Titanacyclobutenes or titanium vinyl carbene complexes? Reactivity of organotitanium species generated by the reaction of γ-chloroallyl sulfides with a titanocene(II) reagent

Article abstract of DOI:10.1002/chem.200601418

The reactivity of the organotitanium species generated by the reductive titanation of γ-chloroallyl sulfides with the titanocene(II) reagent [Cp₂Ti{P(OEt)₃}₂] was studied. The organotitanium species formed from α-monosubstituted γ-chloroallyl sulfides reacted with 1,5-diphenylpentan-3-one and styrene to produce conjugated dienes and vinyl cyclopropanes as major products, thus suggesting the formation of vinyl carbene complexes as intermediates. On the contrary, the organotitanium species generated from acyclic β,γ-disubstituted γ-chloroallyl sulfides revealed titanacyclobutene-like reactivity, and their reaction with 1,5-diphenylpentan-3-one produced homoallyl alcohols. These organotitanium species did not react with styrene, but did react with dichlorophenylphosphine to afford phosphacyclobutenes. In the case of β-monosubstituted, γ-monosubstituted, and α,γ- disubstituted γ-chloroallyl sulfides, the organotitanium species reacted with both 1,5-diphenylpentan-3-one and styrene. The former reaction produced homoallyl alcohols and the latter gave vinyl cyclopropanes or unconjugated dienes. These results suggest that titanacyclobutenes and/or titanium vinyl carbene complexes are produced by the reductive titanation of γ-chloroallyl sulfides depending on their substitution patterns.

Full text of DOI:10.1002/chem.200601418

DOI: 10.1002/chem.200601418
Titanacyclobutenes or Titanium Vinyl Carbene Complexes? Reactivity of
Organotitanium Species Generated by the Reaction of g-Chloroallyl Sulfides
with a Titanocene(II) Reagent
Tomohiro Shono, Rie Kurashige, Ryo Mukaiyama, Akira Tsubouchi, and
Takeshi Takeda*[a]
Abstract: The reactivity of the organo-
titanium species generated by the re-
ductive titanation of g-chloroallyl sul-
fides with the titanocene(II)reagent
ganotitanium species generated from
acyclic b,g-disubstituted g-chloroallyl
sulfides revealed titanacyclobutene-like
reactivity, and their reaction with 1,5-
diphenylpentan-3-one produced homo-
allyl alcohols. These organotitanium
species did not react with styrene, but
did react with dichlorophenylphosphine
to afford phosphacyclobutenes. In the
case of b-monosubstituted, g-monosub-
stituted, and a,g-disubstituted g-chlor-
oallyl sulfides, the organotitanium spe-
cies reacted with both 1,5-diphenylpen-
tan-3-one and styrene. The former re-
action produced homoallyl alcohols
and the latter gave vinyl cyclopropanes
or unconjugated dienes. These results
suggest that titanacyclobutenes and/or
titanium vinyl carbene complexes are
produced by the reductive titanation of
g-chloroallyl sulfides depending on
their substitution patterns.
[Cp2Ti{PACHTREUNG(OEt)3}2] was studied. The or-
ganotitanium species formed from a-
monosubstituted g-chloroallyl sulfides
reacted with 1,5-diphenylpentan-3-one
and styrene to produce conjugated
dienes and vinyl cyclopropanes as
major products, thus suggesting the for-
mation of vinyl carbene complexes as
intermediates. On the contrary, the or-
Keywords: alkenes · heterocycles ·
ketones · metallacycles · titanium
Introduction
Doxsee et al. suggested the above equilibrium for the iso-
merization of a-isopropenyl-b-ethyltitanacyclobutene into
a-(1-ethylethenyl)-b-methyltitanacyclobutene.[1] The process,
however, has not been fully explored. Binger et al. reported
the selective formation of these two organotitanium species:
a,b-diphenyltitanacyclobutene is exclusively formed by the
Whether metallacyclobutenes exist in equilibrium with vinyl
carbene complexes is one of the key issues in organo-transi-
tion-metal chemistry. Decisive experimental evidence for
the equilibrium between titanacyclobutenes 1 and titanium
vinyl carbene complexes 2 (Scheme 1)has not yet appeared.
reaction of 1,2-diphenylcyclopropene with [Cp2TiACHTREUNG(PMe3)2]
(Cp=cyclopentadienyl), whereas the g,g-diphenylvinylcar-
bene complex is produced by a similar reaction of 3,3-diphe-
nylcyclopropene.[2] Titanacyclobutenes 1 bearing two identi-
cal substituents at the a- and b-positions have been pre-
pared by the reaction of symmetrical alkynes with titano-
cene methylidene.[3] On the basis of an investigation into
their reactivity toward various organic compounds,[3,4] it has
been suggested that the titanacyclobutenes 1 formed are not
in equilibrium with vinyl carbene complexes 2. Furthermore,
Grubbs and co-workers ruled out the possibility of this pro-
cess in the insertion reaction of carbon monoxide into a,b-
disubstituted titanacyclobutenes on the basis of kinetic stud-
ies.[5]
Scheme 1. The equilibrium between titanacyclobutenes 1 and titanium
vinyl carbene complexes 2.
[a] T. Shono, R. Kurashige, R. Mukaiyama, Dr. A. Tsubouchi,
Prof. Dr. T. Takeda
Department of Applied Chemistry
Graduate School of Engineering
Tokyo University of Agriculture and Technology
Koganei, Tokyo 184–8588 (Japan)
Fax : (+81)42-388-7034
To clarify the structure-dependent reactivity of organotita-
nium species 1 and 2 toward organic molecules, we have ex-
plored a versatile method for the preparation of these spe-
E-mail: takeda-t@cc.tuat.ac.jp
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Chem. Eur. J. 2007, 13, 4074 – 4080

FULL PAPER
cies. Herein, we describe the formation of organotitanium
species by the reductive titanation of g-chloroallyl sulfides 3
with a titanocene(II)reagent 4 and their dual reactivity as
titanacyclobutenes 1 and vinyl carbene complexes 2 depend-
ing on the substitution patterns of 3 (Table 1).
Scheme 3. Reaction of titanium vinyl carbene complexes 2 with carbonyl
compounds.
Table 1. The formation of titanacyclobutenes 1 and/or titanium vinyl car-
bene complexes 2 by the reaction of g-chloroallyl sulfides 3 with titano-
ACHTREUNGcene(II)reagent 4.
six-membered titanacycles 9 when treated with ketones and
aldehydes (Scheme 4).[4a] Doxsee and Mouser reported that
regioisomers 10 were also formed by the insertion of car-
3
R1
R2
R3
Ratio of stereoisomers
3a
3b
3c
3d
3e
3 f
3g
3h
3i
H
H
H
Ph
H
H
H
H
H
Me
Et
H
H
H
H
Et
Ph
H
H
H
H
H
H
100:0
100:0
82:18
95:5
Me
Hex
Ph
Ph
Ph
Et
92:8
100:0
100:0
59:41
–
–(CH2)4–
3j
3k
3l
Ph
Ph
Me
Ph
Me
Et
Ph
Ph
96:4
Scheme 4. Reaction of titanacyclobutenes 1 with carbonyl compounds.
