Alkylation and cyclopentannulation of phospholene derivatives

Article abstract of DOI:10.1016/j.tet.2004.12.004

The deprotonation of 1-phenyl-3-phospholene 1-oxide, 1-sulfide or 1-borane with 1 or 2 equiv of LDA, followed by quenching with electrophiles gave a range of 2-mono- or 2,5-disubstituted phospholene derivatives in good yield. Only trans substitution in re

Full text of DOI:10.1016/j.tet.2004.12.004

Tetrahedron 61 (2005) 1481–1492
Alkylation and cyclopentannulation of phospholene derivatives
Zbigniew Pakulski,a Renata Kwiatoszb and K. Michał Pietrusiewicza,b,
*
aInstitute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland
bDepartment of Organic Chemistry, Maria Curie-Skłodowska University, Gliniana 33, 20-614 Lublin, Poland
Received 1 September 2004; revised 5 November 2004; accepted 2 December 2004
Available online 22 December 2004
Dedicated to Professor Mieczysław Ma˛kosza on the occasion of his 70th birthday
Abstract—The deprotonation of 1-phenyl-3-phospholene 1-oxide, 1-sulfide or 1-borane with 1 or 2 equiv of LDA, followed by quenching
with electrophiles gave a range of 2-mono- or 2,5-disubstituted phospholene derivatives in good yield. Only trans substitution in relation to
the P-Ph group was observed. Treatment of lithiated phospholene intermediates with 1,3-dihaloalkanes afforded annulated 2-phenyl-2-
phosphabicyclo[3.3.0]oct-3-ene derivatives. The annulation reactions occurred with high regio- and stereoselectivity and led to the exclusive
formation of the exo-Ph-P substituted products.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
Many chiral phosphine ligands of different structure have
been reported to induce high enantioselectivity in asym-
metric processes catalyzed by transition metals.1,2 Among
them, the ligands in which ligating phosphorus centers are
part of a five-membered phospholane ring constitute one of
the most effective classes. The fundamental discovery of
BPE and DuPHOS bis(phospholane) ligands by Burk et al.3
in the early 90s has been quickly followed by the
development of a series of other successful monodentate
and bidentate ligands possessing substituted phospholane
ring in their structure (Fig. 1). The catalytic ability and
excellent enantiorecognition of the metal complexes of
these ligands have recently been well demonstrated.2–4
The construction of the substituted phospholane units in
those ligands has been typically accomplished by the
reaction of primary phosphine anions with 1,4-cyclic sulfate
or bis(mesylate) derived from a suitably substituted 1,4-
diol.3,4 More recently, however, the syntheses of such
ligands which are based on extant phospholanes or
phospholenes have also begun to emerge.5,6 In the course
of our study on phospholenes6 we decided to check the
viability of the synthesis of the substituted monocyclic and
bicyclic phospholene systems via simple alkylation of
Figure 1. Selected chiral phospholane ligands.
2-phospholene and 3-phospholene derivatives. The parent
phospholene derivatives could be promptly obtained from
butadienes and dihalophosphines via McCormack cyclo-
Keywords: Phospholene; Alkylation; Cyclopentannulation.
* Corresponding author. Tel.: C48 22 3432007; fax: C48 22 632 66 81;
e-mail: kmp@icho.edu.pl
addition route, and the presence of endocyclic allylic
functionality in their structure was expected to facilitate
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.12.004

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Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
and direct the desired deprotonations in the ring. The model
substrates selected for the study are presented in Figure 2.
introduction of a substituent at the position a to phosphorus.
Our own screening of alkylation conditions for 1-phenyl-3-
phospholene derivatives revealed that the use of LDA in
THF gave the best selectivity and the best yields of
alkylated products. Other tested base systems either
decomposed the starting phospholene or gave mixtures of
cis and trans alkylated products. For example, reaction of 1
with n-BuLi/2,2,6,6-tetramethylpiperidine followed by
methyl iodide gave a mixture of cis- and trans-2-methyl-
1-phenyl-3-phospholene 1-oxide together with 4-methyl-1-
phenyl-2-phospholene 1-oxide. Treatment of phospholene 1
with n-butyllithium in THF at K78 8C, or with LDA in Et2O
at K78 8C, caused decomposition of the starting material.
Similarly, all attempts to deprotonate the parent 1-phenyl-2-
phospholene 1-oxide (7) under variety of conditions and at
low temperature led only to the decomposition of 7.
Figure 2. The model phospholenes.
The results of the studied alkylations of phospholenes with
the use of LDA as a base are collected in Table 1. The
formation of only trans alkylation products in the relation to
the P-phenyl group was observed (Scheme 1). In most cases
studied, the formation of the monoalkylated product was
accompanied by the formation of some amounts of the
disubstituted derivative but the two products could typically
be separated by chromatography. Depending on the
electrophile and the proportion of phospholene to halide
used, mono- or disubstituted products could be selectively
obtained in good yields. Alkylation of unsubstituted
phospholenes 1, 2 and 6 occurred preferentially at the a
position of the phospholene ring. Methylation of phospho-
lene 1 could be finely tuned to provide either mono- or
disubstituted product selectively. Similar methylations of
sulfide 2 and borane 6 gave, however, mixtures of mono-
and disubstituted products. Alkylation of 3-methyl-1-
phenyl-2-phospholene 1-oxide (8) with methyl iodide
gave the 2-substituted product 13 in good yield, although
in this case a small amount of a side alkylation product 17
1-Phenyl-3-phospholene 1-oxide (1), 3-methyl-1-phenyl-3-
phospholene 1-oxide (3), and 3,4-dimethyl-1-phenyl-3-
phospholene 1-oxide (5) were prepared according to the
known procedure7 involving addition of P,P-dibromo-
phenylphosphine to 1,3-butadiene, isoprene or 2,3-
dimethyl-1,3-butadiene, respectively. The use of P,P-
dichlorophenylphosphine for condensation with butadiene
or isoprene afforded 1-phenyl-2-phospholene 1-oxide (7) or
1-phenyl-3-methyl-2-phospholene 1-oxide (8). 1-Phenyl-3-
phospholene 1-sulfide (2) and 1-phenyl-3-phospholene
1-borane (6) were obtained by phenylsilane reduction of
18 followed by addition of elemental sulfur or borane–THF
complex, respectively.6a Similarly, 4 was prepared by
phenylsilane reduction of 3 and reaction of phosphine
obtained with elemental sulfur.
It was already known from the early work of Mathey et al.9
that treatment of 3-phospholene derivatives with n-butyl-
lithium/TMEDA followed by an electrophile led to the
Table 1. Alkylation of phospholene derivativesa
Entry
Starting
material
Y
R1
R2
LDA (equiv) RX (equiv)
Monoalkylated
product (%)b
Dialkylated
product (%)b
1
2
3
4
5
6
7
8
1
1
1
2
2
3
6
6
8
1
2
3
1
2
1
1
1
2
5
1
1
O
O
O
S
S
O
H
H
H
H
H
Me
H
H
H
H
H
H
1.5
1.1
2.5
2.1
2.1
1.2
1.5
2.1
1.2
1.1
2.1
1.2
2.1
2.1
1.2
2.4
1.2
1.2
1.2
1.2
1.2
MeI (1.1)
MeI (1.0)
MeI (15.0)
MeI (2.2)
MeI (10.0)
MeI (1.1)
MeI (1.1)
MeI (10.0)
MeI (1.1)
iso-PrI (7.5)
iso-PrI (2.2)
iso-PrI (2.0)
AllBr (1.1)
AllBr (1.1)
o-BrC6H4CH2Cl (1.1)
o-BrC6H4CH2Cl (2.2)
o-BrC6H4CH2Br (1.1) 26 (47)
o-BrC6H4CH2Br (1.1) 28 (71)
o-BrC6H4CH2Br (1.1) 29 (55)
9 (63)12
9 (59)
10 (9)
—
—
10 (83)
12 (59)
12 (68)
14 (62)
16 (47)
16 (75)
—
19 (25)
20 (28)
—
24 (19)
25 (38)
27 (24)
27 (33)
—
11 (37)12
11 (21)
13 (9)
15 (24)
15 (traces)
13 (49) 17 (6)c
18 (48)12
—
9
10
11
12
13
14
15
16
17
18
19
20
21
O
S
O
O
S
O
O
O
S
O
O
O
H
H
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
H
H
21 (34) 22 (10)d
23 (26)
—
26 (11)
—
—
—
31 (29)
33 (16)
Me
H
H
BnOCH2Cl (1.1)
AllOCH2Cl (1.1)
30 (20)
32 (27)
a THF, K78 8C, LDA, RX.
b Isolated yield.
c Recovered 8 (34%) was also isolated.
d Recovered 3 (22%) was also isolated.

Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
1483
Interestingly, in the case of the non-symmetrical 3-methyl-
1-phenyl-3-phospholene 1-oxide (3) the alkylation occurred
exclusively at the more crowded of the two a positions, i.e.
at the position 2.
Scheme 1. Alkylation of phospholene derivatives.
was also isolated. Lithiated 3-methyl-3-phospholene
1-oxide (3) showed again high regioselectivity in its
reactions with alkyl halides. As exemplified in Table 1 the
new alkyl substituent has been preferentially introduced at
the 2-position of the phospholene ring. Reaction of 3 with
methyl iodide yielded 2-methyl derivative 13 as the
monosubstituted product; more bulky isopropyl iodide led
to the formation of 2-alkylated derivative 21 and also to the
formation of 4-substituted 2-phospholene derivative 22.
Deprotonated sulfide 2 was more reactive against isopropyl
iodide and allyl bromide then the corresponding oxide 1 and
gave only 2,5-disubstituted products.
Figure 3. Selected NOE contacts indicated by arrows.
By comparison, when benzophenone was used as a carbonyl
electrophile for lithiated 1-phenyl-3-phospholene deriva-
tives, it was directed to position 3 (Scheme 2). Yields
were moderate to good (42–74%) and the 4-substituted
2-phospholene derivatives were the sole reaction products.
These results complement the findings by Mathey et al.9
who reported that similar reactions of ring substituted 3,4-
dimethyl-1-phenyl-3-phospholene 1-oxide (5) with ketones
such as acetone, acetophenone, and bezophenone, led
preferentially to the 2-substituted products whereas its
reaction with benzaldehyde afforded the 4-substituted
derivative.
Functionalized electrophiles such as 2-bromobenzyl
bromide, 2-bromobenzyl chloride, benzyloxymethyl
chloride and allyloxymethyl chloride afforded products
containing reactive sites in the side chains which can be
potentially useful in further elaboration of their structure.
The use of 2-bromobenzyl bromide as alkylating agent gave
monosubstituted products in good yield. In turn, with an
excess of 2-bromobenzyl chloride a dialkylated derivative
27 was formed exclusively. For benzyloxymethyl and
allyloxymethyl chlorides mixtures of mono and disubsti-
tuted products were isolated.
An attempt was also made to prepare alkylated phospholene
derivatives in the enantioenriched form via enantioselective
deprotonation of the starting phospholenes by means of the
sec-BuLi/(K)-sparteine base system.10 Examples of suc-
cessful enantioselective deprotonation of unsubstituted as
well as substituted phospholanes and phosphines by this
chiral base have been already reported.5a,6b,11 However,
when phospholenes 1, 2, or 6 were treated with sec-BuLi/
(K)-sparteine in diethyl ether at low temperature followed
by quenching with an alkyl halide either complete
decomposition of the starting material (for 1 or 2) or no
reaction was observed (for 6). Apparently, the presence of
the double bond in the ring had an unfavorable effect. By
changing the base to n-BuLi/(K)-sparteine and using THF
as solvent it was possible to obtain some mono- and
dialkylated products but the conversions were nevertheless
very low and the products were found to be racemic.5
Scheme 2. Reaction of 3-phospholene derivatives with benzophenone.
