Bifunctionalized allenes, VII: Two methods for one-pot synthesis of sulfonyl-functionalized allenecarboxylates and phosphorylated allenes

Article abstract of DOI:10.1080/00397910600639042

Two new approaches to the synthesis of sulfonyl-functionalized allenecarboxylates and phosphorylated allenes are described. 2-Sulfonyl-alka-2,3-dienoates were readily prepared in an one-pot reaction by [2,3]-sigmatropic rearrangement of sulfinato-substitu

Full text of DOI:10.1080/00397910600639042

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Bifunctionalized Allenes, VII: Two
Methods for One‐Pot Synthesis of
Sulfonyl‐Functionalized Allenecarboxylates
and Phosphorylated Allenes
Dr Valerij C. Christov a & Jordanka G. Ivanova a
a Department of Chemistry , University of Shumen , Shumen, Bulgaria
Published online: 16 Feb 2007.
To cite this article: Dr Valerij C. Christov & Jordanka G. Ivanova (2006) Bifunctionalized Allenes, VII: Two
Methods for One‐Pot Synthesis of Sulfonyl‐Functionalized Allenecarboxylates and Phosphorylated Allenes,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
36:15, 2231-2244, DOI: 10.1080/00397910600639042
To link to this article: http://dx.doi.org/10.1080/00397910600639042
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Synthetic Communicationsw, 36: 2231–2244, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600639042
Bifunctionalized Allenes, VII: Two Methods
for One-Pot Synthesis of Sulfonyl-
Functionalized Allenecarboxylates and
Phosphorylated Allenes
Valerij C. Christov and Jordanka G. Ivanova
Department of Chemistry, University of Shumen, Shumen, Bulgaria
Abstract: Two new approaches to the synthesis of sulfonyl-functionalized allenecar-
boxylates and phosphorylated allenes are described. 2-Sulfonyl-alka-2,3-dienoates
were readily prepared in an one-pot reaction by [2,3]-sigmatropic rearrangement of
sulfinato-substituted 2-alkynoates, in situ generated from ethyl propynoate and sub-
sequent treatment with lithium diisopropyl (LDA), ketone, trimethylchlorosilane
(TMSCl), and the corresponding sulfinyl chlorides. Preparation of 1-sulfonyl-
alka-1,2-dienephosphonates and -1,2-dienyl phosphine oxides consists of the
reaction of the lithio compounds, in situ generated from phosphorylated allenes and
LDA, with the corresponding sulfonyl chlorides.
Keywords: [2,3]-Sigmatropic rearrangement, 1-sulfonyl-alka-1,2-dienephosphonates,
1-sulfonyl-alka-1,2-dienyl phosphine oxides, 2-sulfonyl-alka-2,3-dienoates, synthesis
Allenes are attractive starting points for synthesis, in large part because of the
high reactivity engendered by strain. In the past three decades, synthesis and
use[1] of allene derivatives have been expanded in preparative organic
chemistry.[2] An impressive number of heterocyclic systems has been
prepared from allenic starting materials. The electrophilic cyclization[3] of a
variety of monofunctionalized allenes such as alcohols,[4] carboxylic acids
and their esters,[5] sulfoxides,[6a] sulfinates,[6b] sulfones,[6b–d] phosphonates,[7]
phosphinates,[7] and phosphine oxides[6] to heterocyclic systems has received
Received in the UK October 7, 2005
Address correspondence to Dr. Valerij C. Christov, Department of Chemistry,
University of Shumen, 115, Universitetska str., Shumen BG-9700, Bulgaria.
Fax: þ359-54-830 371; E-mail: vchristo@shu-bg.net
2231

2232
V. C. Christov and J. G. Ivanova
considerable attention because of its synthetic utility and remarkable
stereoselectivity.[3d,4,5b,5f,6c,6d,7]
Reaction of propargyl alcohols with halogen-containing reagents such as
sulfenyl halides[8] and sulfinyl chlorides[9] is a convenient method for prep-
aration of propargyl compounds (sulfenates or sulfinates), which usually
undergo [2,3]-sigmatropic rearangement to allenic products[8–11] (sulfoxides
or sulfones). Synthesis of alkyl 2,3-alkadienoates by the Wittig reaction[12]
and by other methods have been reviewed.[13] The synthesis of a-thioallene-
carboxylates by metallation of an allene sulfide, followed by treatment with
methyl chloroformate, was mentioned by H. G. Viehe[14a] without the exper-
imental datails. An alternative route that enables the preparation of thio-,[14b]
sulfinyl-,[14b,14c] and sulfonyl-substituted[14b] allenecarboxylates starts from
methyl 4-hydroxy-2-alkynoate.
