A general and stereoselective method for synthesis of tri- and tetrasubstituted alkenes

Article abstract of DOI:10.1016/S0040-4020(03)00977-3

A convenient, general and stereoselective synthesis of trisubstituted alkenes and tetrasubstituted alkenes containing a cyanide function as well as trisubstituted episulphides have been elaborated. Methodology described for the preparation of these compounds is based on the corresponding readily available selenophosphates 1 and thiophosphates 2.

Full text of DOI:10.1016/S0040-4020(03)00977-3

Tetrahedron 59 (2003) 6057–6066
A general and stereoselective method for synthesis of tri- and
tetrasubstituted alkenes
*
´
I. Macia˛giewicz, P. Dybowski and A. Skowronska
´ ´
Centre of Molecular and Macromolecular Studies, Department of Heteroorganic Chemistry, Polish Academy of Sciences, 90-363 Łodz,
Sienkiewicza 112, Poland
Received 25 March 2003; revised 27 May 2003; accepted 19 June 2003
Abstract—A convenient, general and stereoselective synthesis of trisubstituted alkenes and tetrasubstituted alkenes containing a cyanide
function as well as trisubstituted episulphides have been elaborated. Methodology described for the preparation of these compounds is based
on the corresponding readily available selenophosphates 1 and thiophosphates 2.
q 2003 Elsevier Ltd. All rights reserved.
1. Introduction
2. Results and discussion
Carbon–carbon double bonds are present in a variety of
organic molecules including natural products.1 In recog-
nition of their importance many synthetic methods have
been devised over the years.2 But construction of particu-
larly important trisubstituted and tetrasubstituted alkenes
with a high degree of stereocontrol remains a significant
challenge in organic synthesis.
The selenophosphates 1 and thiophosphates 2 were readily
prepared on a large scale from the corresponding ketones 3,
adopting the method previously described by us for less
substituted phosphates.10 Treatment of ketones 3 with
trimethylsilyl chloride in the presence of sodium iodide
and triethyl amine gave silyl enol ethers 4. Addition of in
situ generated phosphonium salt 5 to 4 afforded selenopho-
sphates 1, whereas addition of sulphenyl chloride 6 to 4
gave thiophosphates 2 (Scheme 1).
The most important role in the conversion of carbonyl
compounds into unsaturated ones is played by the venerable
Wittig reaction and the Horner–Wadsworth–Emmons
modification based on phosphoroorganic reagents.3 But
when trisubstituted and tetrasubstituted alkenes are formed
via the Wittig reaction, some problems are well documen-
ted.4 Our contribution in this area involves the use of
intermediate thiophosphates and selenophosphates, which
are readily available from the corresponding ketones.5
Using this methodology we elaborated general efficient, and
in some cases stereoselective syntheses of episulphides6 and
a variety of unsaturated systems7 including disubstituted
alkenes.6,8 In this paper we describe our results of the
stereoselective construction of tri- and tetrasubstituted
alkenes, as well as trisubstituted episulphides.9 For this
purpose, we prepared a variety of the corresponding
selenophosphates 1 and thiophosphates 2.
Both compounds 1 and 2 were formed in high yield. They
are stable at 08C over 10 months.
We have examined reactions of selenophosphates 1 with
sodium borohydride at room temperature in alcohol.
Quenching with water afforded the corresponding alkenes
10. The basic concept of transformation of 1 into 10 by the
action of nucleophile is illustrated in Scheme 2.
Keywords: ketones; thiophosphates; selenophosphates; trisubstituted
alkenes; tetrasubstituted alkenes; trisubstituted episulphides.
Scheme 1. (i) Me3SiCl, NaI, Et3N, rt 2608C; (ii) (EtO)3PþSeCl SO2Cl2 5,
278–08C; (iii) (EtO)2P(O)SCl 6, 278–08C.
*
Corresponding author. Tel.: þ48-42-684-3120; fax: þ48-42-684-7126;
e-mail: askow@bilbo.cbmm.lodz.pl
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0040-4020(03)00977-3

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I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
giving a mixture of cis and trans episulphides in the ratio of
34:66 and 72:28, respectively (entries b, f).
Episulphides 11 are known precursors of olefins. 11
undergo, in most cases desulphurization by the action of
triethyl phosphite. It is well documented that this reaction is
stereospecific and proceeds with retention of configur-
ation.11 Therefore, the stereochemistry of episulphides 11 is
preserved in the final alkenes 12 (Table 2). It is noteworthy
that the best results were obtained when conversion of silyl
enol ether 4 to final alkene 10, 12 and episulphide 11 was
performed as a one-pot procedure (Scheme 3).
Scheme 2.
Addition of NaBH4 to selenophosphates 1 provides two
diastereoisomeric oxyanions 7. These intermediate anions
undergo rearrangement involving migration of a phosphoryl
group from selenium to oxygen affording selenolate anions
8. Subsequent cyclization with elimination of phosphate
anion proceeds with inversion of configuration at the carbon
atom adjacent to the phosphate moiety and gives episele-
nides 9 of (E) and (Z) configuration, respectively. The latter
lose selenium spontaneously to provide alkenes 10.
Scheme 3.
It was of interest to apply selenophosphates 1 and thiopho-
sphates 2 to the preparation of tetrasubstituted alkenes 13
containing a cyanide functional group. The 2-alkenenitriles
serve as versatile intermediates in organic synthesis.12
Although numerous synthetic routes to 2-alkenenitriles are
known,13 the preparation of a few examples of tetrasub-
stituted alkenes containing cyanide functional group and
exocyclic CvC bond has been published so far.13a,c,d
As shown in Table 1 a variety of selenophosphates have
been successfully applied to the preparation of trisubstituted
alkenes 10 in good yields. In almost all cases (Z)-alkenes are
formed predominantly (entries a, b, c, e) or exclusively
(entry d). However, when R1 and R2 are small alkyl groups,
the ratio of (Z) and (E)-alkenes is nearly 1:1 (entries f, g).
The observed stereochemistry can be satisfactory explained
by kinetically controlled addition of a hydride anion to the
carbonyl function in 1. It obeys the Felkin–Ahn asymmetric
induction model on the assumption that the (EtO)2P(O)Se
group is the largest one.
The alkenes 13 were produced in good yield from both 1 and
2 via reaction with potassium cyanide in the presence of 18-
crown-6 in dimethoxyethane at room temperature
(Scheme 4).
Our previous results prompted us to apply the thiophosphate
variant to the synthesis of trisubstituted episulphides and
consequently to trisubstituted alkenes. Reduction of thio-
phosphates 2 with NaBH4 under the same reaction
conditions as for selenophosphates 1 gave new trisubstituted
episulphides 11 in good yields. The reaction is stereo-
selective in the case of thiophosphates 2c (R1¼Ph, R2¼i-Pr,
R3¼Me) and thiophosphates 2j (R1¼Ph, R2¼Ph, R3¼Me)
Scheme 4.
Reaction is (Z)-stereoselective (entries c, d, e, g, h). When
R2 and R3 are sterically similar the reaction is not
stereoselective (entries b, f). It is noteworthy that higher
stereoselectivity is achieved when selenophosphates 1 are
used as starting materials (entries e, h) (Table 3).
Table 1. Trisubstituted alkenes 10 prepared from intermediate selenophos-
phates 1
The observed stereochemistry is not consistent with simple
Cram and Felkin asymmetric induction models. Our results
imply that addition of CN2 anion to the carbonyl function of
1 and 2 and rearrangement in the next step (Scheme 2) are
reversible. This type of reversible addition and rearrange-
ment is known.14 Transformation of selenophosphates 1 and
thiophosphates 2 into 11, 12 and 13 by the action of a
nucleophile, proceeds as in Scheme 2.
Entry
R1
R2
R3
Yield (%)a
E/Zb
a
b
c
d
e
f
Ph
Ph
Ph
Ph
t-Bu
Me
Me
n-Oct
Bn
Ph
Me
Me
Me
Et
Me
Ph
52
61
51
46
53
63
57
28:72
17:83
24:76
0:100
12:88
50:50
50:50
Ph
n-Pent
Et
n-Pr
g
Ph
a
No attempt was made to optimize the yield.
Determined by 1H NMR (500 MHz).
b
The structures and configuration of alkenes 10, 12 and 13 as

I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
6059
Table 2. Episulphides 11 prepared from intermediate thiophosphates 2 and alkenes 12 from episulphides 11
Entry
R1
R2
R3
Yield of 11 (%)a
trans/cisof 11b
Yield of 12 (%)a
E/Z of 12b
a
b
c
d
e
f
Ph
Ph
Ph
Ph
Ph
Ph
i-Pr
Ph
Me
i-Pr
n-Bu
n-Hex
Bn
Ph
Me
Me
Me
Me
Me
Me
Me
93
67
92
90
83
78
64
50
–
–
–
66:34
50:50
65:35
56:44
28:72
–
43
56
81
53
–
67:33
47:53
66:34
55:45
–
g
h
Me
–CH2–CH2–
–
–
–
–
–
a
No attempt was made to optimize the yield.
Determined by 1H NMR (500 MHz).
b
Table 3. Tetrasubstituted alkenes 13 from selenophosphates 1 and
thiophosphates 2
All reactions were performed under an argon atmosphere. All
yields refer to the analytically pure products. Commercial
reagents were used as received, without additional purifi-
cation. Ketones were obtained by the alkylation reaction of
propiophenone, butyrophenone and phenylacetone using
NaNH2 or NaH and appropriate alkyl halides. Silyl enol
ethers were obtained from the corresponding ketones accord-
ing to the modified published procedure.15 Oxophosphorane-
sulphenyl chloride 616 and phosphonium salt 517 were
obtained according to previously published procedures.
