Carbocupration of diethyl 1-alkynyl phosphonates: Stereo- and regioselective synthesis of 1,2,2-trisubstituted vinyl phosphonates

Full text of DOI:10.1021/jo982123w

2950
J . Org. Chem. 1999, 64, 2950-2953
Ta ble 1. P r ep a r a tion of Dieth yl 2,2-Disu bstitu ted Vin yl
Ca r bocu p r a tion of Dieth yl 1-Alk yn yl
P h osp h on a tes by th e Rea ction of 1-Alk yn ylp h osp h on a tes
P h osp h on a tes: Ster eo- a n d Regioselective
Syn th esis of 1,2,2-Tr isu bstitu ted Vin yl
P h osp h on a tes
w ith Cop p er (I) Rea gen ts (electr op h ile ) H+)
J un Mo Gil and Dong Young Oh*
Department of Chemistry, Korea Advanced of
Science and Technology, 373-1, Kusung-Dong,
Yusung-Gu, Taejon, 305-701
Received October 21, 1998
In tr od u ction
The synthesis of stereoselectively substituted alkenes
is one of the interesting topics in organic synthesis. The
chemistry of organocopper(I) reagents has especially
received a great deal of attention regarding cis-conjugate
addition reactions with acetylenic compounds.1 In the
case of addition to functionalized acetylenes, R,â-acet-
ylenic esters undergo a facile conjugate addition reaction
with lithium diorganocuprates,2 with cis addition taking
place exclusively. 1-Alkynyl sulfoxides and sulfones also
undergo cis-conjugate addition.3 In contrast, the reactions
of organocopper(I) reagents with a number of 1-alkynyl
phosphorus compounds have been observed in a few
cases.4 At the time this work was initiated, no addition
of organocopper(I) reagents to 1-alkynyl phosphonates
had been reported.
Vinyl phosphonates are interesting compounds owing
to their synthetic utility5 and biological activity.6 For the
preparation of the vinyl phosphonates, many reports are
found in the literature.5,7 In contrast, for the synthetic
methods of 2,2-dialkyl vinylic phosphonates, a few meth-
ods are known. One of these methods is the copper-
catalyzed Arbuzov reaction,8 having some limitations
with the preparation of starting compounds. Recently,
we have reported a new synthetic route for the stereo-
defined vinylic phosphonates via t-BuOK-induced cleav-
age of dihydrofuran derivatives.9 However, synthetic
a
b
Isolated yields. Other isomers were not detected in the GC
and NMR studies. c Another isomer (e) was detected as the major
product (3s/3a ) 0.67) at room temperature (1 h). No reaction at
d
room temperature.
Sch em e 1
* Corresponding author. Tel 82-42-869-2859. Fax 82-42-869-2810.
E-mail dyoh@cais.kaist.ac.kr.
(1) For reviews on organocopper(I) chemistry, see (a) Normant, J .
F. Synthesis 1972, 63. (b) Posner, G. H. Org. React. 1972, 19, 1. (c)
J ukes, A. E. Adv. Organomet. Chem. 1975, 12, 215. (d) Posner, G. H.
Org. React. 1978, 22, 253. (e) Normant, J . F.; Alexakis, A. Synthesis
1981, 841.
(2) (a) Corey, E. J .; Katzenellenbogen, J . A. J . Am. Chem. Soc. 1969,
91, 1851. (b) Siddall, J . B.; Biskup, M.; Fried, J . H. Ibid. 1969, 91,
1853. (c) Klein, J .; Turkel, R. M. Ibid. 1969, 91, 6189. (d) Klein, J .;
Aminadav, N. J . Chem. Soc. C 1970, 1380.
(3) (a) Vermeer, P.; Meijer, J .; Eylander, C. Recl. Trav. Chim. Pays-
Bas 1974, 93, 240. (b) Truce, W. E.; Lusch, M. J . J . Org. Chem. 1974,
39, 3174. (c) Truce, W. E.; Lusch, M. J . Ibid. 1978, 43, 2252. (d)
Fiandanese, V.; Marchese, G.; Naso, F. Tetrahedron Lett. 1978, 5131.