On the other hand, a most important aspect for applications of 1-acceptor-
substituted allenes is the relatively high acidity of the hydrogen atom at C-1
atom, for examples, 1-alkoxyallenes,[15] a-allenic esters,[16] 1-allenyl
sulfide,[17a] sulfoxides,[17b] sulfineamides,[17c] and sulfone.[17d] The literature
data show that the proton at the C-1 atom from the allenic system is easy dis-
placeable with different electrophilic reagents. For example, a-metallation of
an allenyl phosphine oxide (introduction of deuterium in the a-position) has
been observed.[18a] Application of allenic phosphonates to the synthesis of
structurally interesting molecules was made by R. S. Macomber,[18b–d] as
shown in the construction of bicyclic cumulatriene as an elegant example.[18e]
As a part of our research program on the chemistry of the heteroatom-
functionalized polyenes, we required convenient methods to introduce
sulfonyl and phosphoryl groups in the a-position to the ester group of allene-
carboxylates. The previously mentioned groups attract increasing attention as
useful functionalities in organic synthesis. Of particular interest are the appli-
cations of these groups as temporary transformers of chemical reactivity of the
allenic system in the synthesis of eventually heterocyclic compounds.
In a continuation of our previous reports on the synthesis[19a,19b] and elec-
trophile-induced cyclization reactions[19c–f] of bifunctionalized allenes, we
have found two efficient methods for synthesis of 2-sulfonyl-alka-2,3-
dienoates as well as 1-sulfonyl-alka-1,2-dienephosphonates and 1,2-dienyl
phosphine oxides.
The first method for one-pot preparation[19b] of ethyl 2-sulfonyl-allene-
carboxylates 3a–c consists of the following cascade steps. Reaction of the
lithio compounds A, generated in situ from ethyl propynoate 1 and LDA,
with acetone or cyclohexanone and subsequent treatment with TMSCl and
after that with methane- or trichloromethanesulfinyl chloride, gives ethoxy-
carbonyl-substituted propargyl sulfinates 2a–c. These are surprisingly stable
and were isolated in 70–73% yield. Reflux of sulfinates 2a–c (which may
be or not be isolated) in toluene provokes a [2,3]-sigmatropic rearangement
to the expected 2-sulfonyl-2,3-alkadienoates 3a–c, according to the reaction
sequence outlined in Scheme 1 and Table 1.

Bifunctionalized Allenes VII
2233
Scheme 1. Synthesis of 2-sulfonyl-substituted allenecarboxylates. Reagents and
conditions: a) LDA, THF, 21008C, 1 h; b) R1R2C55O [R1 ¼ R2 ¼ Me,
R1 þ R2 ¼ 22(CH2)522], THF, 21008C, 10 min; c) TMSCl, THF, 2100 to 2108C,
10 min; d) RS(O)Cl (R ¼ Me, CCl3), THF, 2108C to rt, 1 h; e) toluene, reflux, 3 h.
The starting materials in the synthesis of 1-sulfonyl-functionalized alka-
1,2-dienephosphonates 6a–f and 1,2-dienyl phosphine oxides 7a–d are the
phosphorylated allenes 5a–d. They are readily available by the reaction[20]
of the appropriate alkynols 4a, b with diethyl chlorophosphite or diphenyl
chlorophosphine in the presence of triethyl amine. In this case, in situ
generated alkynyl derivatives B cannot be isolated but rather undergo spon-
taneous [2,3]-sigmatropic rearrangement in the presence of 3 mol% hydro-
chloric acid to the desired allenephosphonates or allenyl phosphine oxides
5a–d (Scheme 2, Table 2).
We found that the phosphorylated allenes 5a–d can smoothly be depro-
tonated at the a-position by LDA in THF under an argon atmosphere. The in
situ resulting lithio compounds C can react with methane-, trichloromethane-,
or trimethylsilyloxy-sulfonyl chlorides, leading to 1-sulfonyl-substituted alle-
nephosphonates 6a–f and allenyl phosphine oxides 7a–d according to the
reaction sequence showed in Scheme 3 and Table 3.
In summary, two convenient and efficient methods for synthesis of a new
family of 1,1-diacceptor-substituted allenes have been described. Further
studies on these potentially important synthetic methodologies are currently
in progress. At the same time, the synthetic application of the prepared
2-sulfonyl-functionalized allenecarboxylates and 1-sulfonyl-functionalized
Table 1. Synthesis of 4-sulfinato-substituted 2-alkynoates 2a–c and 2-sulfonyl-
substituted allenecarboxylates 3a–c according to Scheme 1
Yielda
(%)
Yielda,b
(%)
Entry
R
R1
R2
Alkyne
Allene
1
2
3
Me
Me
Me
Me
2a
2b
2c
73
70
72
3a
3a
3a
49
45
47
22(CH2)522
Me
CCl3
Me
aIsolated yields by chromatographical purification on silica gel.
bOverall yields without isolation of the alkyne.