Entry
R1
R2
R3
X
Yield (%)a
Z/Eb
a
b
c
d
e
f
g
h
i
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
i-Pr
Me
Et
Me
Me
Me
Me
Me
Me
Me
Et
S
Se
S
S
Se
S
S
Se
S
73
82
90
72
63
62
60
71
77
–
53:47
73:27
63:37
80:20
55:45
75:25
90:10
–
i-Pr
n-Bu
Bn
Bn
Ph
Ph
Me
Me
3.2. Synthesis of Se-(b-oxoalkyl) O,O-diethyl seleno-
phosphates 1: general procedure
a
No attempt was made to optimize the yield.
Determined by 1H NMR (500 MHz).
b
SO2Cl2 (6.73 g, 0.050 mol) dissolved in CH2Cl2 (20 mL)
was added dropwise to a stirred solution of O,O,O-triethyl
phosphoroselenoate (7.75 g, 0.050 mol) in CH2Cl2 (40 mL)
at 788C under argon atmosphere. Stirring was continued at
2408C for an additional 1 h. After cooling to 2788C, a
solution of salt (EtO)3PþSeCl SO2Cl2 5 was added
dropwise with stirring to the solution of freshly prepared
silyl enol ether 4 (0.050–0.055 mol) in CH2Cl2 (150 mL).
(from the corresponding ketone by the action of Me3SiCl,
NaI, Et3N in CH3CN, at 608C). The mixture was allowed to
warm to rt, and stirred for 2 h. The volatile components
were removed under reduced pressure, and the crude
product was immediately purified by flash chromatography
using 70–230 mesh silica gel and benzene, and then
benzene and ethyl acetate (2:1) as eluents.
1
well as episulphides 11 were assigned on the basis of H,
13C, NOESY, 1H-1D NOE Difference, IR, MS/CI spec-
troscopy or elemental analysis, and in some cases by
comparison with the data reported in the literature.
In summary, our methodology allows for a general and
stereoselective synthesis of trisubstituted alkenes and
tetrasubstituted alkenes containing a cyanide functional
group suitable for various alkene substituent patterns as well
as for the general preparation of new trisubstituted
episulphides. All reactions proceed under mild conditions
from easily available starting materials.
3. Experimental
3.2.1. Selenophosphoric acid Se-(1-benzoyl-1-methyl-
propyl) ester O,O-diethyl ester (1a). Yield 3.1 g, 71%;
yellow oil; SiO2-TLC (C6H6/AcOEt¼10:7), Rf¼0.51; IR
3.1. Materials and technique
1
(neat) n 1675 (CvO), 1250 (PvO), 1013 (P–OEt); H
IR spectra were obtained on ATI Mattson Infinity Series
60AR FTIR. 1H, 13C and 31P NMR were recorded on Bruker
AC-200 and drx-500 spectrometers. The chemical shifts are
given in units of d relative to CHCl3 (d¼7.27) for CDCl3
solution. For 13C NMR spectra the chemical shifts in CDCl3
are reported to the CDCl3 resonance (d¼77.0). The
chemical shifts of 31P NMR are recorded relative to external
85% H3PO4 (d¼0) with broad-band H decoupling. H-1D
NOE Difference were recorded in CDCl3 solution on Bruker
drx-500 spectrometer. The mass spectra were recorded on
Finnigan MAT 95 apparatus. The elemental analyses were
performed using CHNS-O EA1108 Elemental Analyser.
Column chromatography was performed by using JT Baker
silica gel (0.063–0.200 mm), analytical thin layer chroma-
tography (TLC) was performed on Merck and JT Baker
60F-254 silica gel plates. Gas chromatography was recorded
on a Hewlett Packard 5890.
NMR (200 MHz, CDCl3) d 0.90 (t, 3H, J¼7 Hz, CH3CH2),
1.22 and 1.27 (td, 3H, J¼7 Hz J2¼1 Hz, CH3CH2O), 1.90
(s, 3H, CH3C), 2.15 (m<dq, 1H, J1¼14 Hz J2¼7 Hz,
CHH–CH3), 2.37 (m<sext, 1H, J¼7 Hz, CHH–CH3), 4.05
(m, 4H, OCH2CH3), 7.40–7.60 (m, 3Harom), 8.05 (m,
2Harom); 13C NMR (50 MHz, CDCl3) d 9.54 (CH3CH2C);
15.53, 15.71, 16.43 (CH3CH2O); 25.20, 25.26 (CH3C–);
33.09, 33.23 (CH3CH2C); 63.32, 63.45 and 65.60, 65.84
(CH3CH2O); 127–133 (Carom); 31P NMR (81 MHz, CDCl3)
d 17.59, JPSe¼636.03 Hz. Anal. calcd for C15H23O4PSe: C,
47.75; H, 6.14; P, 8.21. Found: C, 48.04; H, 6.09; P, 7.90.
1
1
3.2.2. Selenophosphoric acid Se-(1-benzoyl-1-methyl-
nonyl) ester O,O-diethyl ester (1b). Yield 2.9 g, 55%;
yellow oil; SiO2-TLC (C6H6/AcOEt¼10:7), Rf¼0.54; IR
1
(neat) n 1676 (CvO), 1252 (PvO), 1017 (P–OEt); H

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I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
NMR (200 MHz, CDCl3) d 0.87 (t, 3H, J¼7 Hz, CH3CH2-
CH2), 1.15 (mc, <14H, CH2), superimposed with 1.25 and
1.32 (td, 3H, J¼7 Hz J2¼1.5 Hz, OCH2CH3), 1.90 [s, 3H,
CH3CC(O)], 2.10 and 2.30 (m, 1H, SeCCH2), 4.10 (m, 4H,
OCH2CH3), 7.40–7.55 (m, 3Harom), 8.10 (m, 2Harom); 31P
NMR (81 MHz, CDCl3) d 17.66, JPSe¼738.40 Hz. Anal.
calcd for C21H35O4PSe: C, 54.66; H, 7.65; P 6.71. Found: C,
54.89; H, 7.29; P 6.59.
yellow oil; IR (neat) n 1677 (CvO), 1253 (PvO), 1016 (P–
1
OEt); H NMR (200 MHz, CDCl3) d 0.82 (t, 3H, J¼7 Hz,
CH3CH2CH2), 1.20 (b sext, 2H, J¼7 Hz, CH3CH2CH2),
1.30 (td, 6H, J¼7 Hz, J2<1 Hz, OCH2CH3), 1.80 and 2.00
(m, 1H, CH2CHPh), 2.09 (s, 3H, CH3CvO), 4.15 (m, 4H,
OCH2CH3), 7.10–7.40 (m, 5Harom); 31P NMR (81 MHz,
CDCl3)
d
18.20, JPSe¼627.40 Hz. Anal. calcd for
C16H25O4PSe: C, 49.11; H, 6.44; P, 7.92. Found: C,
48.93; H, 6.10; P, 7.82.
3.2.3. Selenophosphoric acid Se-(1-benzyl-1-methyl-2-
oxo-2-phenyl-ethyl) ester O,O-diethyl ester (1c). Yield
3.8 g, 86%, pale yellow mass; SiO2-TLC (C6H6/
AcOEt¼10:6), Rf¼0.62; IR (neat) n 1677 (CvO), 1253
(PvO), 1017 (P–OEt); 1H NMR (200 MHz, CDCl3) d 1.22
and 1.31 (td, 3H, J¼7 Hz, J2¼1 Hz, CH3CH2O), 2.32 and
2.33 (2s, 3H, CH3C), 3.64 (AB, 2H, JAB¼12.8 Hz,
dA¼3.44, dB¼3.85, PhCH2), 4.15 (m, 4H, OCH2CH3),
7.00–7.50 (m, 3Harom), 8.00 (m, 2Harom); 31P NMR
(81 MHz, CDCl3) d 17.06, JPSe¼499.30 Hz. Anal. calcd
for C20H25O4PSe: C, 54.68; H, 5.74; P, 7.05. Found: C,
55.01; H, 6.06; P 6.84.
3.3. Synthesis of S-(b-oxoalkyl) O,O-diethyl
thiophosphates 2: general procedure
SO2Cl2 (6.73 g, 0.050 mol) dissolved in CH2Cl2 (20 mL)
was added dropwise to a stirred solution of O,O,O-triethyl
phosphorothioate (5.40 g, 0.050 mol) in CH2Cl2 (40 mL) at
2208C. Stirring was continued at rt for an additional 1 h.
After removal in vacuo of about 80% of solvent the crude
(EtO)2P(O)SCl 6 was added dropwise to a stirred solution of
freshly prepared silyl enol ether 4 (0.050–0.055 mol) in
CH2Cl2 (150 mL) at 2788C. The mixture was allowed to
warm to rt, and stirred for 2 h. The solvent and trimethylsilyl
chloride were removed under reduced pressure, and the
crude product was purified by column chromatography on
silica gel using benzene, and then benzene and ethyl acetate
(2:1) as eluents.
3.2.4. Selenophosphoric acid O,O-diethyl ester Se-(1-
methyl-2-oxo-1,2-diphenyl-ethyl) ester (1d). Yield 4.25 g,
72%, pale yellow mass; SiO2-TLC (C6H6/AcOEt¼10:6),
Rf¼0.57; IR (neat) n 1685 (CvO), 1253 (PvO), 1016 (P–
OEt); 1H NMR (500 MHz, CDCl3) d 1.32 (td, 3H, J¼7 Hz,
J2,1 Hz, CH3CH2O), 2.00 (s, 3H, CH3C), 4.05 (m, 2H,
OCH2CH3), 7.10–7.30 (m, 8Harom), 7.90 (m, 2Harom); 31P
NMR (202 MHz, CDCl3) d 20.03, JPSe¼464.30 Hz. Anal.
calcd for C19H23O4PSe: C, 53.66; H, 5.45; P 7.28. Found: C,
53.87; H, 5.19; P 7.24.