Next, we turned our attention to the reactions of lithiated
phospholenes with 1,3-dihalopropanes and 1,3-dihalo-
butanes as they could potentially offer a route to bicyclic
phospholene derivatives.6a The results of the studied
annulation reactions are shown in Scheme 3 and collected
in Table 2. Deprotonation of 1-phenyl-3-phospholene
1-oxide (1) by 2.1 equiv of LDA followed by quenching
with 1,3-dihalopropane led to the formation of 2-phenyl-2-
phosphabicyclo[3.3.0]oct-3-ene 2-oxide (37).6a,12 1,3-
Dibromopropane yielded the expected bicyclic product 37
as the main product (39–64%) but together with inseparable
monocyclic mono- and dialkylation byproducts. Much
better results were obtained with 1,3-diiodopropane which
afforded 37 as the sole product with high yield (74%).
The regiochemistry of the studied alkylation reaction was
proven by comparing the spectroscopic data of the products
with the pertinent literature data (9,12,13 10,14 11,12 18,12 and
4012) as well as by checking close NOE contacts (Fig. 3). In
the reactions involving alkyl halides as electrophiles the
lithiated phospholenes were alkylated preferentially at the
position a to phosphorus and trans to the P-Ph group.

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Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
products was unequivocally confirmed by the X-ray studies
on 37.6c
The use of 1,3-dihalobutanes in the studied reactions also
resulted in the formation of the expected bicyclic products
possessing an added methyl substituent at the annulated
cyclopentane ring. However, in reactions with 1,3-dibromo-
butane the presence of secondary bromide functionality
apparently slowed down the cyclization step and consider-
able amounts of monocyclic alkylated products were
usually observed.6a The reactions with 1,3-diiodobutane
went more cleanly and provided the possibility of achieving
the selective formation of bicyclic products in good yields
(Scheme 4, Table 3). However, due to the chiral nature of
the 1,3-dihalobutanes used the products were formed as
mixtures of C-6 epimers in a ratio between 1.2:1 and 6.0:1.
In order to utilize this annulation reaction for the preparation
of optically active 2-phosphabicyclo[3.3.0]octenes we
synthesized the corresponding (S)-(C)-1,3-diiodobutane in
the enantiopure form and reacted it with phospholenes 1, 2,
and 5. We were, however, unable to separate the epimeric
Scheme 3. Annulation of 3-phospholene derivatives by 1,3-dihalopropane.
Table 2. Annulation of 3-phospholene derivatives by 1,3-dihalopropanea
Entry
Starting material
RX
Product (%)b
Isomer ratioc
1
2
3
4
5
6
7
8
9
1
1
2
6
6
3
4
4
5
Br(CH2)3Br
I(CH2)3I
Br(CH2)3Br
Br(CH2)3Br
I(CH2)3I
37 (39–64)d
37 (74)
38 (91)
—
—
—
—
39 (53)e
39 (53)e
—
I(CH2)3I
40/41 (72)
42/43 (67)
42/43 (58)
44 (55)
5.5:1.0
2.0:1.0
2.4:1.0
—
Br(CH2)3Br
I(CH2)3I
I(CH2)3I
a THF, K78 8C, LDA (2.1 equiv), RX (1.1 equiv).
b Isolated yield.
c Determined by 31P NMR.
d Contaminated with mono- and dialkylated monocyclic byproducts.
e Contaminated with monoalkylated monocyclic byproduct.
However, the reaction was found to be very difficult to scale
up due to a strong exothermic effect that caused dramatic
decrease in yield (only 15–20% for a 10 mmol scale).
Analogous annulation on 1-phenyl-3-phospholene 1-sulfide
(2) by treatment with 1,3-dibromopropane afforded bicyclic
product 38 in excellent yield irrespective of the reaction
scale (91% yield for the 10 mmol scale).6c
products and to isolate the desired enantiopure
bicyclo[3.3.0]octenes.
The annulation procedure described above could also be
successfully applied to acyclic allylic systems similarly
activated by the adjacent phosphorus substituents. We tested
the reaction of lithiated 2-butene-1,4-bis(phosphonate) 49
Treatment of lithiated borane 6 with 1,3-diiodo- or 1,3-
dibromopropane afforded bicyclic borane 39 but in both
cases contaminated with inseparable monoalkylated pro-
duct. Pure bicyclic borane 39 could be obtained by reduction
of phosphine oxide 37 followed by addition of borane–THF
complex. The borane 39 obtained by this way was found to
be identical in every respect with the compound prepared by
direct annulation of 6.
Annulation of 3-methyl phospholenes 3 and 4 with 1,3-
diiodopropane gave a mixture of regioisomeric products 40
and 41 in high yield (72%) and 42 and 43 (58–67%),
respectively. Reaction of 3,4-dimethyl phospholene 5 under
the same conditions yielded bicyclo[3.3.0]oct-3-ene 44 with
55% yield (Table 2). The cis ring junction in the annulated
Scheme 4. Annulation of 3-phospholene derivatives by 1,3-diiodobutane.

Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
Table 3. Annulation of 3-phospholene derivatives by 1,3-diiodobutanea
1485
Entry
Starting
material
Product (%)b
Epimer ratioc
1
2
3
4
1
2
6
5
45 (67)
46 (53)
47 (32)d
48 (77)
1.2:1.0
1.3:1.0
2.0:1.0
6.0:1.0
Scheme 6. Alkylation of 1-phenyl-3-phospholene 1-oxide (1) with
1-bromo-4-chlorobutane.
a THF, K78 8C, LDA (2.1 equiv), I(CH2)2CH(CH3)I (1.1 equiv).
b Isolated yield.
1
c Determined by H and 31P NMR.
d Approx. 11% of 2,5-dialkylated monocyclic product was also detected.
Table 4. Alkylation of 1-phenyl-3-phospholene 1-oxide (1) with 1-bromo-
4-chlorobutanea
and 2-butene-1-phosphonate-4-phosphinoxide 51 with 1,3-
diiodopropane at K78 8C. Five membered ring annulation
products were obtained in both cases. From 49 a mixture of
two diastereoisomers 50 in a ratio 95:5 was formed, whereas
unsymmetrical 51 afforded a mixture of two regioisomers
52 and 53 in nearly 1:1 ratio, in 40% yield in both cases
(Scheme 5). The trans stereochemistry of the ring
substitution and of the double bond in the products was
tentatively assigned, but it still needs to be unequivocally
confirmed.
Entry
LDA
(equiv)
Br(CH2)4Cl
(equiv)
54 (%)b
55 (%)b
1
2.1
1.2
1.2
1.1
1.1
1.1
—
29
18
35
2c
3e
27d
19f
a THF, K78 8C, LDA (2.1 equiv), Br(CH2)4Cl (1.1 equiv).
b Isolated yield.
c 1.0 mmol scale.
d 54a:54by4.3:1.0.
e 2.0 mmol scale.
f
54a:54by11.5:1.0.
monocyclic as well as the bicyclic phospholene systems.
Their deprotonation with LDA followed by alkylation takes
place with the exclusive anti selectivity of the incoming
electrophile in relation to the P-phenyl group. The products
are obtained with high regioselectivity with the preference
for the positions 2 and 2,5. Placing of the methyl group in
position 3 of the 3-phospholene ring gives additional control
of regiochemistry of alkylation and directs the electrophile
again to the 2-position despite the steric crowding. The
procedure described in this paper constitutes a convenient
synthetic alternative to the McCormack route for the
preparation of 2- and 2,5-substituted phospholene deriva-
tives which avoids the use of slow reacting terminally
substituted dienes7 as well as the formation of stereo-
isomeric products. It offers also the simplest and most
convenient route to the 2-phenyl-2-phosphabicyclo[3.3.0]-
oct-3-ene derivatives which can be now readily synthesized
by the developed cyclopentannulation process.
Scheme 5. Annulation of acyclic allylic derivatives.
2. Experimental
Successful synthesis of 2-phosphabicyclo[3.3.0]oct-3-ene
derivatives prompted us to extend this methodology to a
synthesis of 2-phosphabicyclo[4.3.0]non-3-ene derivative
by treatment of 1-phenyl-3-phospholene 1-oxide (1) with
1,4-dihalobutanes. However, attempted annulations of
lithiated 1 by treatment with 1,4-dibromobutane or with
1,4-diiodobutane in the presence of LDA were all
unsuccessful and resulted in the formation of very complex
mixtures. Reaction with 1-bromo-4-chlorobutane afforded
low yields of mono- and dialkylated products in a ratio
depending on the proportion of the reagents used and on the
reaction scale (Scheme 6, Table 4). In none of the attempts
the expected bicyclic product was detected.
2.1. General methods
The solvents were purified and dried according to literature
methods. TLC was performed on Silica Gel HF-254 and
column chromatography on Silica Gel 230–400 mesh
(Merck). NMR spectra were recorded with a Varian
Mercury 400BB (400 MHz) and Bruker AM-500
(500 MHz) spectrometers in deuterochloroform (CDCl3)
and deuterobenzene (C6D6) with Me4Si as internal standard.
High-resolution mass spectra (HR-MS) were measured with
an AMD-604 and a MARINER mass spectrometers. Optical
rotations were measured with a JASCO DIP-360 automatic
polarimeter. IR spectra were recorded on Perkin–Elmer
1640 FT-IR spectrophotometer.
In summary, we have demonstrated that 1-phenyl-3-
phospholene and 1-phenyl-2-phospholene derivatives, the
readily accessible parent compounds in the phospholene
family, can serve as direct precursors to the more substituted
2.1.1. (S)-(C)-1,3-Diiodobutane. To a suspension of
anhydrous lithium iodide (6.1 g, 45 mmol) in dry dioxane

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Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
(20 mL) was added (R)-(–)-1,3-butanediol dimethane-
sulfonate15 (2.26 g, 9.2 mmol) and stirred at reflux for 6 h.
After cooling to room temperature the mixture was poured
into water (50 mL) and extracted with pentane (5!20 mL).
The combined pentane extracts were washed with water
(4!10 mL), brine (10 mL), dried (Na2SO4) and evaporated
to give 2.39 g (84%) of the title compound. It was
decolorized by addition of small amount of powdered
copper. [a]2D5 C8.1 (c 1.56, chloroform). 1H NMR (CDCl3)
d: 4.28 (m, 1H), 3.18–3.46 (m, 2H), 2.30 (m, 1H), 2.10 (m,
1H), 2.00 (d, 3H, JZ6.9 Hz, CH3). 13C NMR (CDCl3) d:
45.9 (CH2), 29.7 (CHI), 28.8 (CH3), 6.4 (CH2I). HR-MS
(EI) calcd for C4H8I2 (M)C: 309.8716. Found: 309.8720.
2.2. General procedure for the alkylation reaction
To a solution of freshly prepared LDA in THF (6 mL)
cooled to K78 8C a solution of 1-phenyl-3-phospholene
1-oxide (1, 178 mg, 1.0 mmol) in THF (2 mL) was added.