100:0
66:34
74:26
3m
bonyl compounds into the titanium–vinyl bond.[4c] There-
fore, the formation of 5a and 7a suggests that both organo-
titanium species 1 and 2 would act as the intermediates in
the reaction of 3a, though the formation of 5a via a gem-di-
À
Results and Discussion
The treatment of the organotitanium species generated by
the reductive titanation of a-monosubstituted g-chloroallyl
sulfide 3a (2 equiv)with 4 (6 equiv)at 25 8C produced the
organotitanium species that affords the E-conjugated diene
5a stereoselectively on treatment with 1,5-diphenylpentan-
3-one (6; Scheme 2). It is of interest that homoallyl alcohol
7a was also produced as a minor product.
titanium species such as [(Cp2PhSTi)
CHEt], is not neglected at this stage.
ACHTRE(UNG Cp2ClTi)CH CH=
In the reactions of b- and g-monosubstituted and a,g- and
b,g-disubstituted g-chloroallyl sulfides 3 with 6, however, the
exclusive formation of homoallyl alcohols 7 and/or 11 was
observed (Table 2). It was found that the substituent R1 in 7
is absolutely cis to R2 regardless of the stereoisomeric purity
of the starting materials 3. These results indicate that the re-
actions of all these g-chloroallyl sulfides 3 follow a pathway
that involves the titanacyclobutenes 1 (see Scheme 4). Al-
though their regioselectivity is somewhat complicated, the
tendency for a-phenyl-substituted titanacyclobutenes 1 to
preferentially produce products 7 from titanium–alkyl bond
insertion was observed (Table 2, entries 3, 4, and 8). A simi-
lar regioselectivity was observed in the reaction of a,b-di-
phenyltitanacyclobutene prepared from titanocene methyli-
dene and diphenylacetylene with ketones.[4c] The formation
of homoallyl alcohols of the type 7 by the reaction of vinyl
carbene complexes 2 with 6 via the six-membered transition
states 12 (Scheme 5)should be ruled out on the basis of the
formation of another type of homoallyl alcohol 11 and the
results of the reaction with styrene (13; see below).
Scheme 2. Reaction of a-monosubstituted g-chloroallyl sulfide 3a with
1,5-diphenylpentan-3-one (6).
Previously, we reported the formation of conjugated
dienes 5 by the reaction of g-substituted vinyl carbene com-
plexes 2 (R1 =R2 =H; R3 =Ph, alkyl)with carbonyl com-
Vinyl carbene complexes 2 react with terminal olefins to
afford vinyl cyclopropanes,[7] whereas there has been no
report on the reaction of titanacyclobutanes 1 with terminal
olefins. We then studied the reactivity of the organotitanium
intermediates generated from g-chloroallyl sulfides 3 with
different substitution patterns to styrene (13).
pounds
via
oxatitanacyclobutane
intermediates
8
(Scheme 3).[6] Grubbs and Meinhart demonstrated that the
a,b-disubstituted titanacyclobutenes 1 (R1 =R2 =Ph, alkyl;
R3 =H), on the contrary, produce homoallyl alcohols 7 via
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T. Takeda et al.
Table 2. Reaction of g-chloroallyl sulfides 3 with 1,5-diphenylpentan-3-
one (6).
Entry
Sulfide 3
Products[a]
1[b]
3b
Scheme 6. The formation of vinyl cyclopropanes 14 through the reductive
elimination of titanacyclobutanes 15.
2[d]
3[d]
4[d]
3c
3e
3 f
Table 3. Reaction of g-chloroallyl sulfides 3 with styrene (13).
Entry
Sulfide 3
Products[a]
1[b]
3a
2[d]
3b
3[b]
4[b]
5[b]
6[b]
3c
3d
3 f
3g
5[d]
3g
3h
6[b]
7[b]
3i
7[d]
3i
8[b]
3m
8[g]
3m
[a] Yields of the isolated products are given in parentheses. [b] Performed
by using procedure B, as described in the Experimental Section. [c] The
insertion of 6 into the titanium–alkyl and titanium–vinyl bonds affords
the same homoallyl alcohol. [d] Performed by using procedure C, as de-
scribed in the Experimental Section.
[a] Yields of the isolated products are given in parentheses. [b] Performed
by using procedure D, as described in the Experimental Section. [c] Ratio
of isomers. [d] Performed by using procedure E, as described in the Ex-
perimental Section. [e] Obtained as a single isomer. [f] Contaminated
with a trace amount of (E)-1,4-diphenyl-1,4-pentadiene (16a). [g] Per-
formed by using procedure F, as described in the Experimental Section.
monosubstituted g-chloroallyl sulfides 3c and 3d also gave
vinyl cyclopropanes 14c and 14d (Table 3, entries 3 and 4).
The alternative conceivable mode of the reaction via tita-
nacyclobutanes 15 is b-elimination followed by reductive
elimination to produce unconjugated dienes 16 (Scheme 7).
The concomitant formation of conjugated diene 17 by reac-
tion of 3b (Table 3, entry 2), therefore, would be rational-
ized by the isomerization of the initially produced unconju-
gated diene 16a. The stereoselective formation of (E,E)-
dienes 16b and 16c was indeed observed when the a,g-dis-
Scheme 5. A possible pathway for the formation of homoallyl alcohols 7
by the reaction of vinyl carbene complexes 2 with 6.
As is expected from the selective formation of diene 5a
by the reaction of ketone 6, the treatment of a-substituted
g-chloroallyl sulfide 3a with the titanocene(II)reagent 4 in
the presence of 13 gave vinyl cyclopropane 14a through the
reductive elimination of titanacyclobutane intermediate 15
(Scheme 6; Table 3, entry 1). The most significant finding is
that the organotitanium species generated from b-monosub-
stituted g-chloroallyl sulfide 3b, which reacted with 6 via ti-
tanacycle 1, also produced vinyl cyclopropane 14b on reac-
tion with 13 (Table 3, entry 2). Similarly, the reactions of g-
Scheme 7. The formation of unconjugated dienes 16 through the b-elimi-
nation of titanacyclobutanes 15.
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Reactivity of Organotitanium Species
FULL PAPER
ubstituted sulfides 3 f and 3g were employed (Table 3, en-
tries 5 and 6). Although the reaction of cyclic g-chloroallyl
sulfide 3i with 13 gave conjugated diene 18 through the
ring-opening of the initially formed vinyl cyclopropane
(Table 3, entry 7), neither 14 nor 16 were obtained by reac-
tion of acyclic b,g-disubstituted sulfides 3h and 3m with 13;
for example, only the reduction products 19 were produced
in 67% total yield when 3m was employed (Table 3,
entry 8). These results suggest that the organotitanium inter-
mediates generated from acyclic b,g-disubstituted g-chlor-
oallyl sulfides behave as a,b-disubstituted titanacyclobutenes
in the reaction with 13.
It has been reported that the a,b-disubstituted titanacyclo-
butenes 1 are transformed into phospha-,[8] arsa-,[8b] and
stiba-[8e] cyclobutenes. As the above results indicate that the
treatment of b,g-disubstituted g-chloroallyl sulfides 3 with 4
affords the a,b-disubstituted titanacyclobutenes 1 bearing
various substituents, we examined their transformation into
phosphacycles.
