. 31P NMR (202.5 MHz, CD2-
Cl2, H3PO4): δ 2.95 (s). 1H NMR (500 MHz, CD2Cl2): δ 1.43
(d, J ) 8.0, H32), 1.75 (s, H4), 3.37-3.51 (m, anti-H29/H31),
3.91 (s, H10-H14), 4.16 (s, H7), 4.34-4.52 (m, syn-H29/H31),
4.63 (br, H8), 4.82 (s, H9), 5.10 (m, H30), 7.38-7.43 (m, H22-
H26), 7.49 (m, H23/H25), 7.54-7.58 (m, H24), 7.66 (m, H16/
H20), 7.90 (m, H18), 8.25 (m, H17/H19). 13C NMR (125.8 MHz,
CD2Cl2): δ 26.0 (s, C32), 30.2 (s, C4), 61.5 (d, J ) 105.0, C6),
70.8 (d, J ) 83.4, C9), 71.9 (d, J ) 31.0, C7), 71.8 (s, C10-
C14), 75.5 (d, J ) 12.2, C8), 80.6 (s, C5), 128.1 (br, C15), 128.3
(br, C21), 129.2 (d, J ) 13.9, C22/C26), 129.5 (d, J ) 13.7, C17/
C19), 131.5 (br, C16/C20), 132.9 (br, C23/C25), 133.5 (s, C18),
133.7 (s, C24), 187.0 (d, J ) 29.1, C1), 228.0 (s)/228.4 (s)(C27/
C28). IR ν(CO): 1927 (vs), 1833 (vs) cm-1. HRMS (EI, m/z):
calcd for C32H29NPO3IMoFe 786.9333, found 730.9453 (M+
-
2CO). Anal. Calcd for C32H29NPO3IMoFe: C, 48.95; H, 3.72;
N, 1.78. Found: C, 48.95; H, 3.35; N, 2.01.
Syn th esis of 4c. Yield: 61%. 31P NMR (202.5 MHz, CD2-
Cl2, H3PO4): δ 2.89 (s). 1H NMR (500 MHz, CD2Cl2): δ 2.77
(s, H4), 3.20 (m, anti-H29/H31), 3.93 (s, H10-H14), 4.50 (s,
H7), 4.54 (m, syn-H29/H31), 4.78 (m, H8), 5.04 (m, H30), 5.09
(s, H9), 6.62 (m, H33/H37), 6.74 (m, H34/H36), 6.87 (m, H35),
7.15 (m, H24), 7.22 (m, H22/H26), 7.43 (m, H23/H25), 7.64 (m,
H16/H20), 7.76 (m, H17/H19), 7.93 (m, H18). 13C NMR (125
MHz, CDCl3) for selected nuclei: δ 29.1 (s, C4), 72.1 (s, C10-
C14), 188.5 (d, J ) 29.1, C1), 212.3 (s) and 226.6 (s) (C27/C28),
109.9 (s, C30). HRMS (EI, m/z): calcd for C37H31NPO3IMoFe
Syn th esis of 4a . To a solution of 2a (0.81 g, 1.2 mmol) in
THF (20 mL) was added a 2 molar excess of allyl iodide (0.20
mL), and the reaction mixture was stirred under reflux for 2
h. The solvent was removed under vacuum, and the oily
residue was chromatographed on silica gel (eluent: diethyl
ether/MeOH, 8:2) to give dark red solids after usual workups.
Yield: 47%. 31P NMR (202.5 MHz, CD2Cl2, H3PO4): δ 4.48 (s).