2234
V. C. Christov and J. G. Ivanova
Scheme 2. Synthesis of phosphorylated allenes. Reagents and conditions: a) Y2PCl
(Y55MeO, Ph), Et3N, ether, 2128C; b) 3 mol % HCl, ether, 2128C to rt, 3–6 h.
allenephosphonates and allenyl phosphine oxides for preparation of different
heterocyclic compounds is now under investigation as a part of our general
synthetic strategy for investigation of the score and limitations of the electro-
philic cyclization reactions of bifunctionalized allenes. Results of these
investigations will be reported in due course.
EXPERIMENTAL
Method of Analysis
1H and 13C NMR spectra were obtained on a Brucker DRX-250 spectrometer
for solutions in CDCl3. Chemical shifts are in parts per million downfield from
internal TMS. IR spectra were recorded with an IR-72 spectrophotometer
(Carl Zeiss, Jena). Elemental analyses were carried out by the University of
Shumen Microanalytical Service Laboratory. The melting points were
measured in open capillary tubes and are uncorrected. The solvents were
purified by standard methods. Reactions were carried out in oven-dried
glassware under an argon atmosphere and exclusion of moisture. All
compounds were checked for their purity on TLC plates.
Starting Materials
The details of the preparation of the starting dimethyl 3-methyl-buta-1,2-di-
enylphosphonate (5a), dimethyl 2-cyclohexylidene-ethenylphosphonate
Table 2. Synthesis of phosphorylated allenes 5a–d according to
Scheme 2
Entry
Allene
Y
R1
R2
Yielda (%)
1
2
3
4
5a
5b
5c
5d
MeO
MeO
Ph
Me
Me
86
84
75
79
22(CH2)522
Me
Me
Ph
22(CH2)522
aIsolated yields by distillation in vacuo or crystallization.

Bifunctionalized Allenes VII
2235
Scheme 3. Synthesis of 1-sulfonyl-substituted phosphorylated allenes. Reagents and
conditions: a) LDA, THF, 2788C, 1 h; b) RSO2Cl (R ¼ Me, CCl3, TMSO), THF,
2788C to rt, 1 h.
(5b), diphenyl (3-methyl-buta-1,2-dienyl) phosphine oxide (5c), and diphenyl
(2-cyclohexylidene-ethenyl) phosphine oxide (5d) have been described in
earlier articles.[20]
Synthesis of Ethoxycarbonyl-Substituted Propargyl Sulfinates
2a–c; General Procedure
To a solution of LDA, generated in situ from diisopropylamine (1.11 g,
11 mmol) and n-BuLi (1.6 M in hexane, 6.25 mL, 10 mmol), in THF
(20 mL), was added dropwise a solution of ethyl propynoate 1 (0.98 g,
10 mmol) in THF (10 mL) at 21008C. The reaction mixture was stirred at
this temperature for 1 h. After the addition of a solution of acetone (0.58 g,
10 mmol) (for preparation of 2a and 2c) or cyclohexanone (0.98 g,
10 mmol) (for preparation of 2b) in THF (10 mL) at 21008C, the mixture
was stirred at the same temperature for 10 min. TMSCl (1.09 g, 10 mmol) in
THF (10 mL) was added dropwise at 21008C. After the addition was
completed, the mixture was warmed to 2108C and stirred at the same
Table 3. Synthesis of 1-sulfonyl-substituted phosphorylated allenes 6a–f and 7a–d
according to Scheme 3
Entry
Allene
Y
R
R1
R2
Yielda (%)
1
2
6a
6b
6c
6d
6e
6f
MeO
MeO
MeO
Ph
Me
Me
Me
Me
53
55
51
49
51
54
50
55
48
52
22(CH2)522
Me
Me
3
CCl3
Me
Me
Me
4
5
Ph
Ph
Me
CCl3
22(CH2)522
Me
Me
6
Me
Me
7
7a
7b
7c
7d
MeO
MeO
Ph
TMSO
TMSO
TMSO
TMSO
8
22(CH2)522
Me
9
10
Me
Ph
22(CH2)522
aIsolated yield by chromatographical purification on silica gel.

2236
V. C. Christov and J. G. Ivanova
temperature for an additional 10 min. After that, a solution of methanesulfinyl
chloride (0.99 g, 10 mmol) (for preparation of 2a and 2b) or trichloromethane-
sulfinyl chloride (2.02 g, 10 mmol) (for preparation of 2c) in THF (20 mL)
was added dropwise to the reaction mixture at 2108C. The mixture was
stirred at rt for 1 h, quenched with 2 N HCl, extracted with Et2O or EtOAc,
washed with sat. NaCl, and dried over anhydrous Na2SO4. After evaporation
of the solvent, the residue was chromatographied on a column (silica gel,
Kieselgel Merck 60 F254) using a mixture of EtOAc and hexane (1:4) as an
eluent to give the pure propargyl sufinates 2a–c.