The resulting deep red solution was stirred at K78 8C for
10 min and a solution of alkyl halide in THF (2 mL) was
added in one portion. Stirring was continued for 30 min at
K78 8C and the reaction was quenched by addition of a few
drops of water at K78 8C and then allowed to attain room
temperature. Solvents were evaporated. Column chroma-
tography of the residue (hexane–ethyl acetate–methanol,
5:3:1 for phosphine oxides and hexane–ethyl acetate, 9:1 for
phosphine sulfides and phosphine boranes as eluents) gave
pure product.
2.1.2. 1-Phenyl-3-phospholene 1-sulfide (2). A mixture of
1 (5.0 mmol) and phenylsilane (6.0 mmol) in toluene
(2 mL) was heated under argon atmosphere at 100 8C for
4 h. Solvents were evaporated under vacuum and the residue
was dissolved in toluene (5 mL) and powdered sulfur
(10.0 mmol) was added causing strong exothermic reaction.
The suspension was stirred at room temperature overnight
and evaporated to dryness. Column chromatography of the
residue gave sulfide 2 (930 mg, 96%, hexane–ethyl acetate,
9:1 as eluent) as white solid. Mp: 59–60 8C. 1H NMR
(CDCl3) d: 6.04 (dm, 2H, JH,PZ29.9 Hz, H-3,4), 3.08 (m,
2.2.1. 2,5-Dimethyl-1-phenyl-3-phospholene 1-oxide (10).
Yield: 171 mg (83%), colorless oil. H NMR (CDCl3) d:
1
5.96 (dd, 2H, JH,PZ27.7 Hz, JZ0.7 Hz, H-3,4), 2.76 (m,
2H, H-2,5), 1.36 (dd, 6H, JH,PZ14.8 Hz, JMe,2(5)Z7.5 Hz,
CH3). 13C NMR (CDCl3) d: 134.4 (d, JC,PZ100.0 Hz),
133.4 (d, JC,PZ13.8 Hz, C-3,4), 131.7 (d, JC,PZ2.6 Hz),
129.8 (d, JC,PZ9.0 Hz), 128.6 (d, JC,PZ11.1 Hz), 37.8 (d,
JC,PZ66.9 Hz, C-2,5), 14.1 (d, JC,PZ4.2 Hz, CH3). 31P
NMR (CDCl3) d: 55.1. nmax (film): 2968, 2928, 1452, 1437,
1185, 1113, 744, 718, 697, 562 cmK1. HR-MS (EI) calcd
for C12H15OP (M)C: 206.0860. Found: 206.0863.
4H, H-2,20,5,50). 13C NMR (CDCl3) d: 133.4 (d, JC,P
Z
72.3 Hz), 131.7 (d, JC,PZ3.1 Hz), 129.9 (d, JC,PZ10.8 Hz),
128.6 (d, JC,PZ11.7 Hz), 128.3 (d, JC,PZ8.1 Hz), 41.5 (d,
JC,PZ54.1 Hz, C-2,5). 31P NMR (CDCl3) d: 53.8. nmax
(film): 3049, 2934, 2906, 1617, 1436, 1401, 1114, 876, 741,
708, 642 cmK1. HR-MS (EI) calcd for C10H11PS (M)C:
194.0319. Found: 194.0321.
2.2.2. 2,5-Dimethyl-1-phenyl-3-phospholene 1-sulfide
(12). Yield: 151 mg (68%), colorless oil. 1H NMR
(CDCl3) d: 6.01 (dd, 2H, JH,PZ28.0 Hz, J3,2Z0.9 Hz,
H-3,4), 2.98 (m, 2H, H-2,5), 1.32 (dd, 6H, JMe,2Z7.5 Hz,
JC,PZ18.3 Hz, CH3). 13C NMR (CDCl3) d: 134.4 (d, JC,P
11.8 Hz, C-3,4), 132.0 (d, JC,PZ2.9 Hz), 130.6 (d, JC,P
Z
Z
2.1.3. 1-Phenyl-3-methyl-3-phospholene 1-sulfide (4). A
sample of 3 (1.96 g, 10.2 mmol) was reduced with
phenylsilane and treated with sulfur (15 mmol) as desribed
above for 2. Column chromatography (hexane–ethyl
acetate, 9:1 as eluent) gave sulfide 4 (1.88 g, 89%) as thin
oil. 1H NMR (CDCl3) d: 5.64 (dm, 1H, JH,PZ32.3 Hz, H-4),
2.94–3.16 (m, 4H, H-2,20,5,50), 1.88 (m, 3H, CH3). 13C
9.5 Hz), 129.0 (d, JC,PZ11.5 Hz), 41.8 (d, JC,PZ51.9 Hz,
C-2,5), 17.1 (s, CH3). 31P NMR (CDCl3) d: 69.4. nmax (film):
2966, 2922, 1446, 1436, 1105, 727, 701, 693, 524 cmK1
.
HR-MS (EI) calcd for C12H15PS (M)C: 222.0632. Found:
222.0638.
NMR (CDCl3) d: 138.0 (d, JC,PZ9.5 Hz), 133.6 (d, JC,P
Z
2.2.3. 2,3-Dimethyl-1-phenyl-3-phospholene 1-oxide (13).
Yield: 19 mg (9%) from 3 or 101 mg (49%) from 8,
71.6 Hz), 131.6 (d, JC,PZ4.4 Hz), 129.9 (d, JC,PZ10.3 Hz),
128.5 (d, JC,PZ12.1 Hz), 121.9 (d, JC,PZ5.2 Hz), 45.2 (d,
JC,PZ56.0 Hz, CH2), 42.1 (d, JC,PZ52.6 Hz, CH2), 19.6 (d,
JC,PZ11.2 Hz, CH3). 31P NMR (CDCl3) d: 55.3. nmax (film):
2933, 2912, 1436, 1400, 1201, 1119, 1107, 775, 738, 692,
655 cmK1. HR-MS (ESI) calcd for C11H14PS (MCH)C:
209.0548. Found: 209.0536.
colorless oil. 1H NMR (CDCl3) d: 5.63 (m, 1H, JH,P
Z
31.7 Hz, H-4), 2.79 (m, 1H, H-5), 2.70 (m, 1H, H-50), 2.52
(m, 1H, JH,PZJMe,2Z7.5 Hz, H-2), 1.84 (s 3H, CH3), 1.38
(dd, 3H, JH,PZ15.1 Hz, CH3). 13C NMR (CDCl3) d: 143.0
(d, JC,PZ15.1 Hz, C-3), 134.1 (d, JC,PZ89.7 Hz), 131.7 (d,
JC,PZ2.8 Hz), 129.6 (d, JC,PZ9.2 Hz), 128.5 (d, JC,P
11.2 Hz), 119.7 (d, JC,PZ8.3 Hz, C-4), 40.5 (d, JC,P
70.4 Hz, C-2), 32.8 (d, JC,PZ64.1 Hz, C-5), 17.9 (d, JC,P
Z
Z
Z
2.1.4. 1-Phenyl-3-phospholene 1-borane (6). A sample of
1 (5.0 mmol) was reduced with phenylsilane and treated
with borane–THF complex (5.0 mmol) as desribed above
for 2. Column chromatography (hexane–ethyl acetate–
methanol, 5:3:1 as eluent) gave borane complex 6
9.8 Hz, CH3), 11.7 (d, JC,PZ2.9 Hz, CH3). 31P NMR
(CDCl3) d: 57.7. nmax (film): 2968, 2931, 1437, 1216,
1178, 1112, 745, 718, 697, 511 cmK1. HR-MS (EI) calcd
for C12H15OP (M)C: 206.0861. Found: 206.0866.
1
(762 mg, 94%) as white solid. Mp: 43–44 8C. H NMR
(CDCl3) d: 6.00 (d, 2H, JH,PZ21.6 Hz, H-3,4), 2.85 (m, 4H,
H-2,20,5,50), 0.00–1.80 (m, 3H, BH3). 13C NMR (CDCl3) d:
133.6 (d, JC,PZ38.0 Hz), 131.5 (d, JC,PZ2.3 Hz), 131.1 (d,
JC,PZ9.2 Hz), 128.8 (d, JC,PZ9.4 Hz), 128.6 (s), 33.3 (d,
JC,PZ35.8 Hz, C-2,5). 31P NMR (CDCl3) d: 24.8 (m). nmax
(film): 2372, 2342, 1437, 1407, 1121, 1060, 744, 718, 693,
657 cmK1. HR-MS (EI) calcd for C10H11P (MKBH3)C:
162.0598. Found: 162.0588.
2.2.4. 2,3,5-Trimethyl-1-phenyl-3-phospholene 1-oxide
(14). Yield: 136 mg (62%), colorless oil. 1H NMR
(CDCl3) d: 5.67 (dm, 1H, JH,PZ30.3 Hz, H-4), 2.73 (m,
1H), 2.52 (m, 1H), 1.86 (bs, 3H, CH3), 1.36 (m, 6H, 2!
CH3). 13C NMR (CDCl3) d: 141.8 (d, JC,PZ14.6 Hz, C-3),
132.1 (d, JC,PZ2.6 Hz), 130.2 (d, JC,PZ9.1 Hz), 128.7 (d,
JC,PZ10.6 Hz), 128.2 (d, JC,PZ11.0 Hz, C-4), 41.1 (d,
JC,PZ67.7 Hz, C-2(5)), 38.2 (d, JC,PZ65.1 Hz, C-2(5)),

Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
1487
18.5 (d, JC,PZ9.9 Hz, CH3), 15.5 (d, JC,PZ3.7 Hz, CH3),
13.7 (d, JC,PZ3.6 Hz, CH3). 31P NMR (CDCl3) d: 56.4. nmax
(film): 2968, 2930, 1437, 1217, 1182, 1111, 729, 715, 696,
596, 536 cmK1. HR-MS (EI) calcd for C13H17OP (M)C:
220.1017. Found: 220.1016.
0.92 (d, 6H, JH,MeZ6.5 Hz, 2!CH3). 13C NMR (CDCl3) d:
131.8 (d, JC,PZ3.1 Hz), 131.3 (d, JC,PZ12.5 Hz), 130.8 (d,
JC,PZ9.8 Hz), 129.1 (d, JC,PZ11.3 Hz, C-3,4), 55.1 (d,
JC,PZ51.0 Hz, C-2,5), 28.8 (d, JC,PZ2.4 Hz), 23.5 (d,
JC,PZ5.6 Hz), 21.2 (d, JC,PZ9.7 Hz). 31P NMR (CDCl3) d:
68.5. nmax (KBr): 2960, 2868, 1471, 1436, 1102, 741, 705,
694, 533 cmK1. HR-MS (EI) calcd for C16H23PS (M)C:
278.1258. Found: 278.1263.
2.2.5. 2-Methyl-1-phenyl-3-phospholene 1-borane (15).