1H NMR (500 MHz, CD2Cl2): δ 2.93 (s, H4), 3.00-3.07 (m,
anti-H29/H31), 4.47-4.07 (m, syn-H29/H31), 4.01 (s, H10-
H14), 4.71 (s, H7), 4.78 (br, H8), 4.89 (s, H9), 5.01 (br, H30),
7.24-7.28 (m, H22/H26), 7.43-7.47 (m, H23/H25), 7.53-7.56
(m, H24), 7.63-7.65 (m, H16/H20), 7.70-7.73 (m, H18), 7.89-
7.92 (m, H17/H19). 13C NMR (125.8 MHz, CD2Cl2): δ 25.0 (s,
C4), 61.0 (br, C6), 71.9 (s, C10-C14), 71.7 (s, C7), 72.1 (br,
C9), 74.8 (s)/75.3 (s) (C29/C31), 76.9 (br, C8), 79.2 (br, C5),
84.9 (d, J P ) 46.7, C2), 117.8 (s, C30), 123.9 (br, C15), 128.4
(br, C21), 129.0 (d, J P ) 12.7, C22/C26), 129.8 (br, C17/C19),
131.8 (br, C16/C20), 133.0 (d, J P ) 11.6, C23/C25), 134.4 (br,
C18), 154.8 (br, C3), 172.8 (d, J P ) 29.6, C1), 227.4 (s)/227.9
(s)(C27/C28). IR ν(CO): 1923 (vs), 1831 (vs) cm-1. HRMS (EI,
m/z): calcd for C31H27NPO3IMoFe 772.9177, found 772.9177.
Anal. Calcd for C31H27NPO3IMoFe: C, 48.30; H, 3.50; N, 1.80.
Found: C, 48.47; H, 3.77; N, 1.62.
848.9490, found 792.9589 (M+ - 2CO). Anal. Calcd for C37H31
-
NPO3IMoFe: C, 52.30; H, 3.65; N, 1.65. Found: C, 52.85; H,
3.95; N, 1.97.
Syn th esis of 5a . The title compound was prepared in the
same manner as described for the preparation of 4a by
replacing 2a with 3a . Yield: 85%. 31P NMR (121 MHz, CDCl3,
H3PO4): δ 4.35 (s). 1H NMR (500 MHz, CD2Cl2): δ 2.76 (s,
H4), 2.98 (m, anti-H29/H31), 4.19 (s, H10-H14), 4.45-4.30
(m, syn-H29/H31), 4.90 (s, H7), 5.03 (m, H8), 5.10 (s, H9), 7.95
(s, H1), 8.14-7.51 (m, H15-H26). 13C NMR (125.8 MHz,
CDCl3): δ 30.2 (s, C4), 69.9 (br, C6), 70.5 (br, C9), 71.6 (br,
C7), 72.6 (br, C8), 72.9 (s, C10-C14), 128.0 (br, C15), 128.2
(br, C21), 129.6 (br, C22/C26), 129.9 (d, J ) 13.3, C17/C19),
131.5 (br, C23/C25), 132.1 (d, J ) 0.8, C16/C20), 133.3 (s, C24),
134.8 (s, C18), 158.3 (br, C3), 177.7 (br, C1), 217.3 (s)/229.3
(s) (C27/C28). IR ν(CO): 1912 (s), 1814 (s) cm-1. HRMS (EI,

1,2-Ferrocenediylazaphosphinines
Organometallics, Vol. 22, No. 7, 2003 1481
m/z): calcd for C31H27NPO3IWFe 858.9632, found 858.9622.
Anal. Calcd for C31H27NPO3IWFe: C, 43.31; H, 3.14; N, 1.63.
Found: C, 43.29; H, 3.68; N, 1.42.
756.9882 (M+), found 756.9873. Anal. Calcd for C29H22NPO4-
ClFeRe: C, 45.97; H, 2.91; N, 1.85. Found: C, 46.02; H, 3.25;
N, 1.97.
Syn th esis of 8a . [Pd(η3-C3H5)Cl]2 (0.12 g, 0.33 mmol) and
1a (0.30 g, 0.66 mmol) were dissolved in CH2Cl2 (5 mL) in a
Schlenk tube. The mixture was stirred at room temperature
for 30 min, after which AgBF4 (0.13 g, 0.66 mmol) was added.