Data
Ethyl 4-methanesulfinyloxy-4-methyl-pent-2-ynoate (2a). Yield: 1.59 g
1
(7.28 mmol; 73%); light yellow oil. H NMR (CDCl3, 250 MHz): d ¼ 1.28
(t, 3H, J ¼ 7.1 Hz, MeCH2O), 1.64 (s, 6H, 2Me), 3.12 (s, 3H, MeSO2), 4.34
(m, 2H, MeCH2O). 13C NMR (CDCl3, 50 MHz): d ¼ 13.0 (CH3), 30.7
(CH3), 43.9 (CH3), 63.2 (C), 64.3 (CH2), 82.1 (C), 88.4 (C), 152.8 (C). IR
;;
;;
(film): 1137 (S55O); 1706 (C55O), 2243 (C C); 3286 (HC ). Anal.
calcd. for C9H14O4S (218.27): C, 49.52; H, 6.46; S, 14.69. Found: C, 49.60;
H, 6.43; S, 14.65.
Ethyl 1-methanesulfinyloxy-cyclohexyl-prop-2-ynoate (2b). Yield: 1.81 g
(7.01 mmol; 70%); light yellow solid; mp 83–848C. 1H NMR (CDCl3,
250 MHz): d ¼ 1.18–2.03 (m, 10H, cyclohexyl), 1.32 (t, 3H, J ¼ 7.0 Hz,
MeCH2O), 3.14 (s, 3H, MeSO2), 4.28 (m, 2H, MeCH2O). 13C NMR
(CDCl3, 50 MHz): d ¼ 13.2 (CH3), 23.1 (CH2), 26.3 (CH2), 40.5 (CH2),
44.4 (CH3), 62.2 (CH2), 66.3 (C), 82.5 (C), 91.4 (C), 153.3 (C). IR (nujol):
;;
;;
1142 (S55O); 1712 (C55O), 2250 (C C); 3292 (HC ). Anal. calcd. for
C12H18O4S (258.34): C, 55.79; H, 7.02; S, 12.41. Found: C, 55.68; H, 6.95;
S, 12.49.
Ethyl 4-methyl-4-trichloromethanesulfinyloxy-pent-2-ynoate (2c). Yield:
2.34 g (7.28 mmol; 72%); light yellow oil. 1H NMR (CDCl3, 250 MHz):
d ¼ 1.29 (t, 3H, J ¼ 7.0 Hz, MeCH2O), 1.65 (s, 6H, 2Me), 4.27 (m, 2H,
MeCH2O). 13C NMR (CDCl3, 50 MHz): d ¼ 14.1 (CH3), 28.4 (CH3), 62.5
(C), 64.3 (CH2), 81.6 (C), 94.41 (C), 129.6 (C), 154.2 (C). IR (film): 1140
;;
;;
(S55O); 1708 (C55O), 2240 (C C); 3287 (HC ). Anal. calcd. for
C9H11Cl3O4S (321.61): C, 33.61; H, 3.45; Cl, 33.07; S, 9.97. Found: C,
33.68; H, 3.38; Cl, 33.14; S, 10.04.
Synthesis of 2-Sulfonyl-Substituted Allenecarboxylates 3a–c;
General Procedure
A solution of ethoxycarbonyl-substituted prorargyl sulfinate 2 in dried toluene
(10 mL) was refluxed for 1 h. After evaporation of the solvent, the crude
product was purified by column chromatography on silica gel (Kieselgel

Bifunctionalized Allenes VII
2237
Merck 60 F254) (eluent: EtOAc–heptane, 1:5) to yield the corresponding
2-sulfonyl-substituted allenecarboxylates 3a–c.
Data
Ethyl 2-methanesulfonyl-4-methyl-penta-2,3-dienoate (3a). According to
the general procedure, propargyl sufinate 2a (1.59 g, 7.28 mmol) was
converted by [2,3]-sigmatropic rearrangement into the allenecarboxylate 3a.
Yield: 0.779 g (3.57 mmol; 49%); light yellow oil. 1H NMR (CDCl3,
250 MHz): d ¼ 1.39 (t, 3H, J ¼ 7.1 Hz, MeCH2O), 1.69 (s, 6H, 2Me), 3.00
(s, 3H, MeSO2), 4.30 (m, 2H, MeCH2O). 13C NMR (CDCl3, 50 MHz):
d ¼ 13.9 (CH3), 22.1 (CH3), 41.2 (CH3), 61.3 (CH2), 95.3 (C), 103.4 (C),
158.4 (C), 204.3 (C). IR (film): 1127, 1341 (SO2); 1706 (C55O), 1958
(C55C55C). Anal. calcd. for C9H14O4S (218.27): C, 49.52; H, 6.46;
S, 14.69. Found: C, 49.58; H, 6.54; S, 14.81.