Yield: 42 mg (24%), colorless oil. 1H NMR (CDCl3) d: 5.94
(d, 2H, JH,PZ20.2 Hz, H-3,4), 3.04 (m, 1H, C-2), 2.88 (m,
1H, C-5), 2.79 (m, 1H, C-50), 1.34 (dd, 3H, JMe,2Z7.5 Hz,
JMe,PZ16.8 Hz, CH3), 0.30–1.10 (m, 3H, BH3). 13C NMR
2.2.10. 2-Isopropyl-3-methyl-1-phenyl-3-phospholene
1-oxide (21). Yield: 80 mg (34%), colorless oil. H NMR
1
(CDCl3) d: 136.0 (d, JC,PZ4.6 Hz), 131.5 (d, JC,P
Z
(CDCl3) d: 5.78 (dm, 1H, JH,PZ30.5 Hz, H-4), 2.75 (m, 1H,
H-5), 2.63 (m, 1H, H-50), 2.44 (bd, 1H, H-2), 2.36 (m, 1H,
CHMe2), 1.84 (d, 3H, JC,PZ1.7 Hz, CH3), 1.21 (dd, 6H,
JMe,CHZ7.0 Hz, JZ2.3 Hz, 2!CH3). 13C NMR (CDCl3) d:
141.5 (d, JC,PZ16.6 Hz, C-4), 135.6 (d, JC,PZ88.8 Hz),
131.5 (d, JC,PZ2.6 Hz), 129.4 (d, JC,PZ8.8 Hz), 128.5 (d,
JC,PZ11.1 Hz), 122.2 (d, JC,PZ8.7 Hz, C-3), 52.3 (d,
JC,PZ67.7 Hz, C-2), 33.6 (d, JC,PZ63.6 Hz, C-5), 28.6 (d,
JC,PZ1.7 Hz, CHMe2), 20.2 (2d, 2!CH3), 19.8 (d, JZ
10.4 Hz, CH3). 31P NMR (CDCl3) d: 57.0. nmax (film): 2960,
48.3 Hz), 131.4 (d, JC,PZ2.4 Hz), 131.1 (d, JC,PZ8.8 Hz),
128.8 (d, JC,PZ9.7 Hz), 126.7 (s), 39.7 (d, JC,PZ34.9 Hz,
C-2), 32.9 (d, JC,PZ35.7 Hz, C-5), 16.0 (d, JC,PZ5.0 Hz,
CH3). 31P NMR (CDCl3) d: 32.6 (m). nmax (film): 2967,
2927, 2377, 2350, 1437, 1134, 1113, 1064, 693 cmK1
.
HR-MS (EI) calcd for C11H13P (MKBH3)C: 176.0755.
Found: 176.0748.
2.2.6. 2,5-Dimethyl-1-phenyl-3-phospholene 1-borane
(16). Yield: 153 mg (75%), colorless oil. 1H NMR
(CDCl3) d: 5.91 (d, 2H, JH,PZ19.4 Hz, H-3,4), 3.02 (m,
2H, H-2,5), 1.33 (dd, 6H, JMe,2Z7.5 Hz, JMe,PZ16.4 Hz,
CH3), 0.35–1.05 (m, 3H, BH3). 13C NMR (CDCl3) d: 134.2
2873, 1437, 1211, 1183, 1111, 768, 745, 696, 515 cmK1
.
HR-MS (EI) calcd for C14H19OP (M)C: 234.1173. Found:
234.1172.
(d, JC,PZ4.0 Hz), 131.9 (d, JC,PZ48.4 Hz), 131.2 (d, JC,P
Z
2.2.11. 4-Isopropyl-3-methyl-1-phenyl-2-phospholene
1-oxide (22). Yield: 23 mg (10%), colorless oil. H NMR
(CDCl3) d: 5.98 (m, 1H, JH,PZ23.9 Hz, H-2), 2.83 (m, 1H,
H-4), 2.27 (m, 1H, CHMe2), 2.10 (m, 1H, H-5), 2.04 (s, 3H,
CH3-ring), 1.94 (m, 2H, H-50), 1.00 (d, 3H, JMe,CHZ6.8 Hz,
CH3), 0.85 (d, 3H, JMe,CHZ6.8 Hz, CH3). 13C NMR
1
4.5 Hz), 131.2 (d, JC,PZ8.4 Hz), 128.7 (d, JC,PZ9.4 Hz),
39.7 (d, JC,PZ34.5 Hz, C-2,5), 16.9 (s, CH3). 31P NMR
(CDCl3) d: 40.2 (m). nmax (film): 2968, 2927, 2378, 2343,
1450, 1437, 1135, 1111, 1065, 741, 707, 693 cmK1. HR-MS
(EI) calcd for C12H15P (MKBH3)C: 190.0911. Found:
190.0913.
(CDCl3) d: 166.3 (d, JC,PZ24.6 Hz, C-3), 134.4 (d, JC,P
Z
98.5 Hz), 131.4 (d, JC,PZ2.8 Hz), 130.4 (d, JC,PZ10.3 Hz),
128.5 (d, JC,PZ11.9 Hz), 122.4 (d, JC,PZ100.0 Hz, C-2),
51.6 (d, JC,PZ8.0 Hz, C-4), 28.1 (d, JC,PZ3.9 Hz, CHMe2),
2.2.7. 3-Ethyl-1-phenyl-2-phospholene 1-oxide (17).
Yield: 12 mg (6%), colorless oil. 1H NMR (CDCl3) d:
5.96 (m, 1H, JH,PZ24.6 Hz, JZ1.5 Hz, H-2), 1.19 (t, 3H,
27.1 (d, JC,PZ69.9 Hz, C-5), 21.4 (s, CH3), 19.2 (d, JC,P
Z
18.9 Hz, CH3-ring), 15.0 (s, CH3). 31P NMR (CDCl3) d:
55.8. nmax (film): 2957, 2869, 1438, 1205, 1179, 1115, 749,
724, 696, 535, 522 cmK1. HR-MS (EI) calcd for C14H19OP
(M)C: 234.1173. Found: 234.1167.
JZ7.4 Hz, CH3). 13C NMR (CDCl3) d: 170.4 (d, JC,P
24.4 Hz, C-3), 131.5 (d, JC,PZ2.8 Hz), 130.5 (d, JC,P
Z
Z
10.4 Hz), 128.5 (d, JC,PZ11.9 Hz), 118.2 (d, JC,PZ100.2 Hz,
C-2), 32.7 (d, JC,PZ8.5 Hz, CH2), 27.9 (d, JC,PZ16.1 Hz,
CH2), 27.1 (d, JC,PZ70.1 Hz, CH2), 11.7 (CH3). 31P NMR
(CDCl3) d: 61.7. nmax (film): 3055, 2969, 2933, 2878, 1605,
1438, 1226, 1194, 1164, 1117, 750, 697, 536 cmK1. HR-MS
(EI) calcd for C12H15OP (M)C 206.0860. Found: 206.0863.
2.2.12. 2-Allyl-1-phenyl-3-phospholene 1-oxide (23).
Yield: 57 mg (26%), colorless oil. H NMR (CDCl3) d:
1
6.05 (dd, 2H, JH,PZ28.3 Hz, JZ0.5 Hz, H-3,4), 5.87 (m,
1H, ]CH), 5.07 (m, 2H, ]CH2), 2.76 (m, 3H), 2.48 (m,
2H). 13C NMR (CDCl3) d: 135.7 (d, JC,PZ9.6 Hz), 133.2 (d,
JC,PZ14.4 Hz), 131.9 (m), 129.7 (d, JC,PZ9.4 Hz), 128.7
(d, JC,PZ11.6 Hz), 126.6 (d, JC,PZ10.3 Hz), 116.8 (s,
2.2.8. 2,5-Diisopropyl-1-phenyl-3-phospholene 1-oxide
(19). Yield: 66 mg (25%), colorless oil. H NMR (CDCl3)
1
d: 6.08 (dd, 2H, JH,PZ28.8 Hz, H-3,4), 2.45 (dd, 2H, JH,P
Z
8.0 Hz, J2(5),CHZ3.6 Hz, H-2,5), 2.22 (m, 2H, CH), 1.06
(dd, 12H, JH,PZ3.7 Hz, JMe,CHZ6.6 Hz, CH3). 13C NMR
(CDCl3) d: 131.8 (d, JC,PZ2.7 Hz), 131.4 (d, JC,PZ13.6 Hz,
C-3,4), 130.2 (d, JC,PZ9.0 Hz), 129.1 (d, JC,PZ11.2 Hz),
52.3 (d, JC,PZ65.5 Hz, C-2,5), 29.0 (d, JC,PZ3.4 Hz, CH),
23.1 (d, JC,PZ4.5 Hz, CH3), 21.6 (d, JC,PZ8.6 Hz, CH3).
31P NMR (CDCl3) d: 55.2. nmax (film): 2958, 2870, 1470,
1737, 1191, 1111, 743, 714, 697, 564 cmK1. HR-MS (EI)
calcd for C16H23OP (M)C: 262.1486. Found: 262.1481.
]CH2), 43.0 (d, JC,PZ67.4 Hz, C-2), 33.8 (d, JC,PZ
65.6 Hz, C-5), 32.9 (d, JC,PZ2.3 Hz, CH2). 31P NMR
(CDCl3) d: 54.9. nmax (film): 3077, 3057, 2978, 2907, 1640,
1438, 1228, 1183, 1113, 747, 716, 696, 558 cmK1. HR-MS
(EI) calcd for C13H15OP (M)C: 218.0860. Found: 218.0863.
2.2.13. 2,5-Diallyl-1-phenyl-3-phospholene 1-oxide (24).
Yield: 49 mg (19%), colorless oil. 1H NMR (CDCl3) d: 6.06
(dd, 2H, JH,PZ27.5 Hz, JZ0.5 Hz, H-3,4), 5.88 (m, 2H,
]CH), 5.07 (m, 4H, ]CH2), 2.70 (m, 4H), 2.33 (m, 2H).
13C NMR (CDCl3) d: 135.8 (d, JC,PZ9.9 Hz), 134.0 (d,
2.2.9. 2,5-Diisopropyl-1-phenyl-3-phospholene 1-sulfide
(20). Yield: 78 mg (28%), white solid. Mp: 75–78 8C. H
1
JC,PZ87.8 Hz), 131.8 (d, JC,PZ13.6 Hz), 131.7 (d, JC,PZ
NMR (CDCl3) d: 6.08 (d, 2H, JH,PZ27.1 Hz, H-3,4), 2.74
(dd, 2H, JH,PZ7.8 Hz, J2(5),CHZ3.3 Hz, H-2,5), 2.26
(m, 2H, CHMe2), 1.05 (d, 6H, JH,MeZ6.7 Hz, 2!CH3),
3.3 Hz), 129.8 (d, JC,PZ9.1 Hz), 128.6 (d, JC,PZ11.2 Hz),
116.7 (s, ]CH2), 43.4 (d, JC,PZ65.7 Hz, H-2,5), 33.4 (d,
JC,PZ3.1 Hz, CH2). 31P NMR (CDCl3) d: 53.8. nmax (film):

1488
Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
3077, 2978, 2908, 1640, 1437, 1189, 1112, 915, 746, 696,
560 cmK1. HR-MS (EI) calcd for C16H19OP (M)C:
258.1173. Found: 258.1164.
phenyl-3-phospholene 1-oxide (29). Yield: 206 mg
(55%), white solid. Mp: 68–70 8C. H NMR (CDCl3) d:
3.40 (m, 1H), 3.20 (m, 1H), 3.02 (m, 1H), 2.89 (m, 1H), 2.63
(m, 1H), 1.80 (s, 3H, CH3), 1.66 (s, 3H, CH3). 13C NMR
1
(CDCl3) d: 139.1 (d, JC,PZ6.5 Hz, C-3(4)), 133.7 (d, JC,P
91.0 Hz), 132.8 (d, JC,PZ11.4 Hz), 132.5 (d, JC,P
Z
Z
2.2.14. 2,5-Diallyl-1-phenyl-3-phospholene 1-sulfide (25).