Any solid impurities were removed by filtration, and the
volume of the filtrate was reduced to about 2 mL. Slow
diffusion of diethyl ether into this solution at room tempera-
ture produced red crystals. A single crystal obtained in this
way was used for the X-ray analysis. Yield: 0.39 g, 86%. 31P
NMR (202 MHz, CDCl3, H3PO4): δ 4.80 (s). 1H NMR (500 MHz,
CD2Cl2): δ 2.58 (s, H4), 2.99-3.30 (m, anti-H27/H29), 3.94 (s,
H10-H14), 4.30-4.06 (m, syn-H27/H29), 4.96 (br, 7H), 5.08
(br, H8), 5.19 (br, H9), 5.58 (m, H28), 7.25 (m, H22/H26), 7.43
(m, H23/H25), 7.56 (m, H24), 7.75 (m, H16/H20), 7.80 (m, H18),
7.90 (m, H17/H19), 8.10 (br, H1). 13C NMR (100.6, CD2Cl2): δ
29.9 (s, C4), 57.5 (br, C7), 60.0 (d, J ) 103.7, C6), 63.3 (br,
C9), 72.9 (s, C10-C14), 74.0 (s, C27/C29), 77.8 (d, J ) 12.0,
C8), 79.5 (br, C5), 96.5 (d, J ) 107.7, C2), 114.4 (s, C28), 127.6
(d, J ) 89.5, C15/C21), 130.3 (d, J ) 13.0, C22/C26), 130.6 (d,
J ) 13.7, C17/C19), 132.4 (br, C16/C20), 133.6 (br, C23/C25),
134.3 (br, C24), 135.5 (br, C18), 158.7 (d, J ) 6.7, C3), 180.0
(d, J ) 31.8, C1). HRMS (EI, m/z): calcd for C29H27NPOFePd
598.0214 (M+), found 598.0212. Anal. Calcd for C29H27NPOBF4-
FePd: C, 50.81; H, 3.97; N, 2.04. Found: C, 50.59; H, 4.06; N,
1.91.
Syn th esis of 6a . A solution of 1a (0.50 g, 1.10 mmol) and
Mn(CO)5Br (0.31 g, 1.10 mmol) in THF (10 mL) in a Schlenk
tube equipped with a condenser was heated under reflux for
5 h. The solvent was removed under vacuum, and the remain-
ing red solid was chromatographed on silica gel (eluent:
diethyl ether/MeOH, 1:9). Recrystallization from CH2Cl2/
hexanes yielded the product as red crystals. Yield: 85%. 31P
NMR (121 MHz, CDCl3, H3PO4): δ 3.56 (s). 1H NMR (400 MHz,
CDCl3): δ 2.87 (s, H4), 3.96 (s, H10-H14), 4.78 (m, H7), 4.89
(m, H8), 5.02 (m, H9), 7.24 (br, H22/H26), 7.40 (br, H23/H25),
7.52 (br, H24), 7.65 (br, H16/H20), 7.70 (br, H18), 8.03 (br,
H17/H19), 8.20 (d, J ) 2.0, H1). 13C NMR (100.6 MHz,
CDCl3): δ 27.5 (s, C4), 69.0 (d, J ) 103.3, C6), 72.4 (d, J )
6.3, C9), 72.5 (d, J ) 7.2, C7), 72.6 (s, C10-C14), 76.7 (d, J )
12.1, C8), 81.3 (d, J ) 7.7, C5), 95.3 (d, J ) 106.0, C2), 124.9
(d, J ) 94.5, C15), 127.7 (d, J ) 89.6, C21), 130.2 (d, J ) 13.2,
C22/C26), 130.4 (d, J ) 13.2, C17/C19), 132.6 (d, J ) 11.6,
C16/C20), 133.6 (d, J ) 10.9, C23/C25), 134.2 (d, J ) 2.8, C24),
135.2 (d, J ) 2.8, C18), 154.4 (d, J ) 7.6, C3), 180.9 (d, J )
30.2, C1), 222.8 (s), 224.7 (s), 225.4 (s) (C27-C29). IR ν(CO):
2018 (vs), 1917 (vs), 1897 (vs) cm-1. HRMS (EI, m/z): calcd
for C29H22NPO4BrFeMn 670.1501 (M+), found 584.8850 (M+
- 3CO). Anal. Calcd for C29H22NPO4BrFeMn: C, 51.97; H,
3.31; N, 2.09. Found: C, 52.08; H, 3.36; N, 1.99.
Syn th esis of 7a . Following the procedure for the synthesis
of 6a except for the replacement of MnBr(CO)5 with ReCl(CO)5,
an orange solid was isolated in 95%. 1H NMR (400 MHz,
CDCl3): δ 2.84 (s, H4), 4.00 (s, H10-H14), 4.83 (m, H7), 4.95
(m, H8), 5.08 (m, H9), 7.26-7.30 (m, H22/H26), 7.41-7.44 (m,
H23/H25), 7.54-7.57 (m, H24), 7.69-7.71 (br, H16/H20), 7.74-
7.77 (m, H18), 8.07-8.11 (m, H17/H19), 8.17 (d, H1, J ) 2.0).