The successive treatment of 3j–m with 4 at 258C for 1 h
and with dichlorophenylphosphine (20)under reflux in THF
for 1 h produced the phosphacyclobutene P-oxides 21 (see
Table 4 and Scheme 8). The formation of 21 is explained by
the oxidation of the initially formed phosphacyclobutenes 22
in air[8c] during the work-up and isolation. A similar treat-
ment of the organotitanium species generated from 3 (other
than the b,g-disubstituted species with at least one phenyl
group)resulted in messy reactions, and no formation of
phosphacycles 21 was observed. These unsuccessful results
would be attributable, at least in part, to the equilibration of
the titanacycles 1 with the vinyl carbene complexes 2.
All the above results indicate that the reaction mode of
the organotitanium intermediates generated from 3 is de-
pendent on their substitution patterns. In the case of the a-
monosubstituted derivatives, the intermediates act as vinyl
carbene complexes 2 for both ketone 6 and styrene (13),
whereas the a,b-disubstituted titanacyclobutenes are pre-
dominant intermediates for the reaction of acyclic b,g-disub-
stituted g-chloroallyl sulfides. The organotitanium species
generated from other g-chloroallyl sulfides show dual reac-
tivity as the titanacyclobutenes 1 for 6 and the vinyl carbene
complexes 2 for 13. Such behavior may be explained by the
equilibrium between 1 and 2.
Conclusion
The present study has demonstrated that organotitanium
species generated by the reaction of g-chloroallyl sulfides
with the titanocene(II)reagent 4 reveal, in principle, dual
reactivity as titanacyclobutenes and vinyl carbene com-
plexes. The a,b-disubstituted titanacyclobutenes formed
from g-chloroallyl sulfides are useful for the regioselective
preparation of unsymmetrically substituted phosphacyclobu-
tenes.
Experimental Section
THF was distilled from sodium and benzophenone. Preparative thin-
layer chromatography (PTLC)was carried out using Wakogel B-5F.
Column chromatography was performed on Merck Si 60. 1H and
13C NMR spectra (300 and 75 MHz, respectively)were recorded in
CDCl3 and chemical shifts (d)are quoted in parts per million from tetra-
methylsilane for 1H NMR and from CDCl3 for 13C NMR spectroscopy
unless otherwise noted. IR absorptions are reported in cmÀ1. All the re-
actions were carried out in an argon atmosphere. g-Chloroallyl sulfide 3a
was prepared from 3-(trimethylsilyl)-2-propyn-1-ol: The alcohol was
transformed into a propargyl sulfide (PhSSPh–Bu3P)[9] and ethylated
(LDA—EtBr; LDA= lithium diisopropylamide). Hydroalumination (di-
Table 4. Reaction of g-chloroallyl sulfides 3 with dichlorophenylphos-
phine (20).[a]
Entry
Sulfide 3
Product 21[b]
1
3j
21a (60)[c]
21b (60)
2
3
4
3k
3l
isobutylaluminum hydride; DIBAL)of the propargyl sulfide followed by
[10]
21c (56)[c]
21d (65)[c]
chlorination (N-chlorosuccinimide; NCS)
and desilylation (KOH/
MeOH)gave 3a. g-Chloroallyl sulfides 3b and 3e–m were prepared
from phenylacetaldehyde or ketones in three steps: The carbonyl com-
pounds were converted into b-chloro-a,b-unsaturated aldehydes by using
the Vilsmeier reagent.[11] These aldehydes were transformed into alcohols
by reduction (LiAlH4)or addition of Grignard reagents. Treatment of
the alcohols with PhSSPh–Bu3P gave 3b and 3e–m. Sulfide 3c was pre-
pared by the treatment of 1,3-dichloro-2-butene with PhSH–KOH. g-
Chloroallyl sulfide 3d was prepared from 2-heptyn-1-ol by hydroalumina-
tion (DIBAL), chlorination (NCS), and the treatment of the resulting al-
cohol with PhSSPh–Bu3P.
3m
[a] Performed by using procedure G, as described in the Experimental
Section. [b] Yield of the isolated products is given in parentheses.
[c] Contaminated with a trace amount of triethylphosphate; the yield was
corrected for this contaminant.
Reaction of g-chloroallyl sulfides 3 with 1,5-diphenylpentan-3-one (6)
Procedure A: Finely powdered molecular sieves 4 Š (MS4A; 150 mg),
magnesium turnings (37 mg, 1.5 mmol), and [Cp2TiCl2] (374 mg,
1.5 mmol)were placed in a flask and dried by heating with a heat gun
under reduced pressure (2–3 mmHg). After the mixture was cooled,
THF (2.5 mL)and P CAHTRE(UNG OEt)3 (0.51 mL, 3 mmol)were added successively
with stirring at 258C. After 3 h, a solution of 3a (107 mg, 0.5 mmol)in
THF (1.7 mL)was added dropwise over 3 min and the reaction mixture
was stirred for 10 min. Then a solution of 6 (60 mg, 0.25 mmol)in THF
Scheme 8. The formation of phosphacyclobutene P-oxides 21 by the reac-
tion of titanacyclobutenes 1 with dichlorophenylphosphine (20).
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T. Takeda et al.
(1.7 mL)was added dropwise over 3 min and the reaction mixture was
stirred for 2 h at 258C. The reaction was quenched by addition of 1m
NaOH, and the insoluble materials were removed by filtration through
Celite and washed with diethyl ether. The layers were separated and the
aqueous layer was extracted with diethyl ether. The combined organic
extracts were dried over Na2SO4. The solvent was removed under re-
duced pressure and the residue was purified by PTLC (eluant: pentane
and then hexane/AcOEt 9:1)to give ( E)-3-phenethyl-1-phenyl-3,5-octa-
diene (5a; 47 mg, 65%)and 4-ethyl-3-phenethyl-1-phenyl-5-hexen-3-ol
(7a; 6 mg, 8%). 5a: 1H NMR (300 MHz, CDCl3): d=1.00 (t, J=7.5 Hz,
3H), 2.10 (dq, J=7.2, 7.2 Hz, 2H), 2.31–2.39 (m, 2H), 2.44–2.53 (m, 2H),
2.67–2.79 (m, 4H), 5.65 (dt, J=15.0, 7.1 Hz, 1H), 5.88 (d, J=10.8 Hz,
1H), 6.21 (dd, J=10.7, 14.9 Hz, 1H), 7.13–7.33 ppm (m, 10H); 13C NMR
(75 MHz, CDCl3): d=13.8, 25.9, 33.1, 34.9, 35.1, 39.3, 125.1, 125.6, 125.8,
125.9, 128.3, 128.4, 135.0, 139.1, 142.1, 142.2 ppm; IR (neat): n˜ =3061,
3026, 2961, 2870, 1602, 1496, 1454, 962, 745, 698 cmÀ1; elemental analysis
calcd (%)for C 22H26: C 90.98, H 9.02; found: C 90.64, H 8.89. 7a:
1H NMR (300 MHz, CDCl3): d=0.88 (t, J=7.3 Hz, 3H), 1.18–1.35 (m,
1H), 1.55 (s, 1H), 1.59–1.73 (m, 1H), 1.76–2.04 (m, 4H), 2.09–2.21 (m,
1H), 2.57–2.81 (m, 4H), 5.18 (dd, J=2.1, 16.9 Hz, 1H), 5.26 (dd, J=2.1,
10.1 Hz, 1H), 5.67 (ddd, J=10.0, 10.0, 17.0 Hz, 1H), 7.14–7.36 ppm (m,
10H); 13C NMR (75 MHz, CDCl3): d=12.7, 21.3, 29.6, 29.7, 38.8, 39.3,
54.4, 74.9, 119.0, 125.8, 128.3, 128.39, 128.44, 138.3, 142.7, 142.8 ppm; IR
(neat): n˜ =3582, 3484, 3062, 3026, 2956, 2871, 1603, 1454, 1378, 1052,
1030, 1004, 940, 915, 748, 699 cmÀ1; elemental analysis calcd (%)for
C22H28O: C 85.66, H 9.15; found: C 85.56, H 8.94.