Ethyl 3-cyclohexylidene-2-methanesulfonyl-acrylate (3b). According to the
general procedure, propargyl sufinate 2b (1.81 g, 7.01 mmol) was converted
by [2,3]-sigmatropic rearrangement into the allenecarboxylate 3b. Yield:
1
0.815 g (3.15 mmol; 45%); light yellow crystals; mp 71–738C. H NMR
(CDCl3, 250 MHz): d ¼ 1.37 (t, 3H, J ¼ 6.9 Hz, MeCH2O), 1.50–2.20
(m, 10H, cyclohexylidene), 3.18 (s, 3H, MeSO2), 3.74–4.18 (m, 2H,
MeCH2O). 13C NMR (CDCl3, 50 MHz): d ¼ 14.5 (CH3), 24.1 (CH2), 26.7
(CH2), 33.5 (CH2), 39.4 (CH3), 61.9 (CH2), 94.8 (C), 104.4 (C), 163.5 (C),
203.7 (C). IR (nujol): 1148, 1350 (SO2); 1711 (C55O), 1960 (C55C55C).
Anal. calcd. for C12H18O4S (258.34): C, 55.79; H, 7.02; S, 12.41. Found: C,
55.86; H, 7.15; S, 12.47.
Ethyl 4-methyl-2-trichloromethanesulfonyl-penta-2,3-dienoate (3c).
According to the general procedure, propargyl sufinate 2c (2.34 g,
7.28 mmol) was converted by [2,3]-sigmatropic rearrangement into the allene-
carboxylate 3c. Yield: 1.10 g (3.42 mmol; 47%); light yellow crystals; mp 91–
1
928C. H NMR (CDCl3, 250 MHz): d ¼ 1.34 (t, 3H, J ¼ 6.7 Hz, MeCH2O),
1.94 (s, 6H, 2Me), 3.68–4.29 (m, 2H, MeCH2O). 13C NMR (CDCl3,
50 MHz): d ¼ 14.4 (CH3), 21.4 (CH3), 61.8 (CH2), 95.7 (C), 103.2 (C),
110.8 (C), 157.0 (C), 204.3 (C). IR (nujol): 1146, 1345 (SO2); 1720
(C55O), 1956 (C55C55C). Anal. calcd. for C9H11Cl3O4S (321.61): C, 33.61;
H, 3.45; Cl, 33.07, S, 9.97. Found: C, 33.74; H, 3.39; Cl, 32.94; S, 10.06.
Synthesis of 1-Sulfonyl-Substituted Phosphorylated Allenes 6a–f,
7a–d; General Procedure
To a solution of LDA, generated in situ from diisopropylamine (1.11 g,
11 mmol) and n-BuLi (1.6 M in hexane, 6.25 mL, 10 mmol) in THF (20 ml),
was added dropwise
a
solution of dimethyl 3-methyl-buta-1,2-

2238
V. C. Christov and J. G. Ivanova
dienylphosphonate 5a (1.76 g, 10 mmol) (for preparation of 6a, 6c, and 7a),
dimethyl 2-cyclohexylidene-ethenylphosphonate 5b (2.16 g, 10 mmol) (for
preparation of 6b and 7b), diphenyl (3-methyl-buta-1,2-dienyl) phosphine
oxide 5c (2.68 g, 10 mmol) (for preparation of 6d, 6f, and 7c), or diphenyl
(2-cyclohexylidene-ethenyl) phosphine oxide 6d (3.08 g, 10 mmol) (for prep-
aration of 6e and 7d) in THF (10 mL) at 2788C. The reaction mixture was
stirred at this temperature for 1 h. A solution of methanesulfonyl chloride
(1.15 g, 10 mmol) (for preparation of 6a, 6b, 6d, and 6e), trichloromethanesul-
fonyl chloride (2.18 g, 10 mmol) (for preparation of 6c and 6f), or trimethylsi-
lylchlorosulfate (1.89 g, 10 mmol) (for preparation of 7a–d) in THF (10 mL)
was added dropwise to the reaction mixture at 2788C. After the addition was
completed, the mixture was warmed to rt and stirred for 1 h. Then the mixture
was quenched with 2N HCl, extracted with Et2O, washed with sat. NaCl, and
dried over anhydrous Na2SO4. After evaporation of the solvent, the residue
was chromatographied on column (silica gel, Kieselgel Merck 60 F254
using a mixture of hexane, EtOAc, and Et2O (3:1:1) as an eluent to give the
)
pure phosphorylated allenes 6a–f and 7a–d.
Data
Dimethyl 1-methanesulfonyl-3-methyl-buta-1,2-dienyl phosphonate (6a).