3.3.1. Thiophosphoric acid S-(1,1-dimethyl-2-oxo-2-phe-
nyl-ethyl) ester O,O-diethyl ester (2a). Yield 8.35 g, 84%,
yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.65; IR
1
(neat) n 1680 (CvO), 1255 (PvO), 1016 (P–OEt); H
NMR (200 MHz, CDCl3) d 1.18 (td, 3H, J¼6.8 Hz,
J2¼1.2 Hz, CH3CH2O), 1.77 and 1.78 [s, 3H, (CH3)2-
CCvO], 3.96 (m, 2H, CH3CH2O), 7.33–8.13 (m, 5Harom);
13C NMR (50 MHz, DEPT, CDCl3) d 15.73, 15.87
(CH3CH2O), 28.97, 29.12 [(CH3)2CCvO], 55.83 [(CH3)2-
CCvO], 63.79, 63.92 (CH3CH2O), 127.95–132.79 (Carom);
31P NMR (81 MHz, CDCl3) d 22.63. Anal. calcd for
C14H21O4PS: C, 53.15; H, 6.69; P, 9.79; S, 10.13. Found: C,
53.20; H, 6.86; P, 9.63; S, 10.04.
3.2.5. Selenophosphoric acid Se-(1-benzoyl-1-phenyl-
propyl) ester O,O-diethyl ester (1e). Yield 3.53 g, 68%,
yellow oil; SiO2-TLC (C6H6/AcOEt¼10:7), Rf¼0.64; IR
1
(neat) n 1675 (CvO), 1252 (PvO), 1017 (P–OEt); H
NMR (200 MHz, CDCl3) d 0.97 (t, 1.5H, J¼7 Hz,
CH3CH2C), 1.03 (td, 1.5H, J¼7 Hz J2¼1 Hz, CH3CH2C),
1.23 (td, 3H, J¼7 Hz J2¼1 Hz, CH3CH2O), 1.26 (t, 3H,
J¼7 Hz, CH3CH2O), 2.49 (sext d, 1H, J¼7 Hz J2¼0.5 Hz,
CH3CH2C), 3.23 (sext, 1H, J¼7 Hz, CH3CH2C), 3.80 (m,
2H, OCH2CH3), 4.05 (m, 2H, OCH2CH3), 7.20–7.60 (mc,
10Harom); 13C NMR (50 MHz, DEPT, CDCl3) d 10.19
(CH3CH2C), 15.37, 15.53, 15.83, 15.97 (OCH2CH3), 29.55
(CH3CH2C), 62.73, 62.86, 62.97, 63.08 (OCH2CH3), 125–
134 (Carom), 200.03 (CvO); 31P NMR (81 MHz, CDCl3) d
18.57, JPSe¼497.80 Hz. Anal. calcd for C20H25O4PSe: C,
54.68; H, 5.74; P, 7.05. Found: C, 54.67; H, 5.62; P, 7.00.
3.3.2. Thiophosphoric acid S-(1-benzoyl-1-methyl-pro-
pyl) ester O,O-diethyl ester (2b). Yield 9.14 g, 95%,
yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.81; IR
1
(neat) n 1678 (CvO), 1253 (PvO), 1016 (P–OEt); H
NMR (200 MHz, CDCl3) d 0.91 (t, 3H, J¼7.9 Hz,
CH3CH2C), 1.20 and 1.51 (td, 3H, J¼7.5 Hz, J2¼1 Hz,
CH3CH2O), 1.77 (s, 3H, CH3C), 2.17 [AB: (part A: ABq,
1H, JAB¼13.9 Hz, Jvic¼7.6 Hz, dA¼2.11) (part B: ABqd,
1H, JAB¼13.9 Hz, Jvic¼7.6 Hz, J3¼2.0 Hz, dB¼2.24),
CH3CH2C], 3.99 (m, 4H, CH3CH2O), 7.46 (m, 3Harom),
8.11 (m, 2Harom); 13C NMR (50 MHz, DEPT, CDCl3) d 8.87
(CH3CH2C), 15.55, 15.69 (CH3CH2O), 24.87, 24.95
(CH3C), 33.23, 33.43 (CH3CH2C), 63.49, 63.62, 63.74
(CH3CH2O), 60.33, 60.41 (CH3CCvO), 127.77, 129.29,
131.65, 136.33 (Carom), 198.97 (CvO); 31P NMR (81 MHz,
CDCl3) d 22.82. Anal. calcd for C15H23O4PS: C, 54.53; H,
7.02; P, 9.38; S, 9.70. Found: C, 54.34; H, 7.28; P, 9.42; S,
9.41.
3.2.6. Selenophosphoric acid O,O-diethyl ester Se-(1-
ethyl-2-oxo-1-phenyl-propyl) ester (1f). Yield 2.82 g,
67%, yellow oil; IR (neat) n 1678 (CvO), 1253 (PvO),
1016 (P–OEt); 1H NMR (200 MHz, CDCl3) d 0.81 (td, 3H,
J¼7.5 Hz, J¼1 Hz, CH3CH2C), 1.31 (td, 6H, J¼7.5 Hz,
J<1 Hz, CH3CH2O), 2.12 (bq, 2H, J¼7.5 Hz, CH3CH2C),
2.10 (s, 3H, CH3CvO), 4.05 (m, 4H, OCH2CH3), 7.20–
7.40 (m, 5Harom); 31P NMR (81 MHz, CDCl3) d 17.42,
JPSe¼610.30 Hz. Anal. calcd for C15H23O4PSe: C, 47.75; H,
6.14; P 8.21. Found: C, 48.11; H, 6.09; P, 8.03.
3.3.3. Thiophosphoric acid S-(1-benzoyl-1,2-dimethyl-
propyl) ester O,O-diethyl ester (2c). Yield 7.78 g, 59%,
yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.66 and
3.2.7. Selenophosphoric acid Se-(1-acetyl-1-phenyl-
butyl) ester O,O-diethyl ester (1g). Yield 3.74 g, 69%,

I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
6061
0.58; IR (neat) n 1678 (CvO), 1253 (PvO), 1034, 1018
(P–OEt); 1H NMR (500 MHz, CDCl3) d [0.74 (d, 3H,
J¼6.74 Hz) and 1.17 (d, 3H, J¼6.74 Hz), (CH3)2CH], [1.15
(t, 3H, J¼7.18 Hz) and 1.20 (t, 3H, J¼7.08 Hz),
CH3CH2O], 1.66 (s, 3H, CH3CS), 2.63 [sept, 1H,
J¼6.75 Hz, (CH3)2CH], 3.85–3.95 and 3.95–4.07 (m, 2H,
CH3CH2O), 7.35–7.40 (m, 2Harom), 7.42–7.49 (m, 1Harom),
8.20 (mh d, 2Harom, J¼7.70 Hz); 13C NMR (50 MHz,
DEPT, CDCl3) d 15.32, 15.45, 15.52 (CH3CH2O), 17.36,
17.49, 18.66 [(CH3)2CH], 21.83 (CH3CS), 34.86, 35.08
[(CH3)2CH], 63.07, 63.30, 63.42, 63.52, 63.66, 63.82
(CH3CH2O), 71.15 (CH3CS), 127.60, 129.47, 131.50,
136.33 (C-48)-Carom, 198.37 (CvO); 31P NMR (81 MHz,
CDCl3) d 23.06. Anal. calcd for C16H25O4PS: C, 55.80; H,
7.32; S, 9.31; P, 8.99. Found: C, 55.64; H, 7.70; S, 8.55; P,
8.80.
1.22 (t, 3H, J¼7.33 Hz, CH3CH2O), 1.80 (s, 3H, CH3CSP),
2.02 [td, 1H, J¼12.25 Hz, J2¼4.30 Hz, CH3(CH2)4CHH],
2.19 [td broad lines, 1H, J¼12.43 Hz, J2<3.90 Hz,
CH3(CH2)4CHH], 3.93–3.99 and 4.00–4.08 (m, 2H,
CH3CH2O), [7.40 (mh t, 2H), 7.49 (mh t, 1H), 8.12
(mh d, 2H)-Harom]; 13C NMR (50 MHz, CDCl3) d 13.55
[CH3(CH2)5], 15.32, 15.46 (CH3CH2O), 21.97, 24.05,
28.87, 30.90 (CH3CH2CH2CH2CH2CH2), 25.35 (CH3CS),
40.12, 40.31 (CH3CH2CH2CH2CH2CH2), 59.63, 59.70
(CH3CS), 63.18, 63.31, 63.42 (CH3CH2O), [127.52,
129.06, 131.40, 136.12 (C-48)-Carom], 198.59 (CvO); 31P
NMR (81 MHz, CDCl3)
d 22.86. Anal. calcd for
C19H31O4PS: C, 59.05; H, 8.08; S, 8.30; P, 8.01. Found:
C, 58.96; H, 8.21; S, 7.60; P, 8.04.