procedure C with 3e (156 mg, 0.6 mmol)and 6 (72 mg, 0.3 mmol). 7d
(67 mg, 63%): 1H NMR (300 MHz, CDCl3): d=1.58 (s, 1H), 1.56–1.91
(m, 4H), 2.52 (d, J=7.5 Hz, 2H), 2.71–2.77 (m, 4H), 6.28 (dt, J=15.8,
7.7 Hz, 1H), 6.53 (d, J=15.8 Hz, 1H), 7.19–7.39 ppm (m, 15H);
13C NMR (75 MHz, CDCl3): d=30.1, 41.3, 43.1, 74.3, 124.9, 125.9, 126.1,
127.4, 128.3, 128.5, 128.6, 134.0, 137.2, 142.2 ppm; IR (neat): n˜ =3563,
3453, 3060, 3025, 2935, 1602, 1495, 1453, 968, 747, 697 cmÀ1; elemental
analysis calcd (%)for C 26H28O: C 87.60, H 7.92; found: C 87.77, H 8.14.
11b (11 mg, 10%): 1H NMR (300 MHz, CDCl3): d=1.45 (s, 1H), 1.63–
1.82 (m, 2H), 1.92–1.97 (m, 2H), 2.60–2.77 (m, 4H), 3.51 (d, J=9.7 Hz,
1H), 5.20 (d, J=17.4 Hz, 1H), 5.21 (dd, J=1.8, 9.3 Hz, 1H), 6.36 (ddd,
J=10.1, 10,1 16.7 Hz, 1H), 7.08–7.34 ppm (m, 15H); 13C NMR (75 MHz,
CDCl3): d=29.9, 38.5, 38.9, 58.1, 75.4, 117.5, 125.8, 125.9, 126.8, 128.27,
128.34, 128.4, 128.45, 128.54, 129.2, 137.6, 140.7, 142.2, 142.3 ppm; IR
(neat): n˜ =3578, 3463, 3061, 3025, 2945, 2868, 1495, 1453, 748, 700 cmÀ1
;
elemental analysis calcd (%)for C 26H28O: C 87.60, H 7.92; found: C
87.23, H 8.20.
(E)-4-Ethyl-3-phenethyl-1,6-diphenyl-5-hexen-3-ol (7e): The reaction was
carried out according to procedure C with 3 f (173 mg, 0.6 mmol)and
6
(72 mg, 0.3 mmol). 7e (97 mg, 84%): 1H NMR (300 MHz, CDCl3): d=
0.91 (t, J=7.3 Hz, 3H), 1.27–1.45 (m, 1H), 1.57 (s, 1H), 1.67–2.04 (m,
5H), 2.33 (dt, J=2.3, 10.5 Hz, 1H), 2.61–2.85 (m, 4H), 6.07 (dd, J=9.9,
15.8 Hz, 1H), 6.53 (d, J=15.9 Hz, 1H), 7.13–7.43 ppm (m, 15H);
13C NMR (75 MHz, CDCl3): d=12.9, 21.8, 29.7, 29.8, 38.9, 39.5, 53.6,
75.5, 125.8, 126.2, 127.4, 128.36, 128.40, 128.45, 128.6, 129.9, 133.9, 137.1,
142.6, 142.7 ppm; IR (neat): n˜ =3572, 3479, 3083, 3060, 3025, 2955, 2871,
1602, 1495, 1453, 1378, 1030, 973, 945, 748, 696 cmÀ1; elemental analysis
calcd (%)for C 28H32O: C 87.45, H 8.39; found: C 87.38, H 8.48.
Procedure B: A solution of 3b (156 mg, 0.6 mmol)in THF (2 mL)was
added dropwise to a solution of 4 in THF (3 mL)(prepared from MS4A
(150 mg), magnesium turnings (44 mg, 1.8 mmol), [Cp2TiCl2] (448 mg,
(E)-3-Phenethyl-1,4,6-triphenyl-5-hexen-3-ol (7 f): The reaction was car-
1.8 mmol), and PACHTREUNG(OEt)3 (0.61 mL, 3.6 mmol)) over 3 min at 258C. The re-
ried out according to procedure C with 3g (202 mg, 0.6 mmol)and
6
(72 mg, 0.3 mmol). 7 f (114 mg, 88%): 1H NMR (300 MHz, CDCl3): d=
1.51 (s, 1H), 1.67–1.86 (m, 2H), 1.96–2.05 (m, 2H), 2.64–2.81 (m, 4H),
3.67 (d, J=9.7 Hz, 1H), 6.52 (d, J=15.8 Hz, 1H), 6.76 (dd, J=9.7,
15.8 Hz, 1H), 7.08–7.41 ppm (m, 20H); 13C NMR (75 MHz, CDCl3): d=
29.99, 30.03, 38.7, 39.1, 57.3, 76.0, 125.86, 125.88, 126.3, 126.9, 127.3, 128.
3, 128.35, 128.43, 128.46, 128.49, 128.6, 129.23, 129.24, 132.5, 137.2, 140.8,
142.09, 142.15 ppm; IR (neat): n˜ =3572, 3469, 3082, 3060, 3025, 2945,
2865, 1601, 1495, 1453, 1053, 1030, 969, 909, 746, 696 cmÀ1; elemental
analysis calcd (%)for C 32H32O: C 88.85, H 7.46; found: C 88.79, H 7.81.
action mixture was stirred for 1 h. Then a solution of 6 (72 mg, 0.3 mmol)
in THF (2 mL)was added dropwise over 3 min and the reaction mixture
heated to reflux for 2 h. The usual work-up and purification by PTLC
(hexane/AcOEt 9:1)gave 3-phenethyl-1,5-diphenyl-5-hexen-3-ol
( 7b;
1
64 mg, 60%). 7b: m.p. 86–888C; H NMR (300 MHz, CDCl3): d=1.56 (s,
1H), 1.67–1.84 (m, 4H), 2.49–2.72 (m, 4H), 2.86 (s, 2H), 5.24 (s, 1H),
5.38 (d, J=1.8 Hz, 1H), 7.00 (d, J=6.8 Hz, 4H), 7.12–7.47 ppm (m,
11H); 13C NMR (75 MHz, CDCl3): d=30.3, 41.2, 44.5, 74.1, 118.1, 125.7,
126.7, 127.7, 128.2, 128.3, 128.6, 142.3, 142.7, 145.6 ppm; IR (KBr): n˜ =
3536, 3024, 2925, 1495, 1452, 1383, 1268, 1103, 926, 768, 749, 719,
701 cmÀ1; elemental analysis calcd (%)for C 26H28O: C 87.60, H 7.92;
found: C 87.46, H 8.12.