(e) Meijer, J .; Vermeer, P. Recl. Trav. Chim. Pays-Bas 1975, 94, 14.
(4) Aguiar, A. M.; Smiley Irelan, J . R. J . Org. Chem. 1969, 34, 4030.
(5) For reviews on vinylphosphonates and their synthetic applica-
tions, see Minami, T.; Motoyoshiya, J . Synthesis 1992, 333.
(6) (a) Engel, R. Chem. Rev. 1977, 77, 349. (b) Breaker. R. R.; Gough,
G. R.; Gilham, P. T. Biochemistry 1993, 32, 9125. (c) Harnden, M. R.;
Parkin, A.; Parratt, M. J .; Perkins, R. M. J . Med. Chem. 1993, 36, 1345.
(7) (a) Tavs, P.; Weitkamp, H. Tetrahedron 1970, 26, 5529. (b) Han,
L.-B.; Tanaka, M. J . Am. Chem. Soc. 1996, 118, 1571.
methods for stereocontrolled 1,2,2-trisubstituted vinylic
phosphonates appear to have never been reported.
Herein, we report a synthetic route (Scheme 1), results
(Table 1) for the preparation of vinylic phosphonates by
the additions of organocopper(I) reagents to 1-alkynyl
phosphonates (1).10 By subsequent capture of the inter-
(8) Axelrad, G.; Laosooksathit, S.; Engel, R. J . Org. Chem. 1981,
46, 5200.
(9) Lee, C.-W.; Hong, J . E.; Oh, D. Y. J . Org. Chem. 1995, 60, 7027.
(10) Gil, J . M.; Sung, J . W.; Park, C. P.; Oh, D. Y. Synth. Commun.
1997, 27, 3171.
10.1021/jo982123w CCC: $18.00 © 1999 American Chemical Society
Published on Web 03/30/1999

Notes
J . Org. Chem., Vol. 64, No. 8, 1999 2951
Ta ble 2. NMR Da ta Du e to th e Allylic Meth yl for Vin ylic
P h osp h on a tes (in CDCl3, p p m (δ) Dow n field r a n ge fr om
tetr a m eth ylsila n e a n d 31P cou p lin g con sta n ts (J ) r a n ge)
product at room temperature. When R was t-Bu, we
obtained the anti-addition products exclusively to our
surprise. In case of R ) t-Bu, R′ ) Et, the reaction time
was very long. When the reaction time was 1 h, the
quenched mixture includes the starting compound and
only the anti-product (j).
The structures of the 2,2-dialkyl vinylic phosphonates
were characterized by one- or two-dimensional NOE
techniques and HRMS. On the basis of these defined
structures, the 1H NMR absorption due to the allylic
methyl protons in the 2,2-dialkyl vinyl phosphonates
showed the lowest downfield peaks and larger phospho-
rus coupling constants when they were cis rather than
trans to the phosphonate group (Table 2).
Ta ble 3. P r ep a r a tion of Dieth yl 1,2,2-Tr isu bstitu ted
Vin yl P h osp h on a tes by th e Rea ction of
1-Hexyn ylp h osp h on a tes w ith Cop p er (I) Rea gen ts a n d
Sever a l Electr op h iles
The poor reactivity of Me2CuLi2I and Me2CuMgBr
toward alkylacetylenes is well-known,11 and so their
lower reactivity toward 1-alkynyl phosphonates required
longer times and higher reaction temperatures. Addition
took place even with a terminal acetylenic phosphonate
with no observable abstraction of the acetylenic proton
with the organocopper reagent (Et2CuMgBr). R′2CuLi2I
or R′2CuMgBr showed similar reactivity in the conversion
of 1-alkynyl phosphonates into vinyl phosphonates.