Yield: 2.54 g (5.31 mmol; 53%); light yellow oil. 1H NMR (CDCl3,
250 MHz): d ¼ 1.73 (d, 6H, J ¼ 7.4 Hz, 2Me), 3.07 (s, 3H, MeSO2), 3.64
(d, 6H, J ¼ 12.3Hz, 2MeO). 13C NMR (CDCl3, 50 MHz): d ¼ 21.5
(d, JCP ¼ 5.1 Hz, CH3), 44.0 (d, JCP ¼ 8.4 Hz, CH3), 51.8 (d, JCP ¼ 14.9Hz,
CH3), 94.5 (d, JCP ¼ 184.8 Hz, C), 103.1 (d, JCP ¼ 14.8Hz, C), 206.3
(d, JCP ¼ 4.7 Hz, C). IR (film): 1054 (P-O-Me); 1122, 1350 (SO2); 1256
(P55O), 1954 (C55C55C). Anal. calcd. for C8H15O5PS (254.24): C, 37.79; H,
5.95; P, 12.18; S, 12.61. Found: C, 37.68; H, 6.00; P, 12.24; S, 12.55.
Dimethyl 2-cyclohexylidene-1-methanesulfonyl-ethenyl phosphonate (6b).
Yield: 1.62 g (5.50 mmol; 55%); light yellow solid; mp 101–1028C. 1H
NMR (CDCl3, 250 MHz): d ¼ 1.40–2.29 (m, 10H, cyclohexylidene), 3.06
(s, 3H, MeSO2), 3.65 (d, 6H, J ¼ 12.4 Hz, 2MeO). 13C NMR (CDCl3,
50 MHz): d ¼ 23.7 (CH2), 24.5 (CH2), 27.1 (d, JCP ¼ 4.3 Hz, CH2),
43.6 (d, JCP ¼ 8.2 Hz, CH3), 52.1 (d, JCP ¼ 14.8 Hz, CH3), 93.9
(d, JCP ¼ 185.1 Hz, C), 104.5 (d, JCP ¼ 14.7 Hz, C), 205.1 (d, JCP ¼ 4.3 Hz,
C). IR (nujol): 1048 (P-O-Me); 1130, 1357 (SO2); 1261 (P55O), 1959
(C55C55C). Anal. calcd. for C11H19O5PS (294.31): C, 44.89; H, 6.51; P,
10.52; S, 10.90. Found: C, 44.92; H, 6.47; P, 10.47; S, 10.99.
Dimethyl 3-methyl-1-trichloromethanesulfonyl-buta-1,2-dienylphospho-
nate (6c). Yield: 1.83 g (5.12 mmol; 51%); light yellow oil. 1H NMR
(CDCl3, 250 MHz): d ¼ 1.75 (d, 6H, J ¼ 7.5 Hz, 2Me), 3.62 (d, 6H,
J ¼ 12.5 Hz, 2MeO). 13C NMR (CDCl3, 50 MHz): d ¼ 20.4
(d, JCP ¼ 5.0 Hz, CH3), 53.4 (d, JCP ¼ 15.1 Hz, CH3), 89.7

Bifunctionalized Allenes VII
2239
(d, JCP ¼ 185.0 Hz, C), 102.5 (d, JCP ¼ 14.3 Hz, C), 107.5 (d, JCP ¼ 7.8 Hz,
C), 207.7 (d, JCP ¼ 4.3 Hz, C). IR (film): 1066 (P-O-Me); 1132, 1363
(SO2); 1265 (P55O), 1957 (C55C55C). Anal. calcd. for C8H12Cl3O5PS
(357.58): C, 26.87; H, 3.38; Cl, 29.74; P, 8.66; S, 8.97. Found: C, 26.76;
H, 3.40; Cl, 29.90; P, 8.56; S, 9.05.
Diphenyl (1-methanesulfonyl-3-methyl-buta-1,2-dienyl) phosphine oxide
(6d). Yield: 2.04 g (5.89 mmol; 59%); light yellow solid; mp 123–1248C.
1H NMR (CDCl3, 250 MHz): d ¼ 1.75 (d, 6H, J ¼ 6.5 Hz, 2Me), 2.97
(s, 3H, MeSO2), 7.88–8.20 (m, 10H, 2Ph). 13C NMR (CDCl3, 50 MHz):
d ¼ 20.7 (d, JCP ¼ 5.3 Hz, CH3), 42.4 (d, JCP ¼ 8.1 Hz, CH3), 100.7
(d, JCP ¼ 183.9 Hz, C), 106.5 (d, JCP ¼ 14.3 Hz, C), 130.2 (d, JCP ¼ 4.6 Hz,
CH), 132.7 (d, JCP ¼ 11.4 Hz, CH), 134.7 (d, JCP ¼ 7.8 Hz, CH), 135.6
(d, JCP ¼ 9.7 Hz, CH), 138.6 (d, JCP ¼ 98.5 Hz, C), 197.4 (d, JCP ¼ 4.1 Hz,
C). IR (nujol): 1140, 1363 (SO2); 1203 (P55O), 1952 (C55C55C). Anal.
calcd. for C18H19O3PS (346.38): C, 62.41; H, 5.53; P, 8.94; S, 9.26. Found:
C, 62.48; H, 5.49; P, 9.02; S, 9.32.