(Z)-3-Phenethyl-1,5,6-triphenyl-5-hexen-3-ol (7g): The reaction was car-
ried out according to procedure B with 3m (202 mg, 0.6 mmol)and
6
(72 mg, 0.3 mmol). 7g (44 mg, 34%): m.p. 106–1088C; 1H NMR
(300 MHz, CDCl3): d=1.45 (s, 1H), 1.82 (t, J=8.7 Hz, 4H), 2.56–2.73
(m, 4H), 2.92 (s, 2H), 6.63 (s, 1H), 6.89–6.92 (m, 2H), 7.08–7.36 ppm (m,
18H); 13C NMR (75 MHz, CDCl3): d=30.3, 41.4, 49.1, 74.9, 125.8, 126.6,
127.5, 127.9, 128.3, 128.4, 128.96, 129.03, 129.1, 131.3, 136.8, 138.7, 141.2,
142.3 ppm; IR (KBr): n˜ =3462, 3025, 2938, 1494, 1449, 1189, 1041, 756,
698 cmÀ1; elemental analysis calcd (%)for C 32H32O: C 88.85, H 7.46;
found: C 88.76, H 7.49.
Procedure C: A solution of 3c (119 mg, 0.6 mmol)in THF (2 mL)was
added dropwise to a solution of 4 in THF (3 mL)(prepared from MS4A
(150 mg), magnesium turnings (44 mg, 1.8 mmol), [Cp2TiCl2] (448 mg,
1.8 mmol), and PACHTREUNG(OEt)3 (0.61 mL, 3.6 mmol)) over 3 min at 258C. The re-
action mixture was stirred for 10 min. Then a solution of 6 (72 mg,
0.3 mmol)in THF (2 mL)was added dropwise over 3 min and the reac-
tion mixture stirred for 1 h at 258C. The usual work-up and purification
by PTLC (hexane/AcOEt 9:1)gave ( E)-3-phenethyl-1-phenyl-5-hepten-
3-ol (7c; 21 mg, 24%)and 4-methyl-3-phenethyl-1-phenyl-5-hexen-3-ol
(11a; 34 mg, 38%). 7c: 1H NMR (300 MHz, CDCl3): d=1.53 (s, 1H),
1.72 (dd, J=1.1, 6.0 Hz, 3H), 1.81–1.85 (m, 4H), 2.30 (d, J=7.1 Hz, 2H),
2.67–2.72 (m, 4H), 5.52 (dtq, J=15.1, 7.2, 1.3 Hz, 1H), 5.62 (dq, J=15.1,
6.0 Hz, 1H), 7.16–7.32 ppm (m, 10H); 13C NMR (75 MHz, CDCl3): d=
18.2, 30.1, 41.1, 42.5, 73.7, 125.6, 125.8, 128.3, 128.4, 130.0, 142.5 ppm; IR
(neat): n˜ =3563, 3450, 3025, 2935, 1496, 1453, 970, 748, 698 cmÀ1; elemen-
tal analysis calcd (%)for C 21H26O: C 85.67, H 8.90; found: C 85.91, H
9.29. 11a: 1H NMR (300 MHz, CDCl3): d=1.09 (d, J=7.0 Hz, 3H), 1.48
(s, 1H), 1.79–1.91 (m, 4H), 2.50 (dq, J=7.2, 7.2 Hz, 1H), 2.59–2.79 (m,
4H), 5.15 (d, J=10.4 Hz, 1H), 5.16 (d, J=17.0 Hz, 1H), 5.89 (ddd, J=
8.7, 10.4, 16.9 Hz, 1H), 7.19–7.31 ppm (m, 10H); 13C NMR (75 MHz,
CDCl3): d=14.5, 29.7, 29.8, 38.5, 38.8, 45.3, 75.0, 116.6, 125.8, 128.3,
128.4, 128.5, 140.0, 142.59, 142.61 ppm; IR (neat): n˜ =3582, 3482, 3062,
3026, 2950, 1496, 1454, 748, 699 cmÀ1; elemental analysis calcd (%)for
C21H26O: C 85.67, H 8.90; found: C 85.91, H 8.62.
4-Ethyl-5-methyl-3-phenethyl-1-phenyl-5-hexen-3-ol (11c): The reaction
was carried out according to procedure B with 3h (136 mg, 0.6 mmol)
and 6 (72 mg, 0.3 mmol). Purification by PTLC (benzene) gave 11c
(53 mg, 55%). 11c: 1H NMR (300 MHz, CDCl3): d=0.85 (t, J=7.3 Hz,
3H,), 1.43–1.67 (m, 3H), 1.78 (s, 3H), 1.80–1.96 (m, 4H), 2.18 (dd, J=
3.1, 11.7 Hz, 1H), 2.58–2.76 (m, 4H), 4.86 (s, 1H), 5.02 (s, 1H), 7.16–
7.32 ppm (m, 10H); 13C NMR (75 MHz, CDCl3): d=12.6, 19.6, 30.16,
30.20, 30.8, 39.0, 39.3, 55.8, 75.3, 115.5, 125.79, 125.83, 128.28, 128.33,
128.4, 128.5, 142.5, 142.6, 145.0 ppm; IR (neat): n˜ =3490, 3026, 2957,
2872, 1496, 1454, 699 cmÀ1; elemental analysis calcd (%)for C 23H30O: C
85.66, H 9.38; found: C 85.28, H 9.58.
3-(2-Methylidenecyclohexyl)-1,5-diphenylpentan-3-ol (11d): The reaction
was carried out according to procedure B with 3i (143 mg, 0.6 mmol)and
6 (72 mg, 0.3 mmol). Purification by PTLC (hexane/benzene 1:2) gave
11d (40 mg, 40%). 11d: 1H NMR (300 MHz, CDCl3): d=1.41–2.08 (m,
11H), 2.13–2.19 (m, 1H), 2.26–2.38 (m, 1H), 2.42 (t, J=5.5 Hz, 1H),
2.58–2.80 (m, 4H), 4.84 (s, 1H), 4.93 (s, 1H), 7.17–7.32 ppm (m, 10H);
13C NMR (75 MHz, CDCl3): d=24.0, 27.8, 27.9, 30.0, 30.1, 35.9, 39.3,
39.6, 49.1, 76.0, 110.9, 125.77, 125.79, 128.3, 128.37, 128.41, 128.44, 142.6,
(E)-3-Phenethyl-1,6-diphenyl-5-hexen-3-ol (7d) and 3-phenethyl-1,4-di-
phenyl-5-hexen-3-ol (11b): The reaction was carried out according to
4078
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ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 4074 – 4080

Reactivity of Organotitanium Species
FULL PAPER
149.4 ppm; IR (neat): n˜ =3583, 3500, 3062, 3026, 2932, 2857, 1496, 1453,
747, 699 cmÀ1; elemental analysis calcd (%)for C 24H30O: C 86.18, H 9.04;
found: C 85.92, H 9.21.