The R-phosphonyl vinylcopper(I) species (2) as 1-metal-
lic vinyl phosphonates are very important intermediates
because they react with a variety of eletrophiles to give
the vinyl phosphonate derivatives. These intermediates
react with several electrophiles having transmetalation
properties (I, Te, Se),12 and the R-phosphonyl vinylcopper-
(I) species (2) are fairly stable. Vinylcopper(I) species
usually dimerize rapidly above -10 °C,11 but solutions
of our adducts can be stirred at refluxing (THF) temper-
ature during several minutes without detectable dimer-
ization. Because of the pronounced thermal stability of
the intermediary adducts, the presence of stabilizing
agents such as trimethyl phosphite prior to the addition
of the electrophile is not required.
The R-functionalization of vinyl phosphonates was
performed by adding several electrophiles to the R-phos-
phonyl vinylcopper(I) intermediates at -78 °C followed
by warming to rt. After workup, the vinyl phosphonates
were obtained as indicated in Table 3. 1-Iodovinylphos-
phonates were obtained by treating the intermediary
adducts with iodine. When phenyltelluryl iodide, phen-
ylselenyl bromide, or trimethylsilyl chloride was added,
vinylic phosphonates substituted with an electron-
withdrawing group were formed, bearing a PhTe,13
PhSe,14 or Me3Si15 group in the R-position. In case of
PhSeBr, the 1-bromo-substituted vinylic phosphonate
was obtained in a considerable amount as a side product.
a
Stereoselectivity was retained from vinylic copper intermedi-
ates (Table 1). Isolated yields. c 1-Brominated vinylic phospho-
nate was obtained in a considerable amount as a side product.
b
mediate 1-phosphonyl-2,2-dialkyl vinylcopper compounds
(2) with several electrophiles, we obtained the 1,2,2-
trisubstituted vinylic phosphonates (3) having high regio-
and stereoselectivity in reasonably good yields (Table 3).
Resu lts a n d Discu ssion
Preliminary experiments involved the treatment of
diethyl 1-alkynyl phosphonates with copper(I) reagents
(1.5 equiv), followed by a protolysis with saturated
ammonium chloride solution (E ) H). As indicated in the
Table 1, the reaction proceeds well for copper(I) reagents
derived from copper iodide. In all cases attack of the alkyl
copper(I) reagents on diethyl 1-alkynyl phosphonates
occurred at the 2-position exclusively without side reac-
tions. The regioselectivity can be rationalized in terms
of a carbanion stabilization by the phosphonyl group.
In all reactions involving the possible formation of
geometrical isomers, the NMR spectra of the crude vinylic
phosphonates showed the stereospecific formation of
essentially only one isomer.
(11) (a) Normant, J . F.; Cahiez, G.; Bourgain, M.; Chuit, C.; Villieras,
J .Bull. Soc. Chim. Fr. 1974, 1656. (b) Westmijze, H.; Meijer, J .; Bos,
H. J . T.; Vermeer, P. Recl. Trav. Chim. Pays-Bas 1976, 95, 299, 304.
(c) Marfat, A.; McQuirk, P. R.; Helquist, P. J . Org. Chem. 1979, 44,
3888.
(12) (a) Neumann, H.; Seebach, D. Chem. Ber. 1978, 111, 2785. (b)
For reviews on vinylic selenides and telluridesspreparation, reactivity,
and their synthetic applications, see Comasseto, J . V.; Ling, L. W.;
Petragnani, N.; Stefani, H. A. Synthesis 1997, 373.
(13) Lee, C.-W.; Koh, Y. J .; Oh, D. Y. J . Chem. Soc., Perkin Trans.
1 1994, 717.
(14) (a) Comasseto, J . V.; Petragnani, N. J . Organomet. Chem. 1978,
152, 295. (b) Mikolajczyk, M.; Grzejszczak, S.; Korbacz, K. Tetrahedron
Lett. 1981, 22, 3097. (c) Khan, N.; Morris, T. H.; Smith, E. H.; Walsh,
R. J . Chem. Soc., Perkin Trans. 1 1991, 865. (d) Shin, W. S.; Lee, K.;
Oh, D. Y. Bull. Korean Chem. Soc. 1996, 17, 981.
It was found that the 1-alkynyl phosphonates undergo
a smooth, stereospecific cis-addition of copper(I) reagents
when R ) H, n-Bu, n-Hex, CH2OBn, Ph, but not t-Bu.