3.3.7. Thiophosphoric acid S-(1-benzoyl-1-methyl-nonyl)
ester O,O-diethyl ester (2g). Yield 9.12 g, 73%, yellow oil;
SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.78; IR (neat) n 1679
(CvO), 1255 (PvO), 1033, 1018 (P–OEt); 1H NMR
(500 MHz, CDCl3) d 0.84 [t, 3H, J¼7.11 Hz, CH3(CH2)7],
1.13–1.18 [m, 12H, CH3(CH2)6CH2], 1.20 and 1.21 (t, 3H,
J¼7.32 Hz, CH3CH2O), 1.80 (s, 3H, CH3CSP), 2.01
[tdh ddd, 1H, J1¼12.14 Hz, J2¼4.52 Hz, CH3(CH2)6CHH],
2.19 [td broad lines, 1H, J1¼12.86 Hz, J2¼3.71 Hz,
CH3(CH2)6CHH], 3.89–3.97 and 3.99–4.09 (m, 2H,
CH3CH2O), [7.40 (mh t, 2H), 7.48 (mh t, 1H), 8.11
(mh d, 2H)-Harom]; 13C NMR (126 MHz, DEPT, CDCl3)
3.3.4. Thiophosphoric acid S-(1-benzoyl-1-methyl-pen-
tyl) ester O,O-diethyl ester (2d). Yield 8.40 g, 89%, yellow
oil; IR (neat) n 1677 (CvO), 1252 (PvO), 1017 (P–OEt);
1H NMR (500 MHz, CDCl3) d 0.80 (t, 3H, J¼7.5 Hz,
CH3CH2CH2CH2), 1.19 and 1.21 (td, 3H, J¼7.2 Hz,
J2¼1 Hz, CH3CH2O), 1.06–1.15 (m, 2H, CH3CH2CH2-
CH2), 1.37–1.46 (m, 2H, CH3CH2CH2CH2), 1.79 (s, 3H,
CH3C), 2.02 and 2.19 (td, 2H, J¼13.2 Hz, J2¼3.8 Hz,
CH3CH2CH2CH2), 3.99 (m, 2H, CH3CH2O), 7.38–7.49 (m,
3Harom), 8.09–8.11 (m, 2Harom); 13C NMR (50 MHz,
CDCl3)
d
13.66 (CH3CH2–CH2CH2), 15.69, 15.84
d
13.73 [CH3(CH2)7], 15.45, 15.47, 15.50, 15.53
(CH3CH2O), 22.73 (CH3CH2–CH2CH2), 25.65, 25.71
(CH3CH2CH2CH2), 26.64 (CH3C), 40.26, 40.44 (CH3CH2-
CH2CH2), 59.98, 60.06 (CH3C), 63.60, 63.73, 63.86
(CH3CH2O), 127.90–136.46 (Carom), 199.09 (CvO); 31P
(CH3CH2O), 22.25, 24.18, 28.70, 28.76, 29.29, 31.40
(CH3CH2CH2CH2CH2CH2), 25.42, 25.45 (CH3CS), 40.28,
40.36 [CH3(CH2)6CH2], 59.78, 59.81 (CH3CS), 63.33,
63.38, 63.44, 63.49 (CH3CH2O), [127.60, 129.16, 131.47,
136.25 (C-48)-Carom], 198.63 (CvO); 31P NMR (81 MHz,
CDCl3) d 22.87. Anal. calcd for C21H35O4PS: C, 60.85; H,
8.51; S, 7.73; P, 7.47. Found: C, 60.81; H, 8.73; S, 7.19; P,
7.41.
NMR (81 MHz, CDCl3)
d 22.82. Anal. calcd for
C17H27O4PS: C, 56.97; H, 7.59; P, 8.64; S, 8.94. Found:
C, 57.18; H, 8.19; P, 7.94; S, 7.47.
3.3.5. Thiophosphoric acid S-(1-benzoyl-1,3-dimethyl-
butyl) ester O,O-diethyl ester (2e). Yield 6.97 g, 62%,
yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.71; IR
(neat) n 1677 (CvO), 1255, 1225 (PvO), 1043, 1018 (P–
OEt); 1H NMR (200 MHz, CDCl3) d 0.68 and 0.95 [d, 3H,
J¼6.62 Hz, (CH3)2CH], 1.20 (tdd, 3H, J¼7.06 Hz
J2¼4.35 Hz, J3¼0.85 Hz, CH3CH2O), 1.79 [nonet, broad
lines, 1H, Jvic<6.60 Hz, (CH3)2CHCH2], 1.86 (s, 3H,
CH3C), 2.12 [ABdd, 2H (part A: JAB¼14.79 Hz, Jvic¼6.34
Hz, J3¼1.69 Hz, dA¼2.24), (part B: JAB¼14.79 Hz,
Jvic¼5.50 Hz, J3¼0.98 Hz, dB¼2.01), (CH3)2CHCH2],
4.01 (m, 2H, CH3CH2O), 7.44 (m, 3Harom), 8.14 (m,
2Harom); 13C NMR (126 MHz, DEPT, CDCl3) d 15.47,
15.52, 15.56 (CH3CH2O), 23.31, 24.39 [(CH3)2CH], 25.27
[(CH3)2CH], 25.87 (CH3C), 48.90, 48.98 [(CH3)CHCH2],
59.97 (CH3C), 63.37, 63.52, 63.56 (CH3CH2O), [127.64,
128.00, 129.55, 131.57, 136.26 (C-48)-Carom], 198.67
(CvO); 31P NMR (81 MHz, CDCl3) d 22.55. Anal. calcd
for C17H27O4PS: C, 56.97; H, 7.59; S, 8.94; P, 8.64. Found:
C, 56.45; H, 7.45; S, 8.94; P, 7.96.
3.3.8. Thiophosphoric acid S-(1-benzyl-1-methyl-2-oxo-
2-phenyl-ethyl) ester O,O-diethyl ester (2h). Yield
12.06 g, 97%, yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1),
Rf¼0.77; IR (neat) n 1678 (CvO), 1253 (PvO), 1016 (P–
1
OEt); H NMR (500 MHz, CDCl3) d 1.19 and 1.22 (t, 3H,
J¼6.64 Hz, CH3CH2O), 1.71 (s, 3H, CH3C), 3.50 (AB, 2H,
JAB¼13.8 Hz, dA¼3.39 dB¼3.61, in part B broad lines,
PhCH2C), 3.91–4.01 and 4.03–4.13 (m, 2H, CH3CH2O),
7.11 (m, 2Harom), 7.23 (m, 3Harom) 7.41–7.52 (m, 3Harom),
8.10–8.12 (m, 2Harom); 13C NMR (50 MHz, DEPT, CDCl3)
d 15.65, 15.79 (CH3CH2O), 25.60, 25.69 (CH3C), 45.72,
45.90 (PhCH2C), 59.78 (CH3CCvO), 63.73, 63.87, 64.03
(CH3CH2O), 127.05–136.50 (Carom), 198.63 (CvO); 31P
NMR (202 MHz, CDCl3) d 23.65. Anal. calcd for
C20H25O4PS: C, 61.21; H, 6.42; P, 7.89; S, 8.17. Found:
C, 61.17; H, 6.51; P, 7.62; S, 7.81.
3.3.9. Thiophosphoric acid S-(1-benzoyl-1-benzyl-pro-
pyl) ester O,O-diethyl ester (2i). Yield 11.22 g, 98%, dark
yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.74; IR
1
3.3.6. Thiophosphoric acid S-(1-benzoyl-1-methyl-hep-
tyl) ester O,O-diethyl ester (2f). Yield 10.32 g, 80%,
yellow oil; SiO2-TLC (C6H6/AcOEt¼1:1), Rf¼0.70; IR
(neat) n 1678 (CvO), 1254 (PvO), 1033, 1018 (P–OEt);
1H NMR (500 MHz, CDCl3) d 0.81 [t, 3H, J¼7.15 Hz,
CH3(CH2)5], 1.10–1.18 [m, 8H, CH3(CH2)4CH2], 1.20 and
(neat) n 1676 (CvO), 1253 (PvO), 1016 (P–OEt); H
NMR (500 MHz, CDCl3) d 1.01 (t, 3H, J¼7.14 Hz,
CH3CH2C), 1.17 and 1.24 (t, 3H, J¼7.14 Hz, CH3CH2O),
2.14 (ABq, 2H, JAB¼15.2 Hz, dA¼2.12 dB¼2.16,
CH3CH2C), 3.58 (AB, 2H, JAB¼14.38 Hz, dA¼3.53
dB¼3.63, PhCH2C), 3.91–4.12 (m, 4H, CH3CH2O),

6062
I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
7.23–7.26 (m, 5Harom), 7.40 and 7.49 (mh quasi t,
1.5Harom), 8.05–8.06 (mh d, 2Harom); 13C NMR (50 MHz,
DEPT, CDCl3) d 9.08 15.67, 15.78, 16.90 (CH3CH2O),
28.81, 28.97 (CH3CH2C), 40.51, 40.61 (PhCH2C), 63.83,
63.95, 64.08 (CH3CH2O), 66.02 (CH3CH2C), 126.83–
137.28 (Carom), 198.95 (CvO); 31P NMR (81 MHz,
CDCl3) d 22.28. Anal. calcd for C21H27O4PS: C, 62.05;
H, 6.70; P, 7.62; S, 7.89. Found: C, 61.86; H, 6.69; P, 7.58;
S, 7.46.
chromatography on silica gel, using benzene or petroleum
ether as eluent.
3.5. Synthesis of trisubstituted alkenes 10 from the
intermediate 1: in one-pot procedure
A solution of SO2Cl2 (2.02 g, 0.015 mol) in CH2Cl2
(10 mL) was added dropwise to O,O,O-triethyl phosphor-
oselenoate (3.67 g, 0.015 mol) in CH2Cl2 (10 mL) at
2788C. Stirring was continued at 2408C for an additional
1 h. After cooling to 2788C, the salt (EtO)3PþSeCl SO2Cl2
5 was added dropwise with stirring to the solution of freshly
prepared silyl enol ether 4 (0.016 mol) in CH2Cl2 (40 mL).
The mixture was allowed to warm to rt, and stirred for
additional 1–2 h. The solvent and volatile components were
removed under reduced pressure to give selenophosphate 1.
Then crude 1 dissolved in dry CH3OH (20 mL) was added
dropwise to a stirred suspension of NaBH4 (0.76 g,
0.020 mol) in CH3OH (40 mL). Stirring was continued for
4 h. Further workup was as described above.