13C NMR (100.6 MHz, CDCl3): δ 29.3 (s, C4), 181.1 (d, J )
31.3, C1), 59.3 (d, J ) 102.7, C6), 73.1 (d, J ) 5.0, C9), 73.2
(d, J ) 3.8, C7), 73.5 (s, C10-C14), 77.1 (d, J ) 12.2, C8),
80.2 (d, J ) 7.6, C5), 98.5 (d, J ) 107.7, C2), 125.7 (d, J )
95.1, C15), 128.0 (d, J ) 90.7, C21), 130.2 (d, J ) 25.7, C22/
C26), 130.3 (d, J ) 10.2, C17/C19), 132.6 (d, J ) 11.4, C16/
C20), 134.1 (d, J ) 12.0, C23/C25), 134.2 (d, J ) 2.8, C24),
135.2 (d, J ) 3.3, C18), 157.8 (d, J ) 8.7, C3), 192.6 (s), 198.2
(s), 199.3 (s) (C27-C29). IR ν(CO): 2013 (vs), 1917 (vs), 1877
(vs) cm-1. HRMS (EI, m/z): calcd for C29H22NPO4ClFeRe
Syn th esis of 8c. 31P NMR (202 MHz, CDCl3, H3PO4): δ
4.48 (s). H NMR (500 MHz, CD2Cl2): δ 2.78 (s, H4), 2.99 (m,
1
anti-H27/H29), 3.86 (s, H10-H14), 4.08 (m, syn-H27/H29), 4.82
(s, H7), 5.01 (m, H8), 5.25 (s, H9), 5.62 (m, H28), 6.85-6.69
(m, 5H, H30-H35), 7.98-7.04 (m, 10H, H15-H26). 13C NMR
(125 MHz, CDCl3): δ 30.5 (s, C4), 62.8 (d, J ) 101.6, C6), 71.5
(s, C27/C29), 73.3 (d, J ) 6.5, C7), 74.3 (d, J ) 8.2, C9), 77.9
(br, C8), 94.6 (d, J ) 101.6, C2), 114.0 (s, C28), 125.7 (d, J )
170.0, C15), 125.7 (d, J ) 16.4, C30), 128.7 (d, J ) 129.5, C21),
129.1 (s, C32/C34), 129.5 (d, J ) 20.9, C22/C26), 130.0 (d, J )
13.2, C17/C19), 131.1 (d, J ) 68.1, C31/C35), 131.8 (s, C33),
133.1 (d, J ) 11.1, C23/C25), 133.0 (d, J ) 7.3, C16/C20), 134.5
(s, C24), 137.3 (s, C18), 160.4 (br, C3), 189.5 (d, J ) 30.3, C1).
HRMS (EI, m/z): calcd for C35H31NPOFePd 674.0527 (M+),
found 674.0526. Anal. Calcd for C35H31BNPOF4FePd: C, 55.19;
H, 4.10; N, 1.84. Found: C, 55.63; H, 4.37; N, 1.31.

1482 Organometallics, Vol. 22, No. 7, 2003
Co et al.
52.5, 41.4, 34.3, 29.7, 22.0, 13.6. MS: m/z (%) 214 (1, M+), 182
(3), 165 (2), 132 (9), 119 (100), 101 (70), 83 (80), 67 (50), 55
(51).
Dim eth yl 2-(1-P h en ylp r op -2-en yl)p r op a n ed ioa te (11a ).
GC (CBP-10) conditions for diastereomeric separation: tR, 22.4
min; oven temp, 100 °C; injection temp, 220 °C, initial time, 2
min; final temp, 200 °C; rate, 5 °C/min; detection temp, 250
°C; column pressure, 100 kPa. IR (KBr): 3031 (w), 2954 (m),
1760 (s), 1740 (s), 1639 (w), 1602 (w), 1494 (w), 1435 (m), 1263
(m), 1198 (m), 1163 (m), 1027 (w), 765 (w) cm-1. 1H NMR (300
MHz, CDCl3): δ 7.32-7.19 (m, 5H), 5.99 (ddd, J ) 17.0, 10.2,
8.1, CH), 5.15-5.06 (m, 2H), 4.14-4.08 (m, CH), 3.87 (d, J )
11.0, CH), 3.74, 3.49 (2s, 6H). 13C NMR (75 MHz, CDCl3): δ
168.2, 167.8, 139.9, 137.8, 128.7, 127.9, 127.1, 116.6, 57.4,-
52.6, 52.4, 49.7. MS: m/z (%) 248 (2, M+), 217 (2), 189 (100),
156 (19), 129 (43), 117 (100), 91 (19).