When R ) Ph, the product was only one isomer at -10
°C, but a mixture (e, h) with the anti adduct as the major
(15) (a) Ahlbrecht, H.; Farnung, W.; Simon, H. Chem. Ber. 1984,
117, 2622. (b) Binder, J .; Zbiral, E. Tetrahedron Lett. 1986, 27, 5829.
(c) Ager, D. Org. React. 1990, 38, 1-223.

2952 J . Org. Chem., Vol. 64, No. 8, 1999
Notes
128.59, 128.22, 126.17, 113.58 (d, J ) 188.625), 61.11 (d, J )
5.70), 32.13 (d, J ) 6.50), 30.69 (d, J ) 3.53), 22.42, 16.13 (d, J
) 2.48), 13.60.
Allylation and methylation were carried out with allyl
bromide and methyl iodide, respectively. However, in case
of the attempted acylation of R-phosphonyl vinylcopper-
(I) intermediates with acetyl chloride and benzoyl chlo-
ride, complications occurred because of the isomerization
of unstable vinylic phosphonates containing a strong
electron-withdrawing R-acyl group and 2,2-dialkyl groups.
Therefore, we could not prepare the corresponding R-acyl
vinylic phosphonates successfully.
In conclusion, the reaction of organocopper(I) reagents
with 1-alkynylphosphonates affords a rapid entry into a
variety of vinylic phosphonates with high regio- and
stereoselectivity and with high yields in a one-pot process.
1-Alkynyl phosphonates (1) are easily converted into
1-phosphonyl-2,2-dialkyl vinylcopper(I) intermediates (2)
by treatment with organocopper(I) reagents. The adducts
(2) react with a variety of electrophiles to give the vinyl
phosphonate derivatives (3) RR′CdC(E)PO3Et2 (E ) H,
I, Me, allyl, SePh, TePh, SiMe3). The stereochemistry of
the carbocupration of 1-alkynyl phosphonates with or-
ganocopper(I) reagents are observed as only syn-addition
(R ) H, n-Bu, n-Hex, CH2OBn, Ph) and unexpected anti-
addition in the case of R ) t-Bu.
(Z)-1-(Dieth yl p h osp h on a to)-2-m eth yl-1-octen e (f): 1H
NMR δ 5.17 (dd, 1H, J ) 19.06, 1.10), 3.61-3.91 (m, 4H), 2.29-
2.35 (m, 2H), 1.71 (s, 3H), 1.20-1.40 (m, 2H), 0.95-1.20 (m,
12H), 0.69 (t, 3H, J ) 6.46); 13C NMR δ 163.22 (d, J ) 7.58),
111.95 (d, J ) 188.33), 60.64 (d, J ) 4.05), 34.67 (d, J ) 6.6),
31.32, 28.92, 27.64 (d, J ) 1.88), 25.14 (d, J ) 24.6), 22.17, 15.96
(d, J ) 6.53), 13.63.
(Z)-1-(Dieth yl p h osp h on a to)-2-m eth yl-1-p r op en yl ben zyl
eth er (g): 1H NMR δ 7.24-7.32 (m, 5H), 5.51 (d, 1H, J ) 23.20),
4.46 (s, 2H), 4.45 (d, 2H, J ) 2.41), 3.96-4.06 (m, 4H), 1.98d,
3H, J ) 0.74), 1.25-1.29 (m, 6H); 13C NMR δ 158.29 (d, J )
21.53), 137.69, 128.10, 127.46, 127.37, 114.47 (d, J ) 186.08),
72.43, 69.82 (d, J ) 7.05), 61.30 (d, J ) 5.55), 23.17 (d, J ) 22.8),
16.30 (d, J ) 6.6).
(Z)-1-(Dieth yl p h osp h on a to)-2-p h en yl-1-h exen e (h ): 1H
NMR δ 7.24-7.33 (m, 5H), 5.68 (d, 1H, J ) 17.7), 3.69-3.86
(m, 4H), 2.46 (t, 2H, J ) 6.59), 1.20-1.45 (m, 4H), 1.04-1.08
(m, 6H), 0.61-0.66 (m, 3H); 13C NMR δ 163.31 (d, J ) 3.75),
139.67 (d, J ) 23.63), 127.78, 127.59, 127.33 (d, J ) 1.73), 113.77
(d, J ) 188.83), 61.09 (d, J ) 6.08), 41.11 (d, J ) 20.85), 29.51,
22.08, 16.02 (d, J ) 8.25), 13.75.