Diphenyl (2-cyclohexylidene-1-methanesulfonyl-ethenyl) phosphine oxide
(6e). Yield: 1.97 g (5.07 mmol; 51%); light yellow solid; mp 132–1338C. 1H
NMR (CDCl3, 250 MHz): d ¼ 1.41–2.47 (m, 10H, cyclohexylidene), 2.95
(s, 3H, MeSO2), 7.79–8.22 (m, 10H, 2Ph). 13C NMR (CDCl3, 50 MHz):
d ¼ 23.9 (CH2), 25.2 (CH2), 26.5 (d, JCP ¼ 4.5 Hz, CH2), 43.0
(d, JCP ¼ 8.1 Hz, CH3), 94.7 (d, JCP ¼ 187.7 Hz, C), 105.4 (d, JCP ¼ 14.8Hz,
C), 129.5 (d, JCP ¼ 4.5 Hz, CH), 133.5 (d, JCP ¼ 11.1Hz, CH), 133.8
(d, JCP ¼ 8.2 Hz, CH), 134.1 (d, JCP ¼ 9.3 Hz, CH), 139.4 (d, JCP ¼ 97.2Hz,
C), 194.5 (d, JCP ¼ 4.4 Hz, C). IR (nujol): 1143, 1361 (SO2); 1198 (P55O),
1957 (C55C55C). Anal. calcd. for C21H23O3PS (386.45): C, 65.27; H, 6.00;
P, 8.02; S, 8.30. Found: C, 65.21; H, 6.14; P, 8.11; S, 8.21.
Diphenyl (3-methyl-1-trichloromethanesulfonyl-buta-1,2-dienyl) phosphine
oxide (6f). Yield: 2.43 g (5.40 mmol; 54%); light yellow oil. 1H NMR
(CDCl3, 250 MHz): d ¼ 1.75 (d, 6H, J ¼ 6.5 Hz, 2Me), 2.97 (s, 3H,
MeSO2), 7.88–8.20 (m, 10H, 2Ph). 13C NMR (CDCl3, 50 MHz): d ¼ 21.0
(d, JCP ¼ 5.2 Hz, CH3), 101.5 (d, JCP ¼ 185.1 Hz, C), 105.8
(d, JCP ¼ 14.7Hz, C), 109.5 (d, JCP ¼ 8.4 Hz, C), 129.3 (d, JCP ¼ 4.5 Hz,
CH), 134.8 (d, JCP ¼ 7.9 Hz, CH), 135.1 (d, JCP ¼ 11.3Hz, CH), 136.2
(d, JCP ¼ 10.8Hz, CH), 142.4 (d, JCP ¼ 95.5Hz, C), 200.5 (d, JCP ¼ 4.5 Hz,
C). IR (film): 1135, 1349 (SO2); 1199 (P55O), 1956 (C55C55C). Anal. Calcd.
for C18H16Cl3O3PS (449.72): C, 48.07; H, 3.59; Cl, 23.65; P, 6.89; S, 7.13.
Found: C, 48.15; H, 3.48; Cl, 23.78; P, 8.97; S, 7.31.
Dimethyl 3-methyl-1-trimethylsilyloxysulfonyl-buta-1,2-dienylphospho-
nate (7a). Yield: 1.64 g (4.99 mmol; 50%); light yellow oil. 1H NMR
(CDCl3, 250 MHz): d ¼ 0.23 (s, 9H, Me3SiO), 1.79 (d, 6H, J ¼ 7.8 Hz,
2Me), 3.59 (d, 6H, J ¼ 11.3 Hz, 2MeO). 13C NMR (CDCl3, 50 MHz):
d ¼ 6.9 (CH3), 18.2 (d, JCP ¼ 5.4 Hz, CH3), 51.5 (d, JCP ¼ 15.0 Hz, CH3),

2240
V. C. Christov and J. G. Ivanova
95.8 (d, JCP ¼ 186.7 Hz, C), 102.9 (d, JCP ¼ 14.7 Hz, C), 205.1 (d,
JCP ¼ 4.9 Hz, C). IR (film): 849 (Si-O-S); 1054 (P-O-Me); 1186, 1319
(SO2); 1274 (P55O), 1954 (C55C55C). Anal. calcd. for C10H21O6PSiS
(328.40): C, 36.57; H, 6.45; P, 9.43; S, 9.76. Found: C, 36.62; H, 6.39;
P, 9.54; S, 9.82.