6.42 (m, 2H), 7.16–7.42 ppm (m, 10H); 13C NMR (75 MHz, CDCl3): d=
13.7, 25.6, 51.4, 126.2, 126.3, 127.1, 128.0, 128.5, 130.0, 130.7, 132.8, 133.4,
137.5, 143.6 ppm; IR (neat): n˜ =3026, 2962, 2931, 1493, 1450, 968, 743,
698 cmÀ1; elemental analysis calcd (%)for C 19H20: C 91.88, H 8.12;
found: C 91.73, H 8.18.
Reaction of g-chloroallyl sulfides 3 with styrene (13)
Procedure D: A solution of 3a (64 mg, 0.3 mmol)in THF (1.2 mL)was
added dropwise to a solution of 4 in THF (1.8 mL)(prepared from
MS4A (54 mg), magnesium turnings (18 mg, 0.7 mmol), [Cp2TiCl2]
AHCTREUNG
(1E,4E)-1,3,5-Triphenyl-1,4-pentadiene (16c):[13] The reaction was car-
ried out according to procedure D with 3g (168 mg, 0.5 mmol)and 13
(0.23 mL, 2 mmol). 16c (77 mg, 53%): 1H NMR (300 MHz, CDCl3): d=
4.35–4.42 (m, 1H), 6.45–6.50 (m, 4H), 7.17–7.41 ppm (m, 15H);
13C NMR (75 MHz, CDCl3): d=51.6, 126.3, 126.6, 127.3, 128.1, 128.5,
128.6, 130.8, 131.9, 137.3, 142.8 ppm; IR (neat): n˜ =3081, 3059, 3026,
1599, 1494, 1448, 967, 908, 741, 694 cmÀ1; elemental analysis calcd (%)
for C23H20: C 93.20, H 6.80; found: C 93.21, H 7.16.
(187 mg, 0.8 mmol), and PACHTRE(UNG OEt)3 (0.26 mL, 1.5 mmol)in the presence of
13 (0.14 mL, 1.2 mmol)) over 3 min at 258C. The reaction mixture was
stirred for 4 h. The usual work-up and purification by PTLC (pentane)
gave (E)-1-(1-butenyl)-2-phenylcyclopropane (14a; 30 mg, 58%)as a
mixture of stereoisomers (85:15). 14a: 1H NMR (300 MHz, CDCl3): d=
0.84 (t, J=7.4 Hz, 0.45H), 0.91–1.08 (m, 1H), 0.97 (t, J=7.4 Hz, 2.55H),
1.13 (ddd, J=5.2, 5.2, 8.4 Hz, 0.85H), 1.17–1.24 (m, 0.15H), 1.57–1.68 (m,
0.85H), 1.74–1.94 (m, 1.45H), 2.02 (ddt, J=1.5, 7.4, 13.8 Hz, 1.7H), 4.76
(ddt, J=8.8, 15.3, 1.5 Hz, 0.15H), 5.14 (ddt, J=8.2, 15.2, 1.5 Hz, 0.85H),
5.58 (dt, J=15.2, 6.4 Hz, 1H), 7.02–7.30 ppm (m, 5H); 13C NMR
(75 MHz, CDCl3): d=11.6, 13.8, 14.0, 16.7, 24.9, 25.5, 25.6, 26.5, 125.4,
125.6, 125.7, 127.8, 127.9, 128.3, 129.1, 130.9, 131.0, 132.6, 142.8 ppm; IR
(neat): n˜ =3025, 2962, 1604, 1497, 1459, 959, 749, 696 cmÀ1; elemental
analysis calcd (%)for C 13H16: C 90.64, H 9.36; found: C 90.42, H 9.41.
1-Methylidene-2-(1-phenylethylidene)cyclohexane (18): The reaction was
carried out according to procedure E with 3i (119 mg, 0.5 mmol)and 13
(0.23 mL, 2 mmol). (E)-18 (43 mg, 43%): 1H NMR (300 MHz, CDCl3):
d=1.56–1.74 (m, 4H), 1.88 (s, 3H), 2.13 (br t, 2H), 2.27 (br t, 2H), 6.47
(d, J=15.9 Hz, 1H), 7.16–7.43 ppm (m, 6H); 13C NMR (75 MHz, CDCl3):
d=19.5, 22.8, 22.9, 25.5, 33.2, 124.9, 126.1, 126.7, 127.6, 127.9, 128.5,
134.9, 138.6 ppm; IR (neat): n˜ =3041, 2926, 1629, 1598, 1495, 1447, 955,
748, 691 cmÀ1; elemental analysis calcd (%)for C 15H18: C 90.85, H 9.15;
found:
C 90.56, H
9.08. (Z)-18 (11 mg, 11%): 1H NMR (300 MHz,
Procedure E: A solution of 3b (130 mg, 0.5 mmol)in THF (2 mL)was
added dropwise to a solution of 4 in THF (3.0 mL)(prepared from
MS4A (126 mg), magnesium turnings (43 mg, 1.8 mmol), [Cp2TiCl2]
CDCl3): d=1.57–1.73 (m, 7H), 1.95–2.04 (m, 2H), 2.04–2.12 (m, 2H),
4.97 (d, J=1.8 Hz, 1H), 5.53 (d, J=1.8 Hz, 1H), 7.21–7.42 ppm (m, 5H);
13C NMR (75 MHz, CDCl3): d=20.6, 23.2, 23.3, 30.4, 31.3, 112.5, 126.2,
127.3, 128.3, 129.8, 132.1, 139.9, 150.2 ppm; IR (neat): n˜ =3080, 3056,
(436 mg, 1.8 mmol), and PACHTRE(UNG OEt)3 (0.6 mL, 3.5 mmol)in the presence of
13 (0.23 mL, 2 mmol)) over 3 min at 25 8C. The reaction mixture was
heated to reflux for 4 h. The usual work-up and purification by PTLC
(hexane)gave a mixture of 1-phenyl-2-(1-phenylethenylc)yclopropane
(14b)and 1,4-diphenyl-1,3-pentadiene ( 17)[12] (74 mg: 14b: 25%, 17:
42%; E/Z=67:33). Mixture of 14b and 17: 1H NMR (300 MHz, CDCl3):
d=1.27 (ddd, J=5.3, 5.3, 8.5 Hz 0.37H), 1.39 (ddd, J=5.0, 6.2, 8.5 Hz,
0.37H), 1.92–2.04 (m, 0.74H), 2.19 (s, 0.63H), 2.27 (s, 1.26H), 5.04 (s,
0.37H), 5.35 (s, 0.37H), 6.31 (d, J=11.2 Hz, 0.21H), 6.53 (d, J=15.8 Hz,
0.21H), 6.61–6.72 (m, 0.84H), 6.86 (dd, J=11.0, 15.6 Hz, 0.21H), 7.09–
7.55 ppm (m, 10.42H); 13C NMR (75 MHz, CDCl3): d=15.9, 16.2, 25.6,
26.4, 27.8, 109.4, 125.6, 125.7, 125.8, 126.1, 126.25, 126.34, 126.7, 127.08,
127. 14, 127.3, 127.4, 127.55, 127.57, 128.17, 128.24, 128.3, 128.39, 128.44,
128.5, 128.6, 131.4, 132.9, 136.8, 137.8, 139.6, 141.1, 141.6, 142.5, 143.0,
148.3 ppm; IR (neat): n˜ =3057, 3028, 1602, 1494, 1443, 1027, 963, 777,
748, 696 cmÀ1; elemental analysis calcd (%)for C 17H16: C 92.68, H 7.32;
found: C 92.52, H 7.52.