(E)-1-(Dieth yl p h osp h on a to)-2-(ter t-bu tyl)-1-p r op en e (i):
1H NMR δ 5.37 (dd, 1H, J ) 17.70, 0.71), 3.92-4.00 (m, 4H),
2.00 (dd, 3H, J ) 3.00, 0.67), 1.17-1.25 (m, 6H), 1.01 (s, 9H);
13C NMR δ 170.23 (d, J ) 4.88), 109.01 (d, J ) 187.50), 60.99
(d, J ) 5.63), 38.25 (d, J ) 20.03), 24.48, 16.36 (d, J ) 8.03),
16.20 (d, J ) 6.3).
(E)-1-(Dieth yl p h osp h on a to)-2-(ter t-bu tyl)-1-bu ten e (j):
1H NMR δ 5.36 (d, 1H, J ) 16.22), 3.93-4.01 (m, 4H), 2.48 (qd,
2H, J ) 7.47, 1.96), 1.20-1.27 (m, 6H), 1.09 (t, 3H, J ) 7.44),
1.05 (s, 9H); 13C NMR δ 176.17 (d, J ) 5.85), 108.76 (d, J )
187.65), 61.00 (d, J ) 5.78), 38.87 (d, J ) 20.55), 29.06, 23.47
(d, J ) 7.58), 16.24 (d, J ) 8.03) 15.73 (d, J ) 2.7).
(E)-1-(Dieth yl p h osp h on a to)-2-(ter t-bu tyl)-1-h exen e (k ):
1H NMR δ 5.27 (d, 1H, J ) 16.03), 3.83-3.93 (m, 4H), 2.29-
2.35 (m, 2H), 1.30-1.41 (m, 2H), 1.18-1.27 (m, 2H), 1.10-1.17
(m, 6H), 0.94 (s, 9H), 0.75 (t, 3H, J ) 7.25); 13C NMR δ 174.67
(d, J ) 5.85), 108.71 (d, J ) 188.18), 60.74 (d, J ) 5.78), 38.61
(d, J ) 20.63), 33.31 (d, J ) 2.40), 30.47 (d, J ) 7.35), 28.92,
23.27, 16.06 (d, J ) 6.38), 13.51.
Syn th esis of Dieth yl 1,2,2-Tr isu bstitu ted Vin ylp h osp h o-
n a tes (a ′-g′). Gen er a l P r oced u r e. Diethyl 1-hexynylphos-
phonates (1 mmol) in THF (3 mL) were added to the organo-
copper(I) reagents (1.5 equiv) at -78 °C, and the reaction
mixtures were allowed to warm at room temperature for several
hours (Table 1). The reaction mixtures were then cooled to -78
°C and several electrophiles (in the cases of a ′, d ′, iodine (2 mmol,
0.508 g, in THF (6 mL)); in the case of b′, phenyl selenyl bromide
(2 mmol, 0.470 g, in THF (4 mL)); in the case of c′, phenyltelluryl
iodide (2 mmol) (prepared by reaction of diphenyl ditelluride (1.0
mmol, 0.410 g) with iodine (1.0 mmol, 0.254 g) in THF (5 mL)
for 1 h at rt); in the case of e′, trimethylsilyl chloride (2 mmol,
0.220 g, in THF (3 mL)); in the case of f′, methyl iodide (2 mmol,
0.13 mL, neat); in the case of g′, allyl bromide (2 mmol, 0.242 g
in THF (3 mL))) were added dropwise. The reaction mixtures
were allowed to warm to rt and were stirred for several minutes
(Table 2) before quenching with saturated NH4Cl (aq), and the
products (colorless oil) were isolated by extraction with diethyl
ether, drying (MgSO4), evaporation, and silica gel chromatog-
raphy (in the cases of a ′, b′, c′, d ′, EtOAc:hexane ) 1: 4; in the
cases of e′, f ′, g′, EtOAc:hexane ) 1:1), respectively.