3.3.10. Thiophosphoric acid O,O-diethyl ester S-(1-
methyl-2-oxo-1,2-diphenyl-ethyl) ester (2j). Yield
8.86 g, 95%, dark yellow oil; SiO2-TLC (C6H6/
AcOEt¼1:1), Rf¼0.74; IR (neat) n 1683 (CvO), 1253
(PvO), 1017 (P–OEt); 1H NMR (200 MHz, CDCl3) d 1.13
and 1.23 (td, 3H, J¼7.1 Hz, J2¼1 Hz, CH3CH2O), 2.26 (s,
3H, CH3C), 3.42–4.10 (m, 4H, CH3CH2O), 7.23–7.58 (m,
10Harom); 13C NMR (50 MHz, DEPT, CDCl3) d 15.53,
15.71, 15.87 (CH3CH2O), 28.65 (CH3C), 63.38, 63.51,
63.61 (CH3CH2O), 65.54 (CH3CCvO), 126.52–134.45
(Carom), 196.63 (CvO); 31P NMR (81 MHz, CDCl3) d
22.76. Anal. calcd for C19H23O4PS: C, 60.31; H, 6.13; P,
8.18. Found: C, 60.49; H, 6.27; P, 8.17.
3.5.1. (2-Methyl-dec-1-enyl)-benzene (10a). Yield 0.78 g,
52%, light yellow oil, isomer ratio¼72:28 (Z/E) (according
to 1H NMR); IR (neat) n 1595 (CvC); 1H NMR (200 MHz,
CDCl3) d 0.88 (m, 3H, CH3CH2CH2), 1.25 (b s<mc, ,14H,
CH2), 2.25 (b q<2t, 2H, vCCH2), 3.26 (s, 0.28£3H,
CH3Cv), 3.49 (s, 0.72£3H, CH3Cv), 6.08 (s, 0.72H,
vCHPh), 6.23 (b s, 0.28H, vCHPh), 7.20–7.60 (m,
5Harom). Anal. calcd for C17H26: C, 88.63; H, 11.37.
Found: C, 88.54; H, 11.20.
3.3.11. Thiophosphoric acid O,O-diethyl ester S-(1,1,3-
trimethyl-2-oxo-butyl) ester (2k). Yield 7.19 g, 100%,
pale yellow oil; IR (neat) n 1710 (CvO), 1255 (PvO),
1
1034, 1020 (P–OEt); H NMR (200 MHz, CDCl3) d 1.10
and 1.14 [s, 3H, (CH3)2CH], 1.32 (td, 3H, J¼7.1 Hz,
J2¼1.1 Hz, CH3CH2O), 1.64 and 1.65 [s, 3H, (CH3)2-
CCvO], 3.36 [sept, 1H, J¼6.7 Hz, (CH3)2CH], 4.13 (m,
2H, CH3CH2O); 13C NMR (50 MHz, DEPT, CDCl3) d
15.77, 15.91 (CH3CH2O), 20.62 [(CH3)2CHCvO], 26.47,
26.61 [(CH3)2CCvO], 34.35 [(CH3)2CHCvO], 58.16
[(CH3)2CCvO], 63.73, 63.87 (CH3CH2O), 211.91
(CvO); 31P NMR (81 MHz, CDCl3) d 23.19. Anal. calcd
for C11H23O4PS: C, 46.80; H, 8.21; P, 10.97. Found: C,
47.11; H, 8.32; P, 10.78.
3.5.2. 1,3-Diphenyl-2-methyl-prop-1-ene (10b)5(12e).18
Yield 0.89 g, 61%, colorless oil, isomer ratio¼83:17 (Z/E)
(according to 1H NMR); IR (neat) n 1608, 1597 (CvC); 1H
NMR (500 MHz, CDCl3) d [1.75 (d, 3H, J¼0.5 Hz,
CH3Cv), 3.55 (s, 2H, PhCH2), 6.47 (s, 1H, PhCHv),
7.10–7.30 (mc, 10Harom)-83% of integration], [1.48 (s, 3H,
CH3Cv), 3.43 (s, 2H, PhCH2), 6.32 (s, 1H, PhCHv),
7.10–7.30 (mc, 10Harom)-17% of integration]; GC (HP1
30 M 50/2/260) 83.2 and 16.8%. Anal. calcd for C16H16: C,
92.26; H, 7.74. Found: C, 91.96; H, 7.81.
3.3.12. Thiophosphoric acid S-(1-benzoyl-cyclopropyl)
ester O,O-diethyl ester (2l). Yield 9.20 g, 58%, yellow oil;
1
IR (neat) n 1675 (CvO), 1252 (PvO), 1017 (P–OEt); H
NMR (500 MHz, CDCl3) d 1.32 (t, 6H, J¼7.38 Hz,
OCH2CH3), [3.67 (ddd, 2H, J1¼15.64 Hz, J2¼6.46 Hz,
J3¼0.86 Hz), 6.98 (dt, 1H, J1¼15.21 Hz, J2¼6.96 Hz), 7.08
(d, 1H, J1¼15.21 Hz), –CH2–CH2–], 4.15 (mc, 4H,
OCH2CH3), [7.45 (t, 2H, J¼7.80 Hz), 7.55 (tt, 1H,
J¼7.8 Hz), 7.93 (m<d, 2H, J<7.5 Hz), Harom]; 31P NMR
(202 MHz, CDCl3) d 27.19. Anal. calcd for C14H19O4PS: C,
53.49; H, 6.09; P, 9.85; S, 10.20. Found: C, 53.10; H, 6.02;
P, 9.57; S, 9.95.
3.5.3. Methylstilbene (10c).19 Yield 0.64 g, 51%, light
yellow oil, isomer ratio¼76:24 (Z/E) (according to 1H
NMR); IR (neat) n 1595 (CvC); 1H NMR (200 MHz,
CDCl3) d [2.21 (d, 3H, J¼1 Hz, CH3Cv), 6.76 (s, 1H,
PhCHv), 7.10–7.40 (mc, 10Harom)-24% of integration],
[2.13 (d, 3H, J¼1 Hz, CH3Cv), 6.39 (s, 1H, PhCHv),
7.10–7.40 (mc, 10Harom)-76% of integration]. Anal. calcd
for C15H14: C, 92.74; H, 7.26. Found: C, 93.03; H, 7.51.
3.5.4. Ethylstilbene (10d). Yield 0.38 g, 46%, light yellow
1
3.4. Synthesis of trisubstituted alkenes 10 from 1:
general procedure
oil, isomer ratio(95:5 (Z/E) (according to H NMR); IR
1
(neat) n 1598 (CvC); H NMR (500 MHz, CDCl3) d 0.98
(t, 3H, J¼7.5 Hz, CH3CH2C), 2.43 (qd, 2H, J¼7.5 Hz,
J2<1.0 Hz, CH3CH2C), 6.31 (bs, 0.2H, PhCHv), 6.36 (bs,
0.8H, PhCHv), 6.90–7.40 (mc, 10Harom)-100% of inte-
gration for Z; [0.94 (t, 3H, J¼7.5 Hz, CH3CH2C), 2.68 (q,
2H, J¼7.5 Hz, CH3CH2C), 6.61 (s, 1H, PhCHv), 6.90–
7.40 (mc, 10Harom). Anal. calcd for C16H16: C, 92.26; H,
7.74. Found: C, 92.31; H, 7.71.
A solution of Se-(b-oxoalkyl) O,O-diethyl selenophosphate
1 (0.010 mol) in dry CH3OH (20 mL) was added dropwise
to NaBH4 (0.57 g, 0.015 mol) suspended in CH3OH
(40 mL). Stirring was usually continued for 4 h. During
that time red or black selenium was precipitated. Then the
reaction mixture was extracted with 2£50 mL of pentane,
the combined organic phases were washed with water, dried
over MgSO4 and alkene 10 was purified by column
3.5.5. 2,2,4-Trimethyl-non-3-ene (10e). Yield 1.08 g, 53%,

I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
6063
1
1
yellowish oil, isomer ratio¼88:12 (Z/E) (according to H
NMR); IR (neat) n 1590 (CvC); 1H NMR (200 MHz,
C6D6) d 0.98 [t, 3H, J¼7 Hz, CH3(CH2)4Cv]-both isomers,
1.02 [bs, ,0.9£9H, (CH3)3C]-major, 1.12 [bs, ,0.1£9H,
(CH3)3C]-minor, 1.22–2.19 (2mc, 2H superimposed with
4H, CH3CH2CH2CH2CH2Cv]-both isomers, 1.92 (bs,d,
w1/2¼6, ,1H, J<1 Hz, CH3Cv); 2.75 (dd,t, 0.88£2H,
J1¼8.8 Hz, J2¼7.5 Hz, CH2Cv)-major, 2.92 (dd,t,
0.12£2H, J1¼8.8 Hz, J2¼7.4 Hz, CH2Cv)-minor, 5.56
(bs,d, 0.88H, J<1 Hz, CHv)-major, 5.71 (bs, 0.12H,
CHv)-minor. Anal. calcd for C12H24: C, 85.63; H, 14.37.
Found: C, 85.49; H 14.39.
1448, 794, 739, 698; H NMR (500 MHz, CDCl3) d 1.26
and 1.74 [s, 3H, (CH3)2C,], 3.97 (s, 1H, PhCHS), 7.21–
7.36 (5Harom); 13C NMR (50 MHz, DEPT, CDCl3) d 23.4
and 30.7 [(CH3)2C,], 47.9 [(CH3)2C,], 51.8 (PhCHS),
[127.0, 127.1, 127.8, 128.8, 136.3 (C-48)-Carom]. Anal. calcd
for C10H12S: C, 73.12; H, 7.36; S, 19.52. Found: C, 72.88;
H, 7.36; S, 19.35.
3.6.2. 2-Isopropyl-2-methyl-3-phenyl-thiirane (11b).