Yield: 104 mg (38%), colorless oil. H NMR (CDCl3) d:
1
13.2 Hz), 131.5 (d, JC,PZ2.6 Hz), 129.8 (d, JC,PZ9.0 Hz),
128.4 (d, JC,PZ11.3 Hz), 128.2 (d, JC,PZ9.4 Hz, C-4(3)),
128.0 (s), 127.3 (s), 124.4 (s), 47.8 (d, JC,PZ67.5 Hz, C-5),
37.9 (d, JC,PZ66.6 Hz, C-2), 34.1 (d, JC,PZ1.4 Hz,
6.09 (d, 2H, JH,PZ27.7 Hz, H-3,4), 5.82 (m, 2H, ]CH),
5.03 (m, 4H, CH2]), 2.98 (m, 2H, H-2,5), 2.71 (m, 2H,
CH2), 2.20 (m, 2H, CH2). 13C NMR (CDCl3) d: 136.3 (d,
JC,PZ12.6 Hz), 132.9 (d, JC,PZ11.6 Hz), 132.2 (d, JC,P
Z
CH2Ar), 16.8 (d, JC,PZ12.7 Hz, CH3), 15.1 (d, JC,P
Z
3.0 Hz), 130.7 (d, JC,PZ9.9 Hz), 129.1 (d, JC,PZ11.7 Hz),
117.5 (s, CH2]), 46.8 (d, JC,PZ50.8 Hz, C-2,5), 36.1 (s,
CH2). 31P NMR (CDCl3) d: 66.8. nmax (film): 3075, 3003,
2977, 2906, 1640, 1436, 1106, 998, 917, 744, 711, 693,
522 cmK1. HR-MS (EI) calcd for C16H19PS (M)C:
274.0945. Found: 274.0943.
11.0 Hz, CH3). 31P NMR (CDCl3) d: 51.2. nmax (KBr): 3056,
2980, 2906, 2858, 1471, 1437, 1210, 1199, 1180, 1022, 745,
694, 529 cmK1. HR-MS (LSIMS) calcd for C19H2179BrOP
(MCH)C: 375.0513. Found: 375.0511.
2.2.19. 2-Benzyloxymethyl-1-phenyl-3-phospholene
1-oxide (30). Yield: 60 mg (20%), colorless oil. H NMR
(CDCl3) d: 6.12 (d, 2H, JH,PZ26.8 Hz, H-3,4), 4.56 (Abq,
1
2.2.15. 2-(2-Bromophenylmethyl)-1-phenyl-3-phos-
pholene 1-oxide (26). Yield: 163 mg (47%), colorless oil.
1H NMR (CDCl3) d: 6.07 and 6.01 (2m, 1H, JH,PZ28.4 Hz,
H-4), 5.92 and 5.86 (2m, 1H, JH,PZ27.3 Hz, H-3), 3.46 (m,
1H, CH2Ph), 3.13 (m, 1H, H-2), 3.02 (m, 1H, CH2Ph), 2.89
(m, 1H, H-5), 2.77 (m, 1H, H-50). 13C NMR (CDCl3) d:
138.8 (d, JH,PZ10.2 Hz), 133.3 (d, JC,PZ90.9 Hz), 132.9
(s), 132.8 (d, JC,PZ12.6 Hz, C-3), 131.9 (d, JC,PZ2.8 Hz),
131.6 (s), 129.8 (d, JC,PZ9.4 Hz), 128.6 (d, JC,PZ11.6 Hz),
128.2 (s), 127.4 (s), 126.6 (d, JC,PZ10.4 Hz, C-4), 124.5 (s),
43.0 (d, JC,PZ66.7 Hz, C-2), 34.7 (d, JC,PZ1.6 Hz,
CH2Ph), 33.9 (d, JC,PZ66.1 Hz, C-5). 31P NMR (CDCl3)
d: 55.9. nmax (film): 3054, 2929, 1471, 1437, 1229, 1187,
1114, 1025, 746, 717, 695, 553 cmK1. HR-MS (EI) calcd
for C17H1679BrOP (M)C: 346.0122. Found: 346.0118.
2H, JHCHZ11.9 Hz, PhCH2), 3.98 (m, 1H, JH,PZJHCH
9.6, JH,H2(H5)Z5.9 Hz, OCHH), 3.79 (m, 1H, JH,H2(H5)
Z
Z
8.2 Hz, OCHH), 3.04 (m, 1H, H-2), 2.85 (m, 1H, H-5), 2.74
(m, 1H, H-50). 13C NMR (CDCl3) d: 138.1 (s), 133.5 (d,
JC,PZ91.9 Hz), 131.9 (d, JC,PZ2.8 Hz), 131.4 (d, JC,P
13.5 Hz, C-3(4)), 129.8 (d, JC,PZ9.4 Hz), 128.7 (d, JC,P
Z
Z
11.6 Hz), 128.3 (s), 127.7 (s), 127.6 (d, JC,PZ22.9 Hz,
C-4(3)), 127.6 (d, JC,PZ12.7 Hz), 73.4 (s, OCH2), 68.4 (s,
OCH2), 44.6 (d, JC,PZ67.5 Hz, C-2), 34.0 (d, JC,P
Z
66.8 Hz, C-5). 31P NMR (CDCl3) d: 54.4. nmax (film):
3056, 2903, 2859, 1437, 1229, 1187, 1113, 1101, 745, 696,
559 cmK1. HR-MS (EI) calcd for C18H19O2P (M)C:
298.1123. Found: 298.1119.
2.2.16. 2,5-Di-(2-bromophenylmethyl)-1-phenyl-3-phos-
pholene 1-oxide (27). Yield: 170 mg (33%), white solid.
2.2.20. 2,5-Dibenzyloxymethyl-1-phenyl-3-phospholene
1-oxide (31). Yield: 121 mg (29%), colorless oil. 1H
NMR (CDCl3) d: 6.15 (d, 2H, JH,PZ26.8 Hz, H-3,4), 4.50
1
Mp: 71–73 8C. H NMR (CDCl3) d: 5.90 (d, 2H, JH,P
Z
26.3 Hz, H-3,4), 3.43 (m, 2H), 3.13 (m, 4H). 13C NMR
(CDCl3) d: 138.6 (d, JH,PZ9.3 Hz), 132.9 (s), 131.9 (s),
131.7 (d, JC,PZ1.3 Hz), 131.3 (d, JC,PZ12.8 Hz), 129.9 (d,
JC,PZ9.3 Hz), 128.5 (d, JC,PZ11.5 Hz), 128.2 (s), 127.4 (s),
(ABq, 4H, JHCHZ11.8 Hz, PhCH2), 3.92 (m, 2H, JH,P
Z
JHCHZ9.6, JH,H2(H5)Z6.3 Hz, OCHH), 3.74 (m, 2H,
JH,H2(H5)Z7.7 Hz, JH,PZ11.0 Hz, OCHH), 3.08 (m, 2H,
H-2,5). 13C NMR (CDCl3) d: 141.0 (s), 138.1 (s), 133.3 (d,
124.4 (s), 43.6 (d, JC,PZ64.8 Hz, C-2,5), 35.0 (d, JC,P
Z
2.9 Hz, CH2Ph). 31P NMR (CDCl3) d: 55.3. nmax (KBr):
2916, 1471, 1438, 1183, 1111, 1021, 762, 752, 744, 693,
637, 550 cmK1. HR-MS (LSIMS) calcd for C24H2279Br2OP
(MCH)C: 514.9775. Found: 514.9771.
JC,PZ91.7 Hz), 131.9 (d, JC,PZ2.8 Hz), 130.9 (d, JC,P
Z
12.2 Hz), 130.0 (d, JC,PZ9.4 Hz), 128.7 (d, JC,PZ11.7 Hz),
128.5 (s), 128.3 (s), 127.7 (s), 127.6 (d, JC,PZ2.5 Hz), 126.9
(s), 73.4 (s, OCH2), 68.4 (s, OCH2), 44.9 (d, JC,PZ66.6 Hz,
C-2,5). 31P NMR (CDCl3) d: 53.4. nmax (film): 3062, 3030,
2861, 1453, 1181, 1101, 737, 696, 561 cmK1. HR-MS (EI)
calcd for C26H27O3P (M)C: 418.1698. Found: 418.1694.
2.2.17. 2-(2-Bromophenylmethyl)-1-phenyl-3-phos-
pholene 1-sulfide (28). Yield: 258 mg (71%), colorless
oil. 1H NMR (CDCl3) d: 6.04 (dm, 1H, JH,PZ28.9 Hz,
H-3(4)), 5.85 (dm 1H, JH,PZ27.8 Hz, H-4(3)), 3.53 (m, 1H,
ArCHH), 3.33 (m, 1H), 3.21 (m, 1H, H-5), 3.04 (m, 1H,
H-50), 2.93 (m, 1H, ArCHH). 13C NMR (CDCl3) d: 139.0 (d,
2.2.21.
2-Allyloxymethyl-1-phenyl-3-phospholene
1
1-oxide (32). Yield: 67 mg (27%), colorless oil. H NMR
(CDCl3) d: 6.12 (m, 2H, H-3,4), 5.88 (m, 1H, CH]), 5.25
(m, 1H, CHH]), 5.15 (m, 1H, CHH]), 4.03 (m, 2H,
OCH2CH]), 3.93 (m, 1H, JHCHZJH,PZ9.4 Hz,
JH,H2(H5)Z5.8 Hz, OCHH), 3.74 (m, 1H, JH,H2Z8.3 Hz,
OCHH), 3.01 (m, 1H, H-2), 2.86 (m, 1H, H-5), 2.74 (m, 1H,
H-50). 13C NMR (CDCl3) d: 134.5 (s, CH]), 133.6 (d,
JC,PZ13.4 Hz), 133.4 (d, JC,PZ97.1 Hz), 133.2 (d, JC,P
Z
12.6 Hz, C-3(4)), 133.0 (s), 131.6 (d, JC,PZ3.0 Hz), 131.6
(s), 130.1 (d, JC,PZ10.2 Hz), 128.6 (d, JC,PZ11.9 Hz),
128.2 (s), 127.4 (s), 127.3 (d, JC,PZ7.7 Hz, C-4(3)), 124.6
(s), 45.9 (d, JC,PZ51.1 Hz, C-2), 41.1 (d, JC,PZ53.7 Hz,
C-5), 36.9 (d, JC,PZ0.8 Hz, CH2Ar). 31P NMR (CDCl3) d:
60.4. nmax (film): 3052, 1470, 1436, 1110, 1025, 746, 712,
693 cmK1. HR-MS (EI) calcd for C17H16PS (MKBr)C:
283.0710. Found: 283.0707.
JC,PZ92.2 Hz), 131.9 (d, JC,PZ2.8 Hz), 131.4 (d, JC,P
13.3 Hz, C-3(4)), 129.8 (d, JC,PZ9.4 Hz), 128.6 (d, JC,P
Z
Z
11.6 Hz), 127.6 (d, JC,PZ10.2 Hz, C-3(4)), 117.0 (s,
CH2]), 72.2 (s, OCH2), 68.2 (s, OCH2), 44.5 (d, JC,P
Z
67.5 Hz, C-2), 33.9 (d, JC,PZ66.9 Hz, C-5). 31P NMR
(CDCl3) d: 54.3. nmax (film): 3054, 2906, 2858, 1438, 1229,
2.2.18.
2-(2-Bromophenylmethyl)-3,4-dimethyl-1-

Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
1489
1185, 1114, 1097, 748, 718, 696, 559 cmK1. HR-MS (EI)
calcd for C14H17O2P (M)C: 248.0966. Found: 248.0977.
calcd for C23H22O2P (MCH)C: 361.1361. Found:
361.1352.