3023, 2925, 2831, 1611, 1492, 1445, 1377, 1028, 897, 778, 708 cmÀ1
.
Procedure F: A solution of 3m (168 mg, 0.5 mmol)in THF (2 mL)was
added dropwise to a solution of 4 in THF (4.8 mL)(prepared from
MS4A (126 mg), magnesium turnings (49 mg, 2 mmol), [Cp2TiCl2]
(498 mg, 2 mmol), and PACHTRE(UNG OEt)3 (0.68 mL, 4 mmol)in the presence of 13
(0.23 mL, 2 mmol)) over 3 min at 25 8C. The reaction mixture was heated
to reflux for 4 h. The usual work-up and purification by PTLC (hexane)
gave a mixture of 1,2-diphenyl-1-propene (19a)and 2,3-diphenyl-1-pro-
pene (19b)(66 mg: 19a: 25%; ratio of stereoisomers=68:32, 19b: 42%) .
Mixture of 19a and 19b: 1H NMR (300 MHz, CDCl3): d=2.19 (d, J=
1.5 Hz, 0.75H), 2.27 (d, J=1.1 Hz, 0.36H), 3.82 (s, 1.26H), 5.00 (m,
0.63H), 5.48 (s, 0.63H), 6.46 (s, 0.25H), 6.84 (s, 0.12H), 6.87–7.53 ppm
(m, 10H); 13C NMR (75 MHz, CDCl3): d=17.4, 27.1, 41.6, 114.6, 125.97,
126.05, 126.06, 126.09, 126.4, 126.48, 126.53, 126.9, 127.2, 127.4, 127.6,
127.7, 127.8, 128.1, 128.2, 128.3, 128.4, 128.7, 128.9, 129.1, 137.4, 137.6,
138.3, 138.7, 139.5, 140.8, 142.1, 143.9, 146.9 ppm; IR (neat): n˜ =3082,
3059, 3026, 2913, 1626, 1600, 1495, 1443, 1029, 900, 777, 758, 725,
697 cmÀ1; elemental analysis calcd (%)for C 15H14: C 92.74, H 7.26;
found: C 92.74, H 7.38.
1-Ethenyl-1-methyl-2-phenylcyclopropane (14c): The reaction was car-
ried out according to procedure D with 3c (99 mg, 0.5 mmol)and 13
(0.23 mL, 2 mmol). 14c (56 mg, 71%, ratio of stereoisomers=76:24):
1H NMR (300 MHz, CDCl3): d=0.88 (s, 2.28H), 1.07–1.14 (m, 1.52H),
1.18–1.26 (m, 0.48H), 1.35 (s, 0.72H), 2.17 (dd, J=11.7, 11.7 Hz, 1H),
4.83–5.02 (m, 2H), 5.20 (dd, J=10.5, 17.2 Hz, 0.24H), 5.61 (dd, J=10.5,
17.1 Hz, 0.76H), 7.15–7.29 ppm (m, 5H); 13C NMR (75 MHz, CDCl3):
d=15.9, 18.8, 19.7, 25.1, 25.5, 30.9, 32.1, 109.8, 111.9, 126.0, 126.1, 129.3,
138.9, 142.3, 147.0 ppm; IR (neat): n˜ =3085, 3062, 2952, 1634, 1604, 1072,
1030, 993, 896, 698 cmÀ1; elemental analysis calcd (%)for C 12H14: C
91.08, H 8.92; found: C 90.60, H 9.18.
Reaction of g-chloroallyl sulfides 4 with dichlorophenylphosphine (20)
Procedure G: A solution of 3j (137 mg, 0.5 mmol)in THF (1.5 mL)was
added dropwise to a solution of 4 in THF (4.8 mL)(prepared from
MS4A (150 mg), magnesium turnings (49 mg, 2 mmol), [Cp2TiCl2]
(498 mg, 2 mmol), and PACHTRE(UNG OEt)3 (0.68 mL, 4 mmol)) over 3 min at 258C.
The reaction mixture was stirred for 1 h. Then 20 (0.17 mL, 1.3 mmol)
was added at 258C and the reaction mixture was heated to reflux for 1 h.
The reaction was quenched by addition of 1m NaOH, and the insoluble
materials were removed by filtration through Celite and washed with di-
ethyl ether. The layers were separated and the aqueous layer was extract-
ed with diethyl ether. The combined organic extracts were dried over
Na2SO4 and concentrated. After removal of triethyl phosphite and trieth-
yl phosphate under reduced pressure (958C, 0.3 mmHg), the residue was
purified by PTLC (hexane/AcOEt 1:2)to give 3-methyl-1,4-diphenyl-1,2-
1-Ethenyl-1-hexyl-2-phenylcyclopropane (14d): The reaction was carried
out according to procedure D with 3d (134 mg, 0.5 mmol)and 13
(0.23 mL, 2 mmol). 14d (69 mg, 60%, ratio of stereoisomers=96:4):
1H NMR (300 MHz, CDCl3): d=0.80 (t, J=6.9 Hz, 3H), 0.84–1.37 (m,
12H), 2.15 (dd, J=7.0, 8.2 Hz, 1H), 4.88–5.01 (m, 2H), 5.22 (dd, J=10.5,
17.4 Hz, 0.04H), 5.81 (dd, J=10.6, 17.2 Hz, 0.96H), 7.12–7.30 ppm (m,
5H); 13C NMR (major isomer; 75 MHz, CDCl3): d=14.0, 17.0, 22.5, 26.8,
29.4, 30.2, 30.8, 31.67, 31.73, 110.7, 125.8, 127.8, 129.0, 138.8, 144.5 ppm;
IR (neat): n˜ =3063, 2999, 2927, 2856, 1634, 1604, 1497, 1455, 992, 896,
780, 698, 447 cmÀ1; elemental analysis calcd (%)for C 17H24: C 89.41, H
10.59; found: C 89.16, H 10.65.