Yield 4.36 g, 67%, light yellow oil, isomer ratio¼66:34
(trans/cis) (according to 1H NMR); IR (neat) n 2980, 2959,
2887, 1490, 1448, 794, 735, 689; 1H NMR (500 MHz,
CDCl3) d 1.16 [d, 0.66£6H, J¼7.1 Hz, CH(CH3)2], 1.17 [d,
0.34£6H, J¼7.1 Hz, CH(CH3)2], 1.11 (s, 0.66£3H,
SCCH3), 1.60 (s, 0.34£3H, SCCH3), 1.39[b sept, 0.66H,
J¼7 Hz, CH(CH3)2], 2.64 [sept, 0.34H, J¼7 Hz,
CH(CH3)2], 3.96 (s, 0.66H, PhCHS), 4.01 (s, 0.34H,
PhCHS), 7.25–7.43 (mc, 5Harom); 13C NMR (126 MHz,
CDCl3) d 15.8, 18.9, 19.8 (CH3)-major, 17.8, 20.8, 22.1
(CH3)-minor, 33.1-minor and 41.6-major [(CH3)2CH], 52.1-
major and 53.7-minor (PhCHS), 57.2-minor and 57.4-major
(SC-iPr), 127.1, 127.1, 127.8, 127.9, 129.0, 130.0, 129.8,
134.1 136.4 (Carom). Anal. calcd for C12H16S: C, 74.94; H,
8.39; S, 16.67. Found: C, 74.49; H, 7.78; S, 12.32.
3.5.6. (1-Ethyl-propenyl)-benzene (10f). Yield 0.92 g,
1
63%, colorless oil, isomer ratio¼50:50 (according to H
NMR); IR (neat) n 1610, 1600 (CvC); 1H NMR (200 MHz,
CDCl3) d 0.98 (t, 3H, J¼7 Hz, CH3CH2Cv), 1.90 (d, 3H,
J¼7 Hz, CH3CHv), 2.54 (q, 2H, J¼7 Hz, CH3CH2Cv),
5.70 (q, 1H, J¼7 Hz, CH3CHv), 7.00–7.50 (m, 5Harom)-E-
isomer; 0.93 (t, 3H, J¼7 Hz, CH3CH2Cv), 1.57 (d, 3H,
J¼7 Hz, CH3CHv), 2.34 (q, 2H, J¼7 Hz, CH3CH2Cv),
5.48 (q, 1H, J¼7 Hz, CH3CHv), 7.00–7.50 (m, 5Harom)-Z-
isomer. Anal. calcd for C11H14: C, 90.35; H, 9.65. Found: C,
90.02; H, 9.56.
3.5.7. (1-Ethylidene-butyl)-benzene (10g). Yield 0.75 g,
1
3.6.3. 2-Butyl-2-methyl-3-phenyl-thiirane (11c). Yield
3.71 g, 92%, colorless oil, isomer ratio¼50:50 (according
57%, colorless oil, isomer ratio¼50:50 (according to H
NMR); IR (neat) n 1610, 1600 (CvC); 1H NMR
(200 MHz, CDCl3) d [0.84 (t, 3H, J¼7 Hz, CH3CH2-
CH2), 1.35 (sext, 2H, J¼7 Hz, CH3CH2CH2), 1.60 (d, 3H,
J¼7 Hz, CH3CHv), 2.43 (t, 2H, J¼7 Hz, PhCCH2), 5.46
(q, 1H, J¼7 Hz, CH3CHv), 7.10–7.30 (m, 5Harom)-E-
isomer], [0.84 (t, 3H, J¼7 Hz, CH3CH2CH2), 1.37 (sext,
2H, J¼7 Hz, CH3CH2CH2), 1.71 (d, 3H, J¼7 Hz,
CH3CHv), 2.45 (t, 2H, J¼7 Hz, PhCCH2), 5.68 (q, 1H,
J¼7 Hz, CH3CHv), 7.10–7.30 (m, 5Harom)-Z-isomer].
Anal. calcd for C12H16: C, 89.94; H, 10.06. Found: C,
90.17; H, 10.42.
to H NMR); IR (neat) n 2956, 2929, 2871, 2859, 1493,
1448, 794, 742, 698; H NMR (500 MHz, CDCl3) d 0.71
1
1
and 0.92 (t, ,1.5H, J¼7.35 Hz, CH2CH2CH2CH3), [1.10
(mh AB sext, 1.2H), 1.35 (mh b sext, 2H), 1.43–1.56 (mc,
0.8H), CH2CH2CH2CH3], 1.20 and 1.68 (s, ,1.5H,
SCCH3), 1.82 (mc¼superimposed 2 ABdd 14 lines, 2H,
CH2CH2–CH2CH3), 3.93 and 3.95 (s, ,0.5H, PhCHS),
7.20–7.34 (mc, 5Harom); 13C NMR (50 MHz, DEPT,
CDCl3) d 13.8, 14.00 (CH2CH2CH2CH3), 20.7, 22.5, 22.7,
27.9 (CH3), 30.0, 36.0, 43.9 (CH2CH2CH2CH3), 51.4, 52.4
(PhCHS), 52.3 (CH3CCH2CH2CH2CH3), 127.0, 127.8,
129.0, 136.2, 136.4 (C-48) [Carom]; GC (HP50þ15M 50/2/
260 20/min) rt 8.12 min/45.25% and rt 8.42 min/45.42%.
Anal. calcd for C13H18S: C, 75.67; H, 8.79; S, 15.54. Found:
C, 75.92; H, 9.01; S, 15.19.
3.6. Synthesis of trisubstituted episulphides 11 from the
intermediate 2: in one-pot procedure
A solution of SO2Cl2 (2.02 g, 0.015 mol) in CH2Cl2
(10 mL) was added dropwise to O,O,O-triethyl phosphor-
othioate (2.97 g, 0.015 mol) in CH2Cl2 (10 mL) at 258C.
Stirring was continued for 30 min at rt. After removal of
about 80% of solvent, the crude (EtO)2P(O)SCl 6 was added
dropwise to a stirred solution of freshly prepared silyl enol
ether 4 (0.016 mol) in CH2Cl2 (40 mL) at 2788C. Stirring
was continued for additional 1–2 h. The solvent and
Me3SiCl were removed under reduced pressure to give 2.
Then, the crude 2 dissolved in dry CH3OH (20 mL) was
added to a vigorously stirred suspension of NaBH4 (0.76 g,
0.020 mol) in a mixture of CH3OH and Et2O (10:40 mL,
respectively). Stirring was usually continued for about 1 h.
Then the reaction mixture was extracted with 2£50 mL of
pentane, the combined organic phases were washed with
water and dried over MgSO4. Solvent was removed under
reduced pressure and episulphide 11 was analytically pure,
without additional purification.
3.6.4. 2-Hexyl-2-methyl-3-phenyl-thiirane (11d). Yield
3.30 g, 90%, yellow oil isomer ratio¼65:35 (trans/cis)
(according to 1H NMR); IR (neat) n 2964, 2957, 2890, 2859,
1
1494, 1445, 794, 738, 693; H NMR (500 MHz, CDCl3) d
0.82 (t, 0.35£3H, J¼7.1 Hz, CH2CH2CH2CH2CH2CH3),
0.92 (bt, 0.65£3H, J<7.0 Hz, CH2CH2CH2CH2CH2CH3),
1.05–1.20 and 1.30–1.41 (2mc, ,6H, CH2CH2CH2CH2-
CH2CH3), 1.24 (s, ,1.4H, CH3CS), 1.72 (s, ,1.6H,
CH3CS), 1.57 (b quin, 2H, J<7.0 Hz, SCCH2CH2), 1.43
[(ABdd, ,1H, JAB¼13.1 Hz, Jvic1¼10.0 Hz, Jvic2¼5.4 Hz,
dB¼1.49 (from I spectral moment), SCCH2CH2], 1.86
[(ABdd, ,1H, JAB¼13.4 Hz, Jvic1¼9.1 Hz, Jvic2¼6.7 Hz,
dA¼1.81 dB¼1.90 (from I spectral moment), SCCH2CH2],
3.97 (s, 0.65H, PhCHS); 3.99 (s, 0.35H, PhCHS), 7.22–7.40
(mc, 5Harom); 13C NMR (126 MHz, CDCl3) d 13.9, 14.0,
20.7, 22.3, 22.5, 25.5 (CH3), 27.7, 27.8, 27.9, 29.1, 29.2,
29.6, 31.4, 31.7, 36.3, 44.2 (CH2), 51.4, 52.3 (PhCHS), 52.2,
52.3 (CH3C,), 127.0, 127.7, 127.8, 128.9, 129.0, 136.2,
136.4 (Carom). Anal. calcd for C15H22S: C, 76.86; H, 9.46; S,
13.68. Found: C, 76.89; H, 9.50; S, 13.62.
3.6.1. 2,2-Dimethyl-3-phenyl-thiirane (11a). Yield 5.11 g,
93%, colorless liquid; IR (neat) n 2975, 2956, 2918, 1493,

6064
I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
3.6.5. 2-Benzyl-2-methyl-3-phenyl-thiirane (11e). Yield
2.14 g, 83%, dendritic white needles, mp 33.5–34.58C
(pentane), isomer ratio¼56:44 (trans/cis) (according to H
graphy on silica gel, using a mixture of pentane and
petroleum ether, and then benzene as eluent.