2.2.22. 2,5-Diallyloxymethyl-1-phenyl-3-phospholene
1-oxide (33). Yield: 51 mg (16%), colorless oil. H NMR
2.2.26. (1-Tio-1-phenyl-2,3-dihydro-1H-phosphol-3-yl)-
diphenylmethanol (35). Yield: 158 mg (42%), colorless
oil. H NMR (CDCl3) d: 6.62 (ddd, 1H, JH,PZ45.8 Hz,
1
1
(CDCl3) d: 6.17 (d, 2H, JH,PZ26.8 Hz, H-3,4), 5.88 (m, 2H,
CH]), 5.25 (m, 2H, CHH]), 5.15 (m, 2H, CHH]), 4.02
(m, 4H, OCH2CH]), 3.89 (m, 2H, JHCHZJH,PZ9.5 Hz,
JH,H2(H5)Z6.2 Hz, OCHH), 3.72 (m, 2H, JH,PZ10.7 Hz,
JH,H2(H5)Z7.9 Hz, OCHH), 3.06 (m, 2H, H-2,5). 13C NMR
(CDCl3) d: 134.5 (s, CH]), 133.4 (d, JC,PZ91.9 Hz), 131.9
J2,3Z7.9 Hz, J2,4Z2.5 Hz, H-2), 6.33 (ddd, 1H, JH,P
Z
27.9 Hz, J3,4Z2.2 Hz, H-3), 4.44 (m, 1H, H-4), 2.57 (m, 1H,
H-5), 2.32 (m, 1H, H-50). 13C NMR (CDCl3) d: 149.7 (d,
JC,PZ16.6 Hz), 145.4 (d, JC,PZ59.0 Hz), 132.3 (d, JC,P
Z
77.5 Hz), 131.8 (d, JC,PZ3.0 Hz), 130.9 (d, JC,PZ11.6 Hz),
130.3 (d, JC,PZ75.1 Hz), 128.6 (d, JC,PZ12.6 Hz), 128.5
(d, JC,PZ2.8 Hz), 131.0 (d, JC,PZ12.2 Hz), 130.0 (d, JC,P
Z
8.2 Hz), 128.6 (d, JC,PZ11.6 Hz, C-3,4), 117.0 (s, CH2]),
72.2 (s, OCH2), 68.2 (s, OCH2), 44.8 (d, JC,PZ66.5 Hz,
C-2,5). 31P NMR (CDCl3) d: 53.0. nmax (film): 2858, 1438,
1190, 1098, 926, 747, 714, 696, 560 cmK1. HR-MS (EI)
calcd for C18H23O3P (M)C: 318.1385. Found: 318.1387.
(d, JC,PZ4.5 Hz), 127.1 (d, JC,PZ4.4 Hz), 125.6 (d, JC,P
20.6 Hz), 79.5 (d, JC,PZ2.4 Hz, C-OH), 54.9 (d, JC,P
Z
Z
6.9 Hz, C-4), 35.8 (d, JC,PZ57.0 Hz, H-5). 31P NMR
(CDCl3) d: 64.9. nmax (KBr): 3051, 3033, 1158, 1492,
1448, 1436, 1107, 861, 783, 755, 743, 717, 700, 667,
650 cmK1. HR-MS (EI) calcd for C23H21OPS (M)C:
376.1051. Found: 376.1045.
2.2.23. 2-(4-Chlorobutyl)-1-phenyl-3-phospholene
1-oxide and 2-(4-bromobutyl)-1-phenyl-3-phospholene
1-oxide (54a and 54b, respectively). Yield: 84 mg (27%),
2.2.27. (1-Boranato-1-phenyl-2,3-dihydro-1H-phosphol-
3-yl)-diphenylmethanol (36). Yield: 179 mg (50%), white
solid. Mp: 63–64 8C. H NMR (CDCl3) d: 6.64 (ddd, 1H,
1
colorless oil. H NMR (CDCl3) d: 6.05 (d, JH,PZ28.2 Hz,
H-3,4), 3.52 (m, 54a), 3.40 (m, 54b), 2.82 (m), 2.70 (m),
1
1.57–2.05 (3m). 13C NMR (CDCl3) d: for 54a–133.4 (d,
JH,PZ33.7 Hz, J2,3Z8.0 Hz, J2,4Z2.2 Hz, H-2), 6.25 (ddd,
1H, JH,PZ30.6 Hz, J3,4Z2.5 Hz, H-3), 4.52 (m, 1H, H-4),
JC,PZ14.3 Hz), 131.9 (d, JC,PZ2.8 Hz), 129.7 (d, JC,P
9.3 Hz), 128.7 (d, JC,PZ11.4 Hz), 126.7 (d, JC,PZ10.8 Hz),
44.7 (s, CH2), 43.4 (d, JC,PZ67.8 Hz, C-2), 33.7 (d, JC,P
Z
0
2.26 (ddd, 1H, JH,PZ5.9 Hz, J5,5 Z15.6 Hz, J5,4Z3.1 Hz,
H-5), 2.07 (dt, 1H, JH,PZ8.6 Hz, J5 ,4Z8.6 Hz, H-50), 0.6–
0
Z
65.9 Hz, C-5), 32.5 (m, CH2), 28.1 (d, JC,PZ2.8 Hz, CH2),
25.6 (m, CH2); for 54b—132.2 (d, JC,PZ13.8 Hz), 129.6 (d,
JC,PZ9.1 Hz), 44.7 (s, CH2), 43.7 (d, JC,PZ66.0 Hz, C-2),
32.5 (m, CH2), 28.9 (d, JC,PZ3.5 Hz, CH2), 25.6 (m, CH2).
31P NMR (CDCl3) d: 55.1 (54a), 54.2 (54b). 54a. HR-MS
(EI) calcd for C14H1835ClOP (M)C: 268.0784. Found:
268.0793. 54b. HR-MS (EI) calcd for C14H1879BrOP (M)C:
312.0279. Found: 312.0279.
1.2 (m, 3H, BH3). 13C NMR (CDCl3) d: 150.4 (d, JC,P
Z
6.3 Hz), 145.4 (d, JH,PZ75.5 Hz), 131.7 (d, JC,PZ9.8 Hz),
131.5 (d, JC,PZ2.4 Hz), 130.1 (d, JC,PZ47.2 Hz), 128.9 (d,
JC,PZ9.8 Hz), 128.6 (d, JC,PZ17.2 Hz), 127.2 (d, JC,P
16.2 Hz), 126.7 (d, JC,PZ48.7 Hz), 125.6 (d, JC,P
10.4 Hz), 79.2 (d, JC,PZ4.6 Hz, COH), 56.8 (s, C-4), 26.1
(d, JC,PZ38.8 Hz, C-5). 31P NMR (CDCl3) d: 47.0 (d, JZ
62.8 Hz). nmax (film): 3058, 3025, 3006, 2379, 1492, 1448,
1437, 1059, 887, 748, 703, 634 cmK1. HR-MS (EI) calcd
for C23H21OP (MKBH3)C: 344.1330. Found: 344.1338.
HR-MS (EI) calcd for C23H2311BOP (MKH)C: 357.1580.
Found: 357.1589.
Z
Z
2.2.24. 2,5-Di-(4-chlorobutyl)-1-phenyl-3-phospholene
1-oxide (55). Yield: 64 mg (18%), colorless oil. H NMR
1
(CDCl3) d: 6.05 (d, 2H, JH,PZ27.7 Hz, H-3,4), 3.51 (m,
4H), 2.65 (m, 2H), 1.94 (m, 2H), 1.78 (m, 4H), 1.59 (m, 6H).
13C NMR (CDCl3) d: 134.4 (d, JC,PZ87.4 Hz), 132.2 (d,
JC,PZ13.7 Hz, C-3,4), 131.8 (d, JC,PZ2.8 Hz), 129.6 (d,
JC,PZ92.0 Hz), 128.7 (d, JC,PZ11.2 Hz), 44.7 (s, CH2),
2.2.28. 5-Methyl-2-phenyl-2-phosphabicyclo[3.3.0]oct-3-
ene 2-oxide (40) and 4-methyl-2-phenyl-2-phospha-
bicyclo[3.3.0]oct-3-ene 2-oxide (41). Yield: 167 mg
(72%, inseparable mixture), colorless oil. NMR data for
43.7 (d, JC,PZ66.1 Hz, C-2,5), 32.4 (s, CH2), 28.9 (d, JC,P
Z
3.4 Hz, CH2), 25.7 (d, JC,PZ7.5 Hz, CH2). 31P NMR
(CDCl3) d: 54.1. nmax (film): 2938, 2863, 1456, 1437,
1188, 1113, 745, 717, 697, 635, 563 cmK1. HR-MS
(LSIMS) calcd for C18H2635Cl2OP (MCH)C: 359.1098.
Found: 359.1111.
40. H NMR (CDCl3) d: 6.83 (dd, 1H, JH,PZ45.3 Hz, JZ
1
8.1 Hz, H-4), 6.11 (dd, 1H, JH,PZ23.0 Hz, JZ8.1 Hz, H-3),
1.36 (s, 3H, CH3). 13C NMR (CDCl3) d: 160.2 (d, JC,P
23.8 Hz, C-3), 134.5 (d, JC,PZ95.6 Hz), 131.5 (d, JC,P
Z
Z
2.8 Hz), 130.4 (d, JC,PZ10.4 Hz), 128.6 (d, JC,PZ11.8 Hz),
123.4 (d, JC,PZ89.4 Hz, C-4), 56.8 (d, JC,PZ12.0 Hz, C-5),
46.2 (d, JC,PZ70.3 Hz, C-1), 40.9 (CH2), 27.3 (d, JC,P
Z
2.2.25. (1-Oxo-1-phenyl-2,3-dihydro-1H-phosphol-3-yl)-
diphenylmethanol (34). Yield: 266 mg (74%), white solid.