(E)-1-(Diet h yl p h osp h on a t o)-1-iod o-2-m et h yl-1-h exen e
(a ′): 1H NMR δ 3.95-4.02 (m, 4H), 2.74 (td, 2H, J ) 7.33, 1.83),
2.04 (t, 3H, J ) 1.67), 1.30-1.40 (m, 4H), 1.21-1.28 (m, 6H),
0.80 (t, 3H, J ) 7.22); 13C NMR δ 166.23 (d, J ) 13.8), 85.17 (d,
J ) 194.1), 62.18 (d, J ) 5.40), 38.63 (d, J ) 4.65), 32.80 (d, J )
16.13), 30.71 (d, J ) 1.65), 22.38, 16.01 (d, J ) 6.75), 13.69;
HRMS exact mass calcd for C11H22IO3P (M+): 360.0351, found:
360.0339.
(E)-1-(Dieth yl p h osp h on a to)-1-p h en ylselen yl-2-m eth yl-
1-h exen e (b′): 1H NMR δ 7.11-7.31 (m, 5H), 3.92-4.06 (m, 4H),
2.82 (td, 2H, J ) 7.50, 1.83), 2.12 (d, 3H, J ) 2.14), 1.45-1.51
(m, 2H), 1.33-1.40 (m, 2H), 1.15-1.20 (m, 6H), 0.90 (t, 3H, J )
7.22); 13C NMR δ 170.76 (d, J ) 16.5), 132.62, 129.37, 128.92,
Exp er im en ta l Section
Gen er a l. All reactions were conducted under an atmosphere
of nitrogen in oven-dried glassware with magnetic stirring. THF
1
was distilled from Na/benzophenone ketyl. H-, 13C-, and NOE-
NMR spectra were recorded at 300 MHz in CDCl3, using TMS
or residual CHCl3 as internal references.
Syn th esis of Dieth yl 2,2-Dia lk yl Vin ylic P h osp h on a tes
(a -k ). Gen er a l P r oced u r e. Diethyl 1-alkynylphosphonates
(1)10 (1 mmol) in THF (3 mL) were added to the organocopper(I)
reagents1 (1.5 equiv) at -78 °C. The reaction mixtures were
allowed to warm at -10 °C, room temperature, or refluxing
(THF) temperature during several hours (Table 1), followed by
protolysis with saturated aqueous NH4Cl, and the products
(colorless oil) were isolated by extraction with diethyl ether,
drying (MgSO4), concentration, and silica gel chromatography
(EtOAc:hexane ) 1:1), respectively.
(E)-1-(Dieth yl p h osp h on a to)-1-p r op en e (a ): 1H NMR δ
6.67-6.84 (m, 1H), 5.49-5.63 (m, 1H), 3.93-4.04 (m, 4H), 2.11-
2.20 (m, 2H), 1.22-1.30 (m, 6H), 0.95-1.03 (m, 3H); 13C NMR δ
154.936 (d, J ) 4.5), 115.61(d, J ) 187.35), 61.413 (d, J ) 5.55),
26.93 (d, J ) 22.2), 16.22 (d, J ) 6.30), 11.71.
(Z)-1-(Dieth yl p h osp h on a to)-2-m eth yl-1-h exen e (b): 1H
NMR δ 5.29 (d, 1H, J ) 18.88), 3.93-4.03 (m, 4H), 2.40-2.43
(m, 2H), 1.63 (s, 3H), 1.30-1.40 (m, 4H), 1.21-1.28 (m, 6H), 0.85
(t, 3H, J ) 7.31); 13C NMR δ 163.63 (d, J ) 7.43), 122.12 (d, J
) 188.175), 61.00 (d, J ) 5.55), 34.72 (d, J ) 6.68), 30.25 (d, J
) 1.8), 25.44 (d, J ) 24.6), 22.62, 16.24 (d, J ) 6.6), 13.82; HRMS
exact mass calcd for C11H23O3P (M+): 234.1384, found: 234.1392.