1
NMR); IR (neat) n 3026, 2918, 1493, 1450, 795, 756, 733,
698; 1H NMR (500 MHz, CDCl3) d 1.17 and 1.61 (s,
,1.5H, CH3CCH2Ph), 2.65 (AB, ,1H, JAB¼14.15 Hz,
dA¼2.52 dB¼2.79, CH3CCH2Ph, isomer 1), 3.16 (AB,
,1H, JAB¼13.66 Hz, dA¼3.14 dB¼3.18, CH3CCH2Ph,
isomer 2), 4.07 and 4.17 (s, ,0.5H, PhCHS), 7.10–7.49
(mc, 10Harom); 13C NMR (50 MHz, DEPT, CDCl3) d 20.9,
27.9 (PhCH2CCH3), 42.3, 49.7 (PhCH2CCH3), 50.6, 51.6
(PhCHS), 52.0, 52.3 (PhCH2CCH3), 126.4, 126.8, 127.2,
127.4, 127.9, 128.1, 128.3, 129.0, 129.2, 129.44, 129.5,
131.1, 136.1 (C-48), 138.4 (C-48), 138.9 (C-48)–Carom; GC
(HP50þ15M 50/2/260 20/min) rt 9.630 min/49.34% and rt
9.775 min/37.39%. Anal. calcd for C16H16S: C, 80.06; H,
7.06; S, 12.89. Found: C, 79.95; H, 6.71; S, 12.34.
3.7.1. (2,3-Dimethyl-but-1-enyl)-benzene (12b). Yield
1.05 g, 43%, yellow liquid, isomer ratio¼67:33 (E/Z)
(according to 1H NMR); IR (neat) n 1596 (CvC); 1H
NMR (500 MHz, CDCl3) d [0.99 (d, 3H, J¼6.83 Hz)-minor,
1.07 (d, 3H, J¼6.77 Hz)-major, (CH3)2CHCv], [1.75 (s,
3H)-minor, 1.78 (s, 3H)-major, CH3Cv], 2.38 (sept, 1H,
J¼6.83 Hz)-major, 2.62 (sept, 1H, J¼6.65 Hz)-minor,
(CH3)2CHCv], [6.17 (s, 1H)-minor, 6.25 (s, 1H)-major,
CHvC–CH3], 7.10–7.55 (m, 5Harom). Anal. calcd for
C12H16: C, 89.94; H, 10.06. Found: C, 89.74; H, 10.00.
3.7.2. (2-Methyl-hex-1-enyl)-benzene (12c).19 Yield
0.83 g, 56%, light yellow oil, isomer ratio¼53:47 (Z/E)
(according to 1H NMR); IR (neat) n 1600, 1595 (CvC); 1H
NMR (500 MHz, CDCl3) d [0.87 (t, 3H, J¼7.51 Hz)-major,
0.92 (t, 3H, J¼7.30 Hz)-minor, CH3CH2–CH2CH2], 1.20–
1.50 (m, 4H, CH3CH2–CH2CH2)-both isomers, 1.82 and
1.85 (s, 3H, CH3Cv)-both isomers, [2.14 (dd<quasi t, 2H,
J¼7.58 Hz)-minor, 2.19 (b dd<quasi t, 2H, J<7.30 Hz)-
major, CH3CH2CH2CH2], 6.23 (b s, 1H, PhCHvC), 7.10–
7.53 (m, 5Harom). Anal. calcd for C13H18: C, 89.59; H,
10.41. Found: C, 89.41; H, 10.28.
3.6.6. 2-Methyl-2,3-diphenyl-thiirane (11f). Yield 1.83 g,
78%, pale yellow oil, isomer ratio¼72:28 (cis/trans)
1
(according to H NMR); IR (neat) n 1493, 1446, 762, 696;
1H NMR (500 MHz, CDCl3) d 1.59 and 2.03 (2s, 3H, CH3),
4.16 and 4.34 (2s, 1H, PhCHS), 6.98–7.55 (m, 10Harom);
13C NMR (50 MHz, DEPT, CDCl3) d 24.4, 33.3 (CH3),
51.4, 51.7 (PhCHS), 52.8, 56.0 (CH3CPh), 126.8, 127.0,
127.1, 127.2, 127.4, 127.5, 128.1, 128.3, 128.5, 128.7,
129.1, 129.6, 135.8 (C-48), 136.2 (C-48), 140.0 (C-48), 144.8
3.7.3. (2-Methyl-oct-1-enyl)-benzene (12d). Yield 0.54 g,
81%, light yellow oil, isomer ratio¼66:34 (E/Z) (according
(C-48)-Carom
;
GC (HP50þ15M 50/2/260 20/min) rt
1
1
9.354 min/100.00%-both isomers. Anal. calcd for
C15H14S: C, 79.60; H, 6.23; S, 14.16. Found: C, 80.01; H,
6.51; S, 13.89.
to H NMR); IR (neat) n 1606, 1599 (CvC); H NMR
(500 MHz, CDCl3) d 0.79–0.90 [m<2t, 3H, CH3(CH2)5]-
both isomers, 1.15–1.49 [mc, 8H, CH3(CH2)4CH2]-both
isomers, [1.16 (s, 3H)-major, 1.77 (s, 3H)-minor, CH3Cv],
[1.92 (dd, 2H, J<7.80 Hz)-major, 2.14 (dd, 2H,
J<7.70 Hz)-minor, CH3(CH2)4–CH2], [6.09 (s, 1H)-
minor, 6.24 (s, 1H)-major, PhCHvC], 7.12–7.54 (mc,
5Harom). Anal. calcd for C15H22: C, 89.04; H, 10.96. Found:
C, 88.90; H, 10.70.
3.6.7. 3-Isopropyl-2,2-dimethyl-thiirane (11g). Yield
7.23 g, 64%, colorless liquid; IR (neat) n 2960, 2929, 2869,
1465, 663, 565; 1H NMR (500 MHz, CDCl3) d 1.06 and 1.13
[d, 3H, J¼6.60 Hz, (CH3)2CHCHS], 1.52 [dquinh dsept, 1H,
J¼10.10 Hz, J2¼6.77 Hz, (CH3)2CHCHS], 1.58 and 1.59 [s,
3H, (CH3)2C,], 2.51 [d, 1H, J¼10.10 Hz, (CH3)2CHCHS];
13C NMR (50 MHz, DEPT, CDCl3) d 21.2, 30.8 [(CH3)2C,],
22.7, 22.8 [(CH3)2CHCHS], 31.5 [(CH3)2CHCHS], 47.4
[(CH3)2C,], 58.0 [(CH3)2CHCHS]. Anal. calcd for
C7H14S: C, 64.55; H, 10.83. Found: C, 64.79; H, 11.00.
3.7.4. 1,3-Diphenyl-2-methyl-prop-1-ene (12e)5(10b).18
Yield 1.13 g, 53%, colorless oil, isomer ratio¼55:45 (E/Z)
1
(according to H NMR).
3.8. Synthesis of tetrasubstituted alkenes 13 from 1 or 2:
general procedure
3.6.8. 2-Phenyl-1-thia-spiro[2.2]pentane (11h). Yield
2.41 g, 50%, pale yellow oil; IR (neat) n 2949, 2859,
1496, 1452, 784, 737, 690; H NMR (500 MHz, CDCl3) d
1
The selenophosphate 1 (0.010 mol) or thiophosphate 2
(0.010 mol) dissolved in DME (10 mL) was added dropwise
to a stirred solution of KCN (1.14 g, 0.017 mol) and 18-
crown-6 ether (20 mg) in dry DME (40 mL) at rt. Stirring
was usually continued for 24 h. Then the reaction mixture
was extracted with 2£50 mL using a mixture of pentane and
diethyl ether (1:1), the combined organic phases were
washed with water and dried over MgSO4. Solvent was
removed under reduced pressure and alkene 13 was purified
by flash chromatography on silica gel using benzene as
eluent.
[2.76 (dt, 1H, J1¼14.76 Hz, J2¼6.93 Hz), 3.38 (dd, 1H,
J1¼14.99 Hz, J2¼6.99 Hz), 5.74 (dt, 1H, J1¼15.27 Hz,
J2¼6.72 Hz), 5.82 (dd, 1H, J1¼15.22 Hz, J2¼6.02 Hz),
–CH2–CH2-], 5.50 (s, 0.5H, PhCHS), 5.51 (s, 0.5H,
PhCHS), 7.15–7.30 (mc, 5Harom); 13C NMR (126 MHz,
CDCl3) d 15.02, 15.78, 15.84 (–CH2–CH2–), 63.46, 63.65
(SC,), 65.61 (PhCHS), 126.11, 128.15, 128.23, 136.42
(Carom). Anal. calcd for C10H10S: C, 70.03; H, 6.21; S,
19.76. Found: C, 69.79; H, 5.99; S, 19.10.
3.7. Synthesis of trisubstituted alkenes 12 from
episulphides 11: general procedure
3.8.1. 3-Methyl-2-phenyl-but-2-enenitrile (13a). Yield
2.82 g, 73%, pale yellow oil; SiO2-TLC (C6H6/
C6H14¼5:1), Rf¼0.49; IR (neat) n 2210 (CuN), 1602
(ArCvC); 1H NMR (200 MHz, CDCl3) d 1.92 and 2.26 [s,
3H, (CH3)2Cv], 7.26–7.44 (m, 5Harom); 13C NMR
(50 MHz, CDCl3) d 21.34, 24.67 [(CH3)2Cv], 111.10
To the appropriate episulphide 11 (0.010 mol) triethyl
phosphite (excess, 5 mL) was added and the mixture was
refluxed for 2–4 h. After removal in vacuo of the excess of
phosphite, the residue was purified by column chromato-

I. Macia˛giewicz et al. / Tetrahedron 59 (2003) 6057–6066
6065
(NuC–CvC), 118.59 (CuN), [127.98, 128.38, 128.82,
133.91 (C-48)-Carom], 154.46 (NuC–C¼C); GC
(HP50þ15M 50/2/260 20/min) rt 7.806 min/93.338%.
Anal. calcd for C11H11N: C, 84.04; H, 7.05; N, 8.91.