4.9 Hz, CH3), 26.9 (d, JC,PZ2.8 Hz, CH2), 26.7 (d,
JC,PZ2.0 Hz, CH2). 31P NMR (CDCl3) d: 62.1. nmax (film):
3055, 2954, 2865, 1583, 1437, 1331, 1184, 1112, 750, 719,
696, 530 cmK1. HR-MS (EI) calcd for C14H17OP (M)C:
232.1017. Found: 232.1016.
1
Mp: 90–92 8C. H NMR (CDCl3) d: 6.82 (ddd, 1H, JH,P
Z
45.1 Hz, J3,2Z8.4 Hz, J3,4Z2.3 Hz, H-3), 6.31 (ddd, 1H,
JH,PZ23.9 Hz, J2,4Z2.3 Hz, H-2), 4.16 (m, 1H, H-4), 2.18
(m, 2H, H-5,50). 13C NMR (CDCl3) d: 153.5 (d, JC,P
Z
20.0 Hz), 145.6 (d, JH,PZ14.0 Hz), 131.8 (d, JC,PZ2.6 Hz),
130.4 (d, JC,PZ10.4 Hz), 128.6 (d, JC,PZ11.9 Hz), 128.3
2.2.29. 5-Methyl-2-phenyl-2-phosphabicyclo[3.3.0]oct-3-
ene 2-sulfide (42) and 4-methyl-2-phenyl-2-phospha-
bicyclo[3.3.0]oct-3-ene 2-sulfide (43). Yield: 166 mg
(67%, inseparable mixture) from 1,3-dibromopropane or
144 mg (58%, inseparable mixture) from diiodopropane,
(d, JC,PZ6.1 Hz), 126.9 (d, JC,PZ3.9 Hz), 125.8 (d, JC,P
Z
Z
7.4 Hz), 79.0 (d, JC,PZ3.7 Hz, COH), 52.3 (d, JC,P
10.1 Hz, C-4), 28.9 (d, JC,PZ70.8 Hz, C-5). 31P NMR
(CDCl3) d: 60.2. nmax (KBr): 3059, 2972, 1449, 1438, 1210,
1160, 1132, 1111, 855, 748, 696, 636 cmK1. HR-MS (ESI)
1
colorless oil. NMR data for 42. H NMR (CDCl3) d: 6.68

1490
Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
(dd, 1H, JH,PZ46.0, JZ7.8 Hz, H-4), 6.02 (dd, 1H, JH,P
Z
(d, JC,PZ12.1 Hz), 128.4 (d, JC,PZ12.1 Hz), 126.1 (d,
JC,PZ75.8 Hz), 60.5 (d, JC,PZ10.5 Hz), 55.5 (d, JC,P
26.7 Hz, JZ7.7 Hz, H-3), 2.53 (m, 2H), 2.18 (m, 1H), 1.65–
2.00 (m, 4H), 1.40 (s, 3H, CH3). 13C NMR (CDCl3) d: 157.3
(d, JC,PZ20.3 Hz, C-3(4)), 131.2 (d, JC,PZ3.1 Hz), 130.6
(d, JC,PZ11.1 Hz), 128.5 (d, JC,PZ12.1 Hz), 124.1 (d,
JC,PZ74.7 Hz, C-3(4)), 59.1 (d, JC,PZ9.9 Hz, C-5), 49.2 (d,
JC,PZ52.1 Hz, C-1), 41.0 (s, CH2), 29.0 (s, CH2), 27.8 (d,
JC,PZ4.1 Hz, CH3), 26.5 (d, JC,PZ2.2 Hz, CH2). 31P NMR
(CDCl3) d: 74.3. HR-MS (ESI) calcd for C14H18PS (MC
H)C: 249.0861. Found: 249.0876.
Z
8.7 Hz), 42.9 (d, JC,PZ54.9 Hz), 42.7 (d, JC,PZ53.5 Hz),
35.5 (d, JC,PZ5.6 Hz, CH2), 33.7 (s, CH2), 27.1 (s, CH2),
26.6 (s, CH2), 19.3 (s, CH3), 15.6 (s, CH3). 31P NMR
(CDCl3) d: 74.2 (minor) and 71.8 (major). nmax (film): 3052,
2954, 2869, 1578, 1456, 1436, 1103, 737, 719, 694 cmK1
.
HR-MS (EI) calcd for C14H17PS (M)C: 248.0789. Found:
248.0789.
2.2.33. 6-Methyl-2-phenyl-2-phosphabicyclo[3.3.0]oct-3-
ene 2-borane (47). Colorless oil, contaminated with approx.
11% of 2,5-dialkylated monocyclic product. 1H NMR
2.2.30. 4,5-Dimethyl-2-phenyl-2-phosphabicyclo[3.3.0]-
oct-3-ene 2-oxide (44). Yield: 135 mg (55%), white solid.
1
Mp: 94–98 8C. H NMR (CDCl3) d: 5.76 (dd, 1H, JH,P
Z
(CDCl3) d: 6.77 (ddd, JH,PZ33.4 Hz, J2,3Z7.9 Hz, J2,4
2.6 Hz, H-3-major), 6.09 (ddd, JH,PZ30.7 Hz, J3,4Z2.5 Hz,
H-4-major), 6.79 (ddd, JH,PZ32.6 Hz, J2,3Z7.8 Hz, J2,4
Z
22.3 Hz, JZ1.1 Hz, H-3), 2.34 (m, 1H), 2.11 (m, 1H), 2.02
(m, 3H, CH3), 1.85 (m, 2H, 1.76 (m, 2H), 1.55 (m, 1H), 1.33
(s, 3H, CH3). 13C NMR (CDCl3) d: 170.5 (d, JC,PZ24.0 Hz,
C-4), 135.5 (d, JC,PZ96.8 Hz), 131.8 (d, JC,PZ2.8 Hz),
131.0 (d, JC,PZ10.2 Hz), 129.0 (d, JC,PZ11.6 Hz), 120.2
(d, JC,PZ96.5 Hz, C-3), 59.4 (d, JC,PZ11.1 Hz, C-5), 49.2
Z
2.5 Hz, H-3-minor), 5.94 (ddd, JH,PZ30.5 Hz, J3,4Z3.0 Hz,
H-4-minor). 31P NMR (CDCl3) d: 56.1 (m, major), 53.3 (m,
minor). HR-MS (EI) calcd for C14H17P (MKBH3)C:
216.1068. Found: 216.1051.
(d, JC,PZ69.7 Hz, C-1), 40.0 (s, CH2), 27.9 (d, JC,P
3.7 Hz, CH2), 27.3 (d, JC,PZ6.6 Hz, CH3), 27.7 (d, JC,P
Z
Z
2.2.34. 4,5,6-Trimethyl-2-phenyl-2-phosphabicyclo-
[3.3.0]oct-3-ene 2-oxide (48). Yield: 200 mg (77%), color-
less oil. 1H NMR (CDCl3) d: 5.79 (dm, JZ22.3, 1.1 Hz, H-3
major), 5.68 (dm, JZ21.8, 1.1 Hz, H-3 minor), 1.98 (s,
CH3), 1.35 (s, CH3), 0.92 (d, JZ7.1 Hz, CH3). 13C NMR
2.9 Hz, CH2), 17.8 (d, JC,PZ19.1 Hz, CH3). 31P NMR
(CDCl3) d: 54.4. nmax (film): 3054, 2955, 2866, 1602, 1437,
1191, 1166, 1145, 1110, 840, 750, 712, 696, 541 cmK1
.
HR-MS (EI) calcd for C15H19OP (M)C: 246.1173. Found:
246.1179.
(CDCl3) d: 168.0 (d, JC,PZ22.3 Hz, C-4), 134.9 (d, JC,P
97.7 Hz), 121.4 (d, JC,PZ96.8 Hz, C-3), 62.1 (d, JC,P
Z
Z
11.2 Hz, C-5), 48.7 (d, JC,PZ70.3 Hz, C-1), 43.3 (s, C-6),
35.7 (d, JC,PZ5.2 Hz, CH2), 27.3 (d, JC,PZ10.3 Hz, CH3),
22.1 (d, JC,PZ2.6 Hz, CH2), 18.5 (d, JC,PZ18.9 Hz, CH3),
16.5 (s, CH3). 31P NMR (CDCl3) d: 50.2 (major) and 52.2
(minor). nmax (film): 3054, 2960, 2931, 2874, 1600, 1455,
1437, 1187, 1111, 846, 749, 714, 695, 544 cmK1. HR-MS
(ESI) calcd for C16H21NaOP (MCNa)C: 283.1222. Found:
283.1232.
2.2.31. 6-Methyl-2-phenyl-2-phosphabicyclo[3.3.0]oct-3-
ene 2-oxide (45). Yield: 155 mg (67%), colorless oil. H
1
NMR (CDCl3) d: 7.04 and 6.95 (2m, H-3), 6.32 (ddd, JH,P
Z
24.1 Hz, J3,2Z8.3 Hz, J3,4Z2.2 Hz, H-4-major), 6.15 (ddd,
JH,PZ23.3 Hz, J3,2Z8.2 Hz, J3,4Z2.1 Hz, H-4-minor),
3.40 (m), 2.97 (m), 2.55 (m), 2.43 (m), 2.29 (m), 2.18
(m), 1.97 (m), 1.74 (m), 1.42 (m), 1.32 (m), 1.12 (2d,
JMe,CHZ6.6, 6.9 Hz, 2!CH3). 13C NMR (CDCl3) d: 154.0
(d, JC,PZ24.0 Hz), 152.2 (d, JC,PZ25.5 Hz), 131.5 (d,
JC,PZ2.9 Hz), 131.4 (d, JC,PZ2.8 Hz), 130.3 (d, JC,P
10.2 Hz), 130.3 (d, JC,PZ10.2 Hz), 128.5 (d, JC,PZ11.8 Hz),
128.5 (d, JC,PZ11.8 Hz), 128.0 (d, JC,PZ91.1 Hz), 124.8 (d,
Z
2.2.35. {2-[(E)-2-(Diethoxyphosphoryl)-vinyl]-cyclo-
pentyl}-phosphonic acid diethyl ester (50). Yield:
147 mg (40%), colorless oil. Major diastereoisomer. 1H
JC,PZ91.2 Hz), 58.3 (d, JC,PZ12.5 Hz), 53.2 (d, JC,P
10.8 Hz), 41.3 (s), 39.7 (d, JC,PZ16.6 Hz), 39.1 (d, JC,P
15.5 Hz), 39.1 (d, JC,PZ0.9 Hz), 35.6 (d, JC,PZ5.3 Hz, CH2),
Z
Z
NMR (CDCl3) d: 6.72 (ddd, 1H, JH,PZ21.8 Hz, JCHZCHZ
17.1, JZ7.8 Hz, CH]), 5.69 (ddd, 1H, JH,PZ20.2 Hz, JZ
1.1 Hz, CH]), 4.08 (m, 8H, 4!CH2), 2.94 (m, 1H), 1.98
(m, 4H), 1.72 (m, 2H), 1.54 (dq, 1H, JZ12.6, 7.9 Hz,
OCH2), 1.32 (m, 12H, 4!CH3). 13C NMR (CDCl3) d: 155.1
(t, JC,P1ZJC,P2Z4.4 Hz, CH]), 116.3 (d, JC,PZ187.9 Hz,
PCH]), 61.6 (m, 4!OCH2), 45.2 (dd, JC,P1Z1.5 Hz,
JC,P2Z22.2 Hz, CH), 40.5 (d, JC,PZ146.3 Hz, CH), 33.4 (d,
JC,PZ10.7 Hz, CH2), 27.5 (d, JC,PZ1.6 Hz, CH2), 25.5 (d,
JC,PZ10.1 Hz, CH2), 16.4 (3d, 3!CH3). 31P NMR (CDCl3)
d: 33.5 and 19.1 (major); 32.7 and 17.3 (minor). nmax (film):
33.6 (s,CH2), 24.5 (d, JC,PZ3.0 Hz, CH2), 24.2 (d, JC,P
Z
2.8 Hz, CH2), 19.2 (s, CH3), 15.1 (s, CH3). 31P NMR (CDCl3)
d: 60.8 (s, major), 59.2 (s, minor). nmax (film): 3054, 2955,
2871, 1578, 1437, 1178, 1115, 835, 749, 723, 695, 611,
541 cmK1. HR-MS (EI) calcd for C14H17OP (M)C: 232.1017.
Found: 232.1021.
2.2.32. 6-Methyl-2-phenyl-2-phosphabicyclo[3.3.0]oct-3-
ene 2-sulfide (46). Yield: 131 mg (53%), colorless oil. H
2982, 2909, 2873, 1632, 1234, 1052, 1025, 963, 791 cmK1
.
1
HR-MS (EI) calcd for C15H30O6P2 (M)C: 368.1518. Found:
368.1523.