Dimethyl 2-cyclohexylidene-1-trimethylsilyloxy-sulfonyl-ethenylphospho-
nate (7b). Yield: 2.02 g (5.48 mmol; 55%); light yellow solid; mp 97–988C.
1H NMR (CDCl3, 250 MHz): d ¼ 0.31 (s, 9H, Me3SiO), 1.41–2.49
(m, 10H, cyclohexylidene), 3.61 (d, 6H, J ¼ 11.5 Hz, 2MeO). 13C NMR
(CDCl3, 50 MHz): d ¼ 7.2 (CH3), 23.1 (CH2), 23.8 (CH2), 24.9 (d,
JCP ¼ 4.3 Hz, CH2), 52.0 (d, JCP ¼ 15.0 Hz, CH3), 94.3 (d, JCP ¼ 190.5 Hz,
C), 102.8 (d, JCP ¼ 14.9 Hz, C), 204.7 (d, JCP ¼ 5.0 Hz, C). IR (film): 852
(Si-O-S); 1047 (P-O-Me); 1183, 1324 (SO2); 1278 (P55O), 1956
(C55C55C). Anal. calcd. for C13H25O6PSiS (368.46): C, 42.38; H, 6.84;
P, 8.41; S, 8.70. Found: C, 42.44; H, 6.77; P, 8.53; S, 8.63.
Diphenyl (3-methyl-1-trimethylsilyloxysulfonyl-buta-1,2-dienyl) phosphine
oxide (7c). Yield: 2.02 g (4.80 mmol; 48%); light yellow oil. 1H NMR
(CDCl3, 250 MHz): d ¼ 0.23 (s, 9H, Me3SiO), 1.85 (d, 6H, J ¼ 7.7 Hz,
2Me), 7.55–7.83 (m, 10H, 2Ph). 13C NMR (CDCl3, 50 MHz): d ¼ 6.8
(CH3), 18.3 (d, JCP ¼ 5.0 Hz, CH3), 94.7 (d, JCP ¼ 185.9 Hz, C), 101.3
(d, JCP ¼ 14.6 Hz, C), 131.5 (d, JCP ¼ 11.1 Hz, CH), 133.2 (d,
JCP ¼ 7.8 Hz, CH), 133.9 (d, JCP ¼ 4.9 Hz, CH), 134.8 (d, JCP ¼ 9.8 Hz,
CH), 137.4 (d, JCP ¼ 93.8 Hz, C), 188.3 (d, JCP ¼ 4.7 Hz, C). IR (film): 853
(Si-O-S); 1131, 1347 (SO2); 1207 (P55O), 1958 (C55C55C). Anal. calcd for
C20H25O4PSiS (420.54): C, 57.12; H, 5.99; P, 7.37; S, 7.63. Found: C,
57.31; H, 6.09; P, 54; S, 7.82.
Diphenyl (2-cyclohexylidene-1-trimethylsilyloxy-sulfonyl-ethenyl) phos-
phine oxide (7d). Yield: 2.40 g (5.21 mmol; 52%); light yellow solid; mp
1
102–1038C. H NMR (CDCl3, 250 MHz): d ¼ 0.28 (s, 9H, Me3SiO), 1.51–
2.48 (m, 10H, cyclohexylidene), 7.68–8.09 (m, 10H, 2Ph). 13C NMR
(CDCl3, 50 MHz): d ¼ 6.7 (CH3), 23.7 (CH2), 24.9 (CH2), 26.0
(d, JCP ¼ 4.8 Hz, CH2), 96.5 (d, JCP ¼ 184.1 Hz, C), 109.5
(d, JCP ¼ 14.9 Hz, C), 129.9 (d, JCP ¼ 10.3 Hz, CH), 131.7
(d, JCP ¼ 7.8 Hz, CH), 132.0 (d, JCP ¼ 5.1 Hz, CH), 134.6 (d, JCP ¼ 9.9 Hz,
CH), 137.4 (d, JCP ¼ 95.0 Hz, C), 191.7 (d, JCP ¼ 4.9 Hz, C). IR (nujol):
858 (Si-O-S); 1137, 1351 (SO2); 1204 (P55O), 1953 (C55C55C). Anal.
calcd for C23H29O4PSiS (460.60): C, 59.97; H, 6.35; P, 6.72; S, 6.96.
Found: C, 60.06; H, 6.24; P, 6.81; S, 7.03.
ACKNOWLEDGMENTS
Financial support from the Research Fund of the University of Shumen
(Project Nos. 33/2004 and 30/2005) is acknowledged.

Bifunctionalized Allenes VII
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