(Z)-1-(Dieth yl ph osph on ato)-2-eth yl-1-h exen e (c): 1H NMR
δ 5.18 (d, 1H, J ) 18.28), 3.85-3.95 (m, 4H), 2.33-2.38 (m, 2H),
2.04 (q, 2H, J ) 7.37), 1.22-1.30 (m, 4H), 1.14-1.22 (m, 6H),
0.90 (t, 3H, J ) 6.78), 0.76 (t, 3H, J ) 7.08); 13C NMR δ 163.56
(d, J ) 6.90), 109.62 (d, J ) 189.075), 60.78 (d, J ) 5.55), 33.46
(d, J ) 7.05), 30.64 (d, J ) 7.05), 30.48 (d, J ) 2.55), 22.60, 16.06
(d, J ) 6.45), 13.62, 11.63; HRMS exact mass calcd for C12H25O3P
(M+): 248.1541, found: 248.1550.
1-(Dieth yl p h osp h on a to)-2-(n -bu tyl)-1-h exen e (d ): 1H
NMR δ 5.18 (d, 1H, J ) 18.64), 3.85-3.94 (m, 4H), 2.31-2.37
(m, 2H), 2.00 (t, 2H, J ) 7.08), 1.20-1.32 (m, 8H), 1.13-1.18
(m, 6H), 0.73-0.78 (m, 6H); 13C NMR δ 167.29 (d, J ) 6.75),
110.65 (d, J ) 188.25), 60.75 (d, J ) 5.55), 37.59 (d, J ) 22.28),
33.24 (d, J ) 7.05), 30.46 (d, J ) 1.88), 29.44, 22.59, 22.05, 16.05
(d, J ) 6.45), 13.81, 11.56; HRMS Exact mass calcd for
C
14H29O3P (M+): 276.1854, found: 276.1877.
(E)-1-(Dieth yl p h osp h on a to)-2-p h en yl-1-h exen e (e): 1H
NMR δ 7.22-7.31 (m, 5H), 5.65 (d, 1H, J ) 17.15), 3.97-4.10
(m, 4H), 2.85-2.95 (m, 2H), 1.20-1.28 (m, 10H), 0.75-0.80 (m,
3H); 13C NMR δ 163.52 (d, J ) 8.63), 140.90 (d, J ) 23.63),

Notes
J . Org. Chem., Vol. 64, No. 8, 1999 2953
125.95, 113.60 (d, J ) 191.93), 62.07 (d, J ) 6.00), 37.52 (d, J )
5.78), 31.16 (d, J ) 1.65), 26.31 (d, J ) 16.43), 22.78, 16.14 (d,
23.03, 22.96, 16.24 (d, J ) 6.68), 13.91, 13.90, 2.31 (d, J ) 2.18);
HRMS exact mass calcd for
found: 348.2217.
C
17H37O3PSi (M+): 348.2250,
J
) 6.75), 13.86; HRMS exact mass calcd for C17H27O3PSe
(M+): 390.0863, found: 390.0820.
(E)-1-(Dieth yl p h osp h on a to)-1-m eth yl-2-(p h en yl)-1-h ex-
en e (f′): 1H NMR δ 7.23-7.33 (m, 3H), 7.01-7.043 (m, 2H),
4.05-4.12 (m, 4H), 2.79-2.83 (m, 2H), 2.62 (d, 3H, J ) 13.71),
1.29-1.32 (m, 6H), 1.20-1.26 (m, 4H), 0.78 (t, 3H, J ) 6.67);
13C NMR δ 168.58 (d, J ) 12.45), 142.03 (d, J ) 22.43), 128.12,
127.32 (d, J ) 0.98), 126.93, 120.37 (d, J ) 175.13), 61.20 (d, J
) 5.70), 36.46 (d, J ) 6.75), 30.34 (d, J ) 1.95), 22.66, 18.20 (d,
J ) 11.40), 16.31 (d, J ) 6.30), 13.83.