NMR (CDCl3) d: 6.84 (ddd, JH,PZ44.2 Hz, J2,3Z7.7 Hz,
J2,4Z2.7 Hz, H-3 major), 6.82 (ddd, JH,PZ45.3 Hz, J2,3
8.0 Hz, J2,4Z2.7 Hz, H-3 minor), 6.20 (ddd, 1H, JH,P
Z
Z
27.9 Hz, J2,3Z7.9 Hz, J2,4Z2.4 Hz, H-4 minor), 6.04 (ddd,
1H, JH,PZ27.5 Hz, J2,3Z7.8 Hz, J2,4Z2.2 Hz, H-5 major),
3.63 (m), 3.15 (m), 2.74 (m), 2.68 (m), 2.55 (m), 2.40 (m),
2.21 (m), 1.94 (m), 1.80 (m), 1.72 (m), 1.40 (m), 1.26 (m),
1.12 (d, JMe,CHZ6.5 Hz, CH3), 1.09 (d, JMe,CHZ6.9 Hz,
CH3). 13C NMR (CDCl3) d: 151.1 (d, JC,PZ20.0 Hz), 149.6
(d, JC,PZ21.6 Hz), 131.3 (2d), 130.7 (d, JC,PZ10.9 Hz),
130.6 (d, JC,PZ10.9 Hz), 128.9 (d, JC,PZ76.0 Hz), 128.5
2.2.36. {(E)-2-[2-(Diphenyl-phosphinoyl)-cyclopentyl]-
vinyl}-phosphonic acid diethyl ester (52) and {2-[(E)-2-
(diphenyl-phosphinoyl)-vinyl]-cyclopentyl}-phosphonic
acid diethyl ester (53). Yield: 173 mg (40%, inseparable
1
mixture), colorless oil. H NMR (CDCl3) d: 52: 6.68 (ddd,
JZ8.0, 16.9, 19.1 Hz, CH]) and 6.27 (ddd, JZ1.0, 16.9,
24.6 Hz, ]CH); 53: 6.45 (ddd, JZ8.6, 17.0, 21.6 Hz,
CH]), 5.08 (ddd, JZ0.9, 17.0, 20.1 Hz, ]CH). 13C NMR

Z. Pakulski et al. / Tetrahedron 61 (2005) 1481–1492
1491
´
Zhang, X. Chem. Rev. 2003, 103, 3029–3069. (f) Crepy,
K. V. L.; Imamoto, T. Top. Curr. Chem. 2003, 229, 1–40.
3. (a) Burk, M. J.; Feaster, J. E.; Harlow, R. L. Organometallics
1990, 9, 2653–2655. (b) Burk, M. J. J. Am. Chem. Soc. 1991,
113, 8518–8519. (c) Burk, M. J.; Feaster, J. E.; Harlow, R. L.
Tetrahedron: Asymmetry 1991, 2, 569–592. (d) Burk, M. J.;
Feaster, J. E.; Nugent, W. A.; Harlow, R. L. J. Am. Chem. Soc.
1993, 115, 10125–10138.
(CDCl3) d: 155.4 (m, C]), 154.1 (m, C]), 121.3 (d, JC,P
Z
102.1 Hz, ]CPPh2), 115.9 (d, JC,PZ187.2 Hz, ]CP(OEt)2),
61.4–61.8 (4!d, OCH2), 45.6 (d, JC,PZ16.9 Hz, CH), 43.7
(d, JC,PZ22.2 Hz, CH), 42.0 (d, JC,PZ73.1 Hz, CH), 40.7 (d,
JC,PZ145.8 Hz, CH), 34.3 (d, JC,PZ4.8 Hz, CH2), 33.7 (d,
JC,PZ11.4 Hz, CH2), 27.6 (d, JC,PZ12.9 Hz, CH2), 26.2 (d,
JC,PZ6.1 Hz, CH2), 25.5 (d, JC,PZ10.3 Hz, CH2), 16.3–16.5
(m, CH3). 31P NMR (CDCl3) d: 52: 35.7 and 19.7. 53: 34.6 and
24.4. nmax (film): 3056, 2981, 2907, 2871, 1631, 1438, 1233,
4. (a) Zhu, G.; Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X.
J. Am. Chem. Soc. 1997, 119, 3836–3837. (b) Chen, Z.; Jiang,
Q.; Zhu, G.; Xiao, D.; Cao, P.; Guo, C.; Zhang, X. J. Org.
Chem. 1997, 62, 4521–4523. (c) Chen, Z.; Zhu, G.; Jiang, Q.;
Xiao, D.; Cao, P.; Zhang, X. J. Org. Chem. 1998, 63,
5631–5635. (d) Holz, J.; Quirmbach, M.; Schmidt, U.; Heller,
1183, 1119, 1052, 1026, 964, 753, 722, 700, 537 cmK1
.
HR-MS (EI) calcd for C23H30O4P2 (M)C: 432.1619. Found:
432.1628.
2.2.37. 2-Phenyl-2-phosphabicyclo[3.3.0]oct-3-ene 2-bor-
ane (39). Phosphine oxide 37 (218 mg, 1 mmol) was treated
with phenylsilane as described for 2. Crude bicyclic
¨
D.; Stu¨rmer, R.; Borner, A. J. Org. Chem. 1998, 63,
8031–8034. (e) Guillen, F.; Fiaud, J. C. Tetrahedron Lett.
1999, 40, 2939–2942. (f) Vedejs, E.; Daugulis, O. J. Am.
Chem. Soc. 1999, 121, 5813–5814. (g) Li, W.; Zhang, Z.;
Xiao, D.; Zhang, X. Tetrahedron Lett. 1999, 40, 6701–6704.
(h) Burk, M. J.; Pizzano, A.; Martin, J. A. Organometallics
2000, 19, 250–260. (i) Holz, J.; Stu¨rmer, R.; Schmidt, U.;
1
phosphine had the following spectroscopic data. H NMR
(C6D6) d: 5.67 (ddd, 1H, JH,PZ14.2 Hz, J3,2Z7.4 Hz, J3,4
Z
2.5 Hz, H-3), 5.54 (ddd, 1H, JH,PZ39.7 Hz, J2,4Z2.3 Hz,
H-2), 2.92 (m, 1H), 1.97 (m, 1H), 1.42 (m, 2H), 1.07 (m,
2H), 0.92 (m, 2H). 13C NMR (C6D6) d: 148.5 (s), 132.2 (d,
JC,PZ19.0 Hz), 128.6 (s), 128.2 (d, JC,PZ6.0 Hz), 53.6 (d,
¨
Drexler, H.; Heller, D.; Krimmer, H.; Borner, A. Eur. J. Org.
JC,PZ4.3 Hz), 44.7 (d, JC,PZ5.1 Hz), 33.6 (d, JC,P
Z
Chem. 2001, 24, 4615–4624. (j) RajanBabu, T. V.; Yan, Y.;
Shin, S. J. Am. Chem. Soc. 2001, 123, 10207–10213. (k) Hoge,
G. J. Am. Chem. Soc. 2003, 125, 10219–10227. (l) Shimizu,
H.; Saito, T.; Kumobayashi, H. Adv. Synth. Catal. 2003, 345,
185–189.
33.6 Hz, CH2), 31.4 (d, JC,PZ3.4 Hz, CH2), 25.9 (d,
JC,PZ5.1 Hz, CH2). 31P NMR (C6D6) d: 25.3.
To the solution of phosphine obtained above in toluene was
added borane–THF complex (1 equiv) and stirred at room
temperature overnight. Evaporation of solvents and column
chromatography (hexane–ethyl acetate, 9:1) of the residue
5. (a) Guillen, F.; Moinet, C.; Fiaud, J.-C. Bull. Soc. Chim. Fr.
1997, 134, 371–374. (b) Guillen, F.; Rivard, M.; Toffano, M.;
Legros, J. Y.; Daran, J. C.; Fiaud, J. C. Tetrahedron 2002, 58,
5895–5904. (c) Blake, A. J.; Hume, S. C.; Li, W. S.; Simpkins,
N. S. Tetrahedron 2002, 58, 4589–4602.
1
gave borane 39 (200 mg, 92%). H NMR (CDCl3) d: 6.70
(ddd, 1H, JH,PZ32.8 Hz, J2,3Z7.8 Hz, J2,4Z2.5 Hz, H-3),
6.00 (ddd, 1H, JH,PZ30.7 Hz, J2,4Z2.4 Hz, H-4), 3.75 (m,
1H), 2.63 (m, 1H), 2.24 (m, 1H), 1.86 (m, 2H), 1.63 (m, 3H),
0.45–1.20 (m, 3H, BH3). 13C NMR (CDCl3) d: 153.5 (d,
JC,PZ9.7 Hz, C-4), 131.6 (d, JC,PZ48.6 Hz), 131.6 (d,
6. (a) A preliminary communication on the developed cyclo-
pentannulation of phospholenes has already appeared:
Pakulski, Z.; Kwiatosz, R.; Pietrusiewicz, K. M. Tetrahedron
Lett. 2003, 44, 5469–5472. (b) Pakulski, Z.; Koprowski, M.;
Pietrusiewicz, K. M. Tetrahedron 2003, 59, 8219–8226. (c)
Pakulski, Z.; Demchuk, O. M.; Frelek, J.; Luboradzki, R.;
Pietrusiewicz, K. M. Eur. J. Org. Chem. 2004, 3913–3918.
7. (a) Hamer, J. In 1,4-Cycloaddition Reactions; Organic
Chemistry, 1963; Vol. 8, Chapter 3. (b) Quin, L. D. The
Heterocyclic Chemistry of Phosphorus; Wiley: New York,
1981. (c) Quin, L. D. A Guide to Organophosphorus
Chemistry; Wiley: New York, 2000.
JC,PZ9.3 Hz), 131.1 (d, JC,PZ2.4 Hz), 128.7 (d, JC,P
Z
9.8 Hz), 122.3 (d, JC,PZ49.8 Hz, C-3), 53.6 (d, JC,PZ2.9 Hz,
C-5), 40.0 (d, JC,PZ37.4 Hz, C-1), 31.9 (d, JC,PZ2.0 Hz,
CH2), 28.9 (d, JC,PZ6.2 Hz, CH2), 26.1 (d, JC,PZ3.3 Hz,
CH2). 31P NMR (CDCl3) d: 54.6 (m). nmax (film): 2955, 2867,
2380, 1436, 1132, 1108, 1057, 743, 693, 678 cmK1. HR-MS
(EI) calcd for C13H15P (MKBH3)C: 202.0911. Found:
202.0910.
8. Marsi, K. L. J. Org. Chem. 1974, 39, 265–267.
9. (a) Mathey, F.; Lampin, J. P. Compt. Rend. Acad. Sci. Paris
1970, 270, 1531–1533. (b) Lampin, J. P.; Mathey, F.; Bartet,
B. Bull. Soc. Chim. Fr. 1971, 317–329. (c) Lampin, J. P.;
Eberhard, L.; Mathey, F.; Longeau, M. Bull. Soc. Chim. Fr.
1972, 3494–3502.
Acknowledgements
This work was supported by the State Committee for
Scientific Research, Poland, grant no. 7 TO9A 068 20.
10. Muci, A. R.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc.
1995, 117, 9075–9076.
11. (a) Wolfe, B.; Livinghouse, T. J. Am. Chem. Soc. 1998, 120,
5116–5117. (b) Imamoto, T.; Watanabe, J.; Wada, Y.;
Masuda, H.; Yamada, H.; Tsuruta, H.; Matsukawa, S.;
Yamaguchi, K. J. Am. Chem. Soc. 1998, 120, 1635–1636. (c)
Yamanoi, Y.; Imamoto, T. J. Org. Chem. 1999, 64,
2988–2989. (d) Kobayashi, S.; Shiraishi, N.; Lam, W. W. L.;
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1492
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