Typ ica l P r oced u r e for Allylic Alk yla tion . To a solution
of dimethylsodium malonate (prepared from dimethyl mal-
onate (40.0 mg, 0.30 mmol) and NaH (5.3 mg, 0.22 mmol) in
2,4-dioxane or THF (1.0 mL) at RT) and allyl substrate (0.17
mmol) was added catalyst (0.025 mmol for Mo- and W-
catalysis; 0.017 mmol for Pd-catalysis). The mixture was
stirred at 80 °C (RT in the case of Pd-catalysis) until the
reaction was complete (as evidenced by TLC), then diluted with
ether (2 mL), and washed successively with 5% aqueous
NaHCO3 and water. The organic phase was dried with MgSO4,
and the solvent was evaporated under reduced pressure. The
oily residue was passed through a short silica gel column to
remove catalyst using a 9:1 hexane-ethyl acetate mixture as
an eluent. The diastereomeric excess (% de) was determined
by GC equipped with a CBP-10 on a Shimadzu GC-17A.
Dim et h yl 2-[(E)-3-P h en ylp r op -2-en yl]p r op a n ed ioa t e
(10b). GC (CBP-10) conditions for diastereomeric separation:
tR, 29.6 min; oven temp, 100 °C; injection temp, 220 °C, initial
time, 2 min; final temp, 200 °C; rate, 5 °C/min; detection temp,
250 °C; column pressure, 100 kPa. Rf ) 0.32 (hexane/EtOAc,
6:1). IR (KBr): 3448 (s), 2359 (w), 1734 (m), 1635 (s), 1435
1
(w), 1261 (w), 1153 (m), 966 (w), 749 (m) cm-1. H NMR (300
MHz, CDCl3): δ 7.20-7.34 (m, 5 arom. CH), 6.48 (d, J ) 15.6,
CH), 6.16 (dt, J ) 15.8, 7.2, CH), 3.74 (s, 2 OCH3), 3.53 (t, J )
14.7, CHCO), 2.80 (dt, J ) 15.9, 1.2, CH2). 13C NMR (75 MHz,
CDCl3): δ 169.1 (CdO), 136.9 (arom. C), 132.8 (CH), 128.4
(CH), 127.3 (CH), 126.1 (CH), 125.3 (CH), 52.4, 51.6 (CH, Me),
32.2 (CH2). MS: m/z (%) 248 (30, M+), 188 (38), 157 (20), 129
(100), 117 (61), 84 (19).
Dim eth yl 2-(1,3-Dip h en ylp r op -2-en yl)p r op a n ed ioa te
(13). 1H NMR (500 MHz, CDCl3): δ 3.51 (s, OCH3), 3.70 (s,
OCH3), 3.95 (d, J ) 11, CHCO), 4.26 (dd, J ) 9 and 11, PhCH),
6.33 (dd, J ) 9 and 16, PhCHdCH), 6.47 (d, J ) 16, PhCHd
CH), 7.18-7.33 (m, Ph). 13C NMR (75 MHz, CDCl3): δ 49.2
(CHPh), 52.5 (OCH3), 52.6 (OCH3), 57.6 (CHCO), 126.4/127.2
(PhCHdCH), 127.6/127.9/128.4/128.7/129.1/131.8/136.8/140.2
(Ph), 167.6/167.8 (CdO).
Typ ica l P r oced u r e for Asym m etr ic Allylic Alk yla tion .