Found: C, 83.34; H, 7.23; N, 9.19.
3.8.6. 3-Methyl-2,4-diphenyl-but-2-enenitrile
(13f)5(13e). Yield 1.82 g, 62%, pale yellow mass, isomer
ratio¼55:45 (Z/E) (according to 1H NMR); SiO2-TLC (C6H6/
C6H14¼5:1), Rf¼0.62 and 0.57; IR (neat) n 2211 (CuN),
1616 (ArCvC), 1601, 1584 (Ar); 1H NMR (200 MHz,
CDCl3) d 1.81 (s, 3H, CH3Cv)-minor, 2.15 (s, 3H, CH3Cv)-
major), 3.58 (s, 3H, PhCH2Cv)-major 3.91 (s, 3H, PhCH2-
Cv)-minor, 7.05–7.08 and 7.26–7.41 (m, 20Harom, both
isomers); 13C NMR (50 MHz, CDCl3) d 19.12, 22.11
(CH3Cv), 39.84, 44.39 (PhCH2Cv), 111.56, 112.46
(NuC–CvC), 118.49, 118.91 (CN), [126.70, 126.88,
128.02, 128.30, 128.44, 128.67, 128.79, 129.03, 133.68 (C-
48), 133.77 (C-48)-Carom], 155.98, 156.51 (NuC–CvC–);
GC (HP50þ15M 50/2/260 20/min) rt 11.198 min/61.563%
and rt 11.274 min/34.627%. Anal. calcd for C17H15N: C,
87.51; H, 6.48; N, 6.00. Found: C, 86.21; H, 7.00; N, 6.00.
3.8.2. 3-Methyl-2-phenyl-pent-2-enenitrile (13b).13d
Yield 3.02 g, 82%, pale yellow oil, isomer ratio¼53:47
(Z/E)
(according
to
1H
NMR);
SiO2-TLC
(C6H6/C6H14¼5:1), Rf¼0.64; IR (neat) n 2210 (CuN),
1619 (ArCvC); 1H NMR (200 MHz, CDCl3) d 1.06 (t, 3H,
J¼7.57 Hz, CH3CH2Cv)-minor, 1.22 (t, 3H, J¼7.54 Hz,
CH3CH2Cv)-major, 1.89 (s, 3H, CH3Cv)-major, 2.23
(s, 3H, CH3Cv)-minor, 2.22 (q, 2H, J¼7.58 Hz,
CH3CH2Cv)-minor, 2.60 (q, 2H, J¼7.54 Hz, CH3CH2-
Cv)-major, 7.24–7.55 (m, 10Harom)-both isomers; 13C
NMR (50 MHz, DEPT, CDCl3) d 12.10, 12.24 (CH3CH2-
Cv), 18.71, 21.42 (CH3Cv), 27.17, 31.49 (CH3CH2Cv),
109.89, 110.42 (NC–CvC–), 118.28, 118.58 (CN),
159.55, 159.80 (NC–CvC–), [126.97, 127.91, 128.31,
128.42, 128.60, 128.81, 133.83 (C-48), 133.92 (C-48)-
Carom]; GC (HP50þ15M 50/2/260 20/min) rt
8.156 min/85.15%-both isomers. Anal. calcd for C12H13N:
C, 84.17; H, 7.65; N, 8.18. Found: C, 83.92; H, 8.03; N, 7.13.
3.8.7. 2,3-Diphenyl-but-2-enenitrile (13g). Yield 1.71 g,
60%, yellow oil, isomer ratio¼75:25 (Z/E) (according to 1H
NMR); E-isomer—colorless needles, mp 65–66.58C; SiO2-
TLC (C6H6/C6H14¼5:1), Rf¼0.64 and 0.61; IR (neat) n
1
2211 (CuN), 1597, 1582 (ArCvC); H NMR (300 MHz,
CDCl3) d 2.25 (s, 3H, CH3Cv)-minor, 2.59 (s, 3H,
CH3Cv)-major, 7.05–7.54 and 7.94–7.97 (m, 20Harom)-
both isomers; 13C NMR (50 MHz, CDCl3) d 19.32
(CH3Cv)-major, 21.90 (CH3Cv)-minor, 113.05, 154.87
(NC–CvC), 118.93 (CuN), 125.51–138.96-Carom. Anal.
calcd for C16H13N: C, 87.64; H, 5.98; N, 6.39. Found: C,
86.40; H, 6.00; N, 6.21.
3.8.3. 3,4-Dimethyl-2-phenyl-pent-2-enenitrile (13c).
Yield 2.78 g, 90%, yellow oil, isomer ratio¼73:27 (Z/E)
1
(according to H NMR); SiO2-TLC (C6H6), Rf¼0.63 and
0.59; IR (neat) n 2209 (CuN), 1615 (CvC), [1444.56,
762.23, 701.09 (Ph)]; H NMR (200 MHz, CDCl3) d [1.01
1
(d, 6H, J¼6.81 Hz)-minor, 1.16 (d, 6H, J¼6.78 Hz)-major,
(CH3)2CH], [1.78 (s, 3H)-major, 2.14 (s, 3H)-minor,
CH3Cv], [2.87 (sept, 1H, J¼6.78 Hz)-minor, 3.37 (sept,
1H, J¼6.78 Hz)-major, (CH3)2CH], 7.23–7.45 (m, 5Harom);
MS/CI (isobutane) 186.1 (Mþ1). Anal. calcd for C13H15N:
C, 84.28; H, 8.16; N, 7.56. Found: C, 84.11; H, 8.28; N,
7.64.
3.8.8. 2,3-Diphenyl-pent-2-enenitrile (13h). Yield 1.22 g,
71%, pale yellow mass, isomer ratio¼90:10 (Z/E) (accord-
ing to 1H NMR); IR (neat) n 2210 (CuN), 1582 (CvC); 1H
NMR (500 MHz, CDCl3) d [0.95 (t, 3H, J¼7.5 Hz, CH3-
CH2Cv), 2.60 (q, 2H, J¼7.5 Hz, CH3CH2Cv), 7.20–7.50
(mc, 10Harom)-major], [1.03 (t, 3H, J¼7.5 Hz, CH3CH2-
Cv), 3.09 (q, 2H, J¼7.5 Hz, CH3CH2Cv), 7.20–7.50 (mc,
10Harom)-minor]. Anal. calcd for C17H15N: C, 87.52; H,
6.48; N, 6.00. Found: C, 87.54; H, 6.50; N, 5.99.
3.8.4. 3-Methyl-2-phenyl-hept-2-enenitrile (13d). Yield
1.54 g, 72%, yellow oil, isomer ratio¼63:37 (Z/E) (accord-
1
ing to H NMR); SiO2-TLC (C6H6/C6H14¼5:1), Rf¼0.64
3.8.9. 2-Isopropyl-3-methyl-but-2-enenitrile (13i). Yield
1.66 g, 77%, pale yellow oil; SiO2-TLC (C6H6/C6H14¼5:1),
and 0.57; IR (neat) n 2211 (CuN), 1617 (CvC); 1H NMR
(500 MHz, CDCl3) d [0.78 (t, 3H, J¼7.32 Hz)-minor, 0.94
(t, 3H, J¼7.32 Hz)-major, CH3CH2–CH2CH2], [1.18 (sext,
2H, J¼7.34 Hz)-minor, 1.40 (sext, 2H, J¼7.37 Hz)-major,
CH3CH2CH2CH2], [1.39 (quin, 2H, J¼7.60 Hz)-minor,
1.55 (quin, 2H, J¼7.59 Hz)-major, CH3CH2CH2CH2],
[1.85 (s, 3H)-major, 2.19 (s, 3H)-minor, CH3Cv], [2.15
(m<dd, 2H, J<7.80 Hz)-minor, 2.55 (m<dd, 2H,
J<7.70 Hz)-major, CH3CH2CH2CH2], 7.21–7.36 (mc,
5Harom); 13C NMR (50 MHz, DEPT, CDCl3) d 13.42,
13.63 (CH3CH2CH2CH2), 19.20, 21.87 (CH3Cv), 22.15,
29.59, 29.83, 33.68, 38.07 (CH3CH2CH2CH2), 110.51,
110.75 (CN–CvC), 118.45, 118.59 (CN), [127.91,
128.32, 128.38, 128.71, 128.81, 133.90 (C-48)-Carom],
158.54 (CN–CvC–CH3); GC (HP50þ15M 50/2/260 20/
min) rt 8.96 min/63.279% and rt 9.07 min/35.063%. Anal.
calcd for C14H17N: C, 84.37; H, 8.60; N, 7.03. Found: C,
84.15; H, 9.08; N, 7.23.
1
Rf¼0.59; IR (neat) n 2210 (CuN), 1635 (CvC); H NMR
(200 MHz, CDCl3) d 1.10 [d, 6H, J¼6.80 Hz, (CH3)2CH],
1.84 and 2.04 [s, 3H, Me2Cv], 2.75 [sept, 1H, J¼6.80 Hz,
(CH3)2CH];13C NMR (50 MHz, CDCl3) d 20.93 [(CH3)2CH],
24.41, 27.70 [(CH3)2Cv], 76.99 [(CH3)2CH], 116.36 (NC–
Cv), 117.26 (CN), 149.18 [CvC(CH3)2]; GC (HP50þ15M
50/2/260 20/min) rt 4.349 min/98.877%. Anal. calcd for
C8H13N: C, 77.99; H, 10.64. Found: C, 77.83; H, 10.66.
Acknowledgements
This work was supported by the Polish State Committee for
Scientific Research (grant 3T09A 10018).
References
3.8.5. 3-Methyl-2,4-diphenyl-but-2-enenitrile
(13e)5(13f). Yield 2.00 g, 63%, pale yellow mass, isomer
ratio¼80:20 (Z/E) (according to H NMR).
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