(Z)-1-(Dieth yl p h osp h on a to)-1-a llyl-2-(eth yl)-1-h exen e
(g′): 1H NMR δ 5.65-5.80 (m, 1H), 4.91-5.01 (m, 1H), 3.90-
4.00 (m, 4H), 2.95 (dd, 2H, J ) 17.52 J ) 5.80), 2.45-2.50 (m,
2H), 2.11 (qd, 2H, J ) 7.46, 0.77), 1.28-1.40 (m, 4H), 1.21-
1.26 (m, 6H), 0.96 (t, 3H, J ) 7.35), 0.86 (t, 3H, J ) 7.07); 13C
NMR δ 162.56 (d, J ) 11.18), 136.23 (d, J ) 1.65), 120.08 (d, J
) 177.00), 114.81, 61.00 (d, J ) 5.555), 33.78, 33.65 (d, J ) 3.53),
31.24 (d, J ) 2.25), 25.87 (d, J ) 19.13), 23.04, 16.22 (d, J )
6.53), 13.89, 12.61 (d, J ) 2.55); HRMS exact mass calcd for
C15H29O3P (M+): 288.1854, found: 288.1831.
(E)-1-(Dieth yl p h osp h on a to)-1-p h en yltellu r yl-2-m eth yl-
1-h exen e (c′): 1H NMR δ 7.55-7.58 (m, 2H), 7.14-7.17 (m, 3H),
3.98-4.07 (m, 4H), 2.85 (td, 2H, J ) 7.44, 1.90), 2.15 (d, 3H, J
) 1.79), 1.40-1.44 (m, 2H), 1.29-1.36 (m, 2H), 1.21-1.26 (m,
6H), 0.88 (t, 3H, J ) 7.26); 13C NMR δ 171.82 (d, J ) 11.1),
136.00, 129.22, 127.18, 116.61, 103.09 (d, J ) 176.63), 62.06 (d,
J ) 5.93), 37.56 (d, J ) 7.28), 32.13 (d, J ) 19.58), 31.37 (d, J )
1.58), 22.77, 16.27 (d, J ) 6.6), 13.88; HRMS exact mass calcd
for C17H27O3PTe (M+): 440.0760, found: 440.0705.
(E)-1-(Dieth yl ph osph on ato)-1-iodo-2-eth yl-1-h exen e (d ′):
1H NMR δ 3.89-4.00 (m, 4H), 2.68 (td, 2H, J ) 7.34, 1.75), 2.34
(q, 2H, J ) 7.51), 1.23-1.35 (m, 4H), 1.18-1.20 (m, 6H), 0.92 (t,
3H, J ) 7.49), 0.77 (t, 3H, J ) 7.18); 13C NMR δ 170.67 (d, J )
12.53), 84.22 (d, J ) 192.98), 62.09 (d, J ) 5.33), 37.95 (d, J )
15.68), 33.95 (d, J ) 4.65), 31.14 (d, J ) 1.73), 22.51, 15.92 (d,
J ) 6.53), 13.57, 11.22 (d, J ) 2.33); HRMS exact mass calcd
for C12H24IO3P (M+): 374.0508, found: 374.0524.
1-(Dieth yl p h osp h on a to)-1-tr im eth ylsilyl-2-(n -bu tyl)-1-
h exen e (e′): 1H NMR δ 3.89-3.96 (m, 4H), 2.63-2.65 (m, 2H),
2.22 (t, 2H, J ) 6.92), 1.25-1.40 (m, 8H), 1.20-1.24 (m, 6H),
0.82-0.88 (m, 6H), 0.16 (t, 9H, J ) 0.83); 13C NMR δ 177.75,
122.85 (d, J ) 147.38), 60.38 (d, J ) 5.7), 38.63 (d, J ) 28.05),
36.06 (d, J ) 10.95), 32.22 (d, J ) 2.10), 31.53 (d, J ) 1.65),
Su p p or tin g In for m a tion Ava ila ble: 1H NMR, 13C NMR,
HRMS, NOE spectra of compounds a -k , a ′-g′. This material
is available free of charge via the Internet at http://pubs.acs.org.
J O982123W