A mixture of chiral ligand (0.02 mmol) and [Pd(η3-C3H5)Cl]2
(0.02 mmol) in a dry solvent (2 mL) was stirred at RT in a
Schlenk tube. To this Pd-catalyst generated in situ was added
a solution of 1,3-diphenyl-2-propenyl acetate (12) (0.13 g, 0.50
mmol) in the same solvent (2 mL), followed by the addition of
dimethyl malonate (0.17 mL, 1.50 mmol), KOAc (0.001 g, 0.01
mmol), and N,O-bis(trimethylsilyl)acetamide (0.37 mL, 1.50
mmol). The reaction mixture was heated under reflux for 24
h. After cooling to room temperature, the reaction mixture was
diluted with diethyl ether (10 mL) and water, and the organic
layer was washed with brine and dried over MgSO4. After
evaporation of solvent in vacuo, the residue was purified by
column chromatography on silica gel (eluent, hexane-ethyl
acetate, 9:1). The enantioselectivity was determined by HPLC
analysis with a chiral column (Chiralcel OD-H; 25 cm × 0.46
cm; hexane/i-PrOH, 99:1; flow rate, 0.6 mL/min; tR, 21.680; tS,
23.301 min) and 1H NMR analysis with chiral shift reagent
Eu(hfc)3 (one of two methyl ester groups that appears at 3.70
was split into two peaks, for example, at 3.78 (R) and 3.74 (S)
when 0.5 equiv of the chiral shift reagent was added).22
X-r a y Str u ctu r e Deter m in a tion . Crystallographic data
for 3a and 8a are collected in Tables 1 and 2. An ORTEP
drawing showing the numbering scheme used in refinement
is presented in Figures 1 and 2. Intensity data were collected
at room temperature with
a CAD4 diffractometer using
monochromated Mo KR radiation (λ ) 0.71073 Å). Lorentz and
polarization reflections were applied and absorption correc-
tions made with 3 Ψ scans. The structures were solved by
direct methods and refined by full-matrix least-squares meth-
ods based on F2 using SHELXS-97 and SHELXL-97.23 Non-
hydrogen atoms were refined anisotropically, and hydrogen
atoms were included in calculated positions. Additional crys-
tallographic data are available in the Supporting Information.
Dim eth yl 2-[(E)-Hex-2-en yl]p r op a n ed ioa te (10a ). This
was obtained as the product from the reaction of (E)-1-acetoxy-
2-hexene with dimethylsodium malonate. GC (CBP-10) condi-
tions for diastereomeric separation: tR, 15.4 min; oven temp,
100 °C; injection temp, 220 °C, initial time, 2 min; final temp,
200 °C; rate, 5 °C/min; detection temp, 250 °C; column
pressure, 100 kPa. IR (KBr): 2958 (s), 2930 (m), 2850 (m), 1737
(s), 1457 (m), 1379 (m), 1274 (s), 1146 (m), 973 (m), 745 (w)
Ack n ow led gm en t. T.J .K. gratefully acknowledges
KRF for financial support (Grant No.: PBRG 070-
C00055) and KBSI for NMR and mass spectral mea-
surements.
cm-1 1H NMR (300 MHz, CDCl3): δ 5.79 (m, 1H), 5.56 (m,
.
1H), 4.59 (d, J ) 6.3, 2H), 3.75 (s, 6H), 3.40 (br, 1H), 2.02 (dq,
J ) 21.3, 6.9, 2H), 1.42 (sextet, J ) 36.9, 2H), 0.90 (t, J )
14.7, 3H). 13C NMR (75 MHz, CDCl3): δ 169.1, 137.1, 123.2,
Su ppor tin g In for m ation Available: Tables giving atomic
coordinates, displacement parameters, and bond distances and
angles for 3a and 8a . This material is available free of charge
via the Internet at http://pubs.acs.org.
OM020929N
(22) (a) Ahn, K. H.; Cho, C.-W.; Park, J . W.; Lee, S. W. Tetrahedron
Asymmetry 1997, 8, 1179. (b) Chelucci, G.; Deriu, S.; Pinna, G. A.; Saba,
A.; Valenti, R. Tetrahedron Asymmetry 1999, 10, 3803. (c) You, S.-L.;
Hou, X.-L.; Dai, L.-X.; Yu, Y.-H.; Xia, W. J . Org. Chem. 2002, 67, 4684.
(23) Sheldrick, G. M. SHELXS-86; Universita¨t Go¨ttingen: 1986;
SHELXS-97; Universita¨t Go¨ttingen: 1997.