dihydrophosphete P-oxide (21a; 77 mg)contaminated with
a trace
amount of triethyl phosphate. The yield was corrected for the contami-
nant (60%). 21a: m.p. 140–1438C (recrystallized from hexane/AcOEt);
1H NMR (300 MHz, C6D6): d=1.59 (d, J=3.3 Hz, 3H), 2.36 (dd, J=12.8,
12.8 Hz, 1H), 2.83 (dd, J=17.6, 17.6 Hz, 1H), 6.88–7.11 (m, 6H), 7.26 (d,
J=7.9 Hz, 2H), 7.88–7.95 ppm (m, 2H); 13C NMR (75 MHz, CDCl3): d=
ACHTREUNG(1E,4E)-1,3-Diphenyl-1,4-hepatdiene (16b): The reaction was carried
out according to procedure D with 3 f (144 mg, 0.5 mmol)and 13
(0.23 mL, 2 mmol). 16b (79 mg, 63%): 1H NMR (300 MHz, CDCl3): d=
1.01 (t, J=7.4 Hz, 3H), 2.09 (dq, J=7.1, 7.1 Hz, 2H), 4.16 (m, 1H), 5.57
(ddt, J=0.8, 15.8, 5.8 Hz, 1H), 5.70 (ddt, J=6.6, 15.4, 1.2 Hz, 1H), 6.38–
3
1
17.9 (d, JC,P =34.7 Hz), 44.8 (d, JC,P =59.5 Hz), 127.4, 127.5, 128.2, 128.7,
128.8, 128.9, 130.9, 131.0, 132.08, 132.12 ppm; 31P NMR (121 MHz, C6D6;
relative to external H3PO4): d=21.5 ppm; IR (KBr): n˜ =3057, 2925, 1440,
Chem. Eur. J. 2007, 13, 4074 – 4080
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4079

T. Takeda et al.
1213, 1196, 1125, 1111, 840, 769, 732, 699 cmÀ1; elemental analysis calcd
(%)for C 16H15OP: C 75.58, H 5.95; found: C 75.91, H 5.98.
[1] K. M. Doxsee, J. J. J. Juliette, J. K. M. Mouser, K. Zientara, Organo-
metallics 1993, 12, 4742–4744.
[2] a)P. Binger, P. Mꢁller, R. Benn, R. Mynott, Angew. Chem. 1989,
101, 647–648; Angew. Chem. Int. Ed. Engl. 1989, 28, 610–611; b)P.
Binger, P. Mꢁller, A. T. Herrmann, P. Philipps, B. Gabor, F. Lan-
ghauser, C. Krꢁger, Chem. Ber. 1991, 124, 2165–2170.
3-Ethyl-1,4-diphenyl-1,2-dihydrophosphete P-Oxide (21b): The reaction
was carried out according to procedure G with 3k (144 mg, 0.5 mmol)
and 20 (0.17 mL, 1.3 mmol). 21b (81 mg, 60%): m.p. 140–1438C (recrys-
tallized from hexane/AcOEt); 1H NMR (300 MHz, C6D6): d=0.76 (t, J=
7.5 Hz, 3H), 2.20 (dt, J=3.8, 7.5 Hz, 2H), 2.50 (dd, J=13.8, 15.9 Hz,
1H), 2.89 (dd, J=15.9, 19.1 Hz, 1H), 6.88–7.05 (m, 3H), 7.07–7.13 (m,
3H), 7.38 (d, J=8.2 Hz, 2H), 7.89–7.96 ppm (m, 2H); 13C NMR
[3] a)F. N. Tebbe, G. W. Parshall, D. W. Ovenall, J. Am. Chem. Soc.
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4
3
(75 MHz, CDCl3): d=11.3 (d, JC,P =2.5 Hz), 24.5 (d, JC,P =32.3 Hz), 41.7
(d, 1JC,P =59.3 Hz), 127.5, 124.6, 128.19, 128.21, 128.7, 128.8, 129.0, 130.9,
131.1, 132.07, 132.11 ppm; 31P NMR (121 MHz, C6D6; relative to external
H3PO4): d=20.7 ppm; IR (KBr): n˜ =3056, 2971, 2933, 2907, 1439, 1206,
1105, 772, 723, 699 cmÀ1; elemental analysis calcd (%)for C 17H17OP: C
76.10, H 6.39; found: C 76.15, H 6.47.
4-Methyl-1,3-diphenyl-1,2-dihydrophosphete P-Oxide (21c): The reaction
was carried out according to procedure G with 3l (137 mg, 0.5 mmol)and
20 (0.17 mL, 1.3 mmol). 21c (72 mg, 56%): m.p. 105–1088C (recrystal-
lized from hexane/AcOEt); 1H NMR (300 MHz, C6D6): d=1.73 (dt, J=
17.2, 2.2 Hz, 3H), 2.80 (ddq, J=14.5, 14.5, 1.8 Hz, 1H), 3.14 (ddq, J=
14.8, 18.9, 2.5 Hz, 1H), 7.06–7.21 (m, 8H), 7.81–7.88 ppm (m, 2H);
13C NMR (75 MHz, CDCl3): d=12.4, 41.1 (d, 1JC,P =58.9 Hz), 128.17,
128.19, 128.79, 128.82, 128.9, 130.0, 131.0, 131.1, 132.06, 132.10 ppm;
31P NMR (121 MHz, C6D6; relative to external H3PO4): d=21.0 ppm; IR
(KBr): n˜ =3052, 2956, 2920, 1439, 1207, 1162, 1108, 762, 745, 691 cmÀ1; el-
emental analysis calcd (%)for C 16H15OP: C 75.58, H 5.95; found: C
75.97, H 5.98.
1,3,4-Triphenyl-1,2-dihydrophosphete P-oxide (21d):[8c] The reaction was
carried out according to procedure G with 3m (168 mg, 0.5 mmol)and 20
(0.17 mL, 1.3 mmol). 21d (103 mg, 56%): m.p. 125–1288C (recrystallized
from hexane/AcOEt); 1H NMR (300 MHz, C6D6): d=2.80 (dd, J=14.0,
15.5 Hz, 1H), 3.29 (dd, J=15.6, 19.6 Hz, 1H), 6.85–7.10 (m, 9H), 7.29
(dd, J=1.7, 8.0 Hz, 2H), 7.39–7.42 (m, 2H), 7.97–8.04 ppm (m, 2H);
13C NMR (75 MHz, CDCl3): d=42.2 (d, 1JC,P =59.6 Hz), 127.5, 127.6,
128.11, 128.14, 128.69, 128.72, 128.8, 128.9, 129.1, 130.5, 130.6, 131.0,
131.2, 131.9, 132.19, 132.23, 133.3, 133.8, 147.0, 147.1 ppm; 31P NMR
(121 MHz, C6D6; relative to external H3PO4): d=18.9 ppm; IR (KBr):
n˜ =3048, 2956, 2914, 1439, 1218, 1185, 1108, 767, 749, 734, 693 cmÀ1; ele-
mental analysis calcd (%)for C 21H17OP: C 79.73, H 5.42; found: C 79.92,
H 5.46.
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Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research
(No. 18350018)and a Grant-in-Aid for Scientific Research on Priority
Areas “Advanced Molecular Transformations of Carbon Resources”
(No. 18037017)from the Ministry of Education, Culture, Sports, Science
and Technology, Japan. This study was also carried out under the 21st
Century COE program of “Future Nanomaterials” (Tokyo University of
Agriculture and Technology).
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Received: October 4, 2006
Revised: January 16, 2007
Published online: March 1, 2007
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