Reaction of bicyclo[2.2.1]hepta-2,5-diene with the arenesulfenamide-phosphorus(v) oxohalide system: Chemo-, regio-, and steroselectivity

Article abstract of DOI:10.1023/A:1020910906470

The chemo-, regio- and stereoselectivities of electrophilic sulfenylation of bicyclo[2.2.1]hepta-2,5-diene with arenesulfenamides activated by phosphorus(v) oxohalides were studied. The ratio of the products of endo- to exo-attack of the diene by the electrophilic species depends on the solvent nature. The proportions of the products formed upon addition to one double bond and upon homoallylic participation of the second double bond depend on solvent polarity, the nature of the halogen, the substituents in the sulfenamide benzene ring, and on the reaction time. In addition, the formation of mixed adducts was proven for the reaction carried out in acetonitrile and the formation of disulfenylation products was found in the reaction with excess sulfenylating reagent. Isomerization of exo-3-arylthio-endo-2-halobicyclo[2.2.1]hept-5-enes to the products formed with homoallylic participation of the second double bond, exo-5-arylthio-endo-3-halotricyclo[2.2.1.0^2,6]heptanes, was shown to be possible.

Full text of DOI:10.1023/A:1020910906470

1468
Russian Chemical Bulletin, International Edition, Vol. 51, No. 8, pp. 1468—1477, August, 2002
Reaction of bicyclo[2.2.1]heptaꢀ2,5ꢀdiene
with the arenesulfenamide—phosphorus(V) oxohalide system:
chemoꢀ, regioꢀ, and steroselectivity
N. V. Zyk, E. K. Beloglazkina,ꢀ M. A. Belova,ꢀ I. F. Leshcheva, and N. S. Zefirov
Department of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (095) 939 0290. Eꢀmail: bel@org.chem.msu.su
The chemoꢀ, regioꢀ and stereoselectivities of electrophilic sulfenylation of biꢀ
cyclo[2.2.1]heptaꢀ2,5ꢀdiene with arenesulfenamides activated by phosphorus(V) oxohalides
were studied. The ratio of the products of endoꢀ to exoꢀattack of the diene by the electrophilic
species depends on the solvent nature. The proportions of the products formed upon addition
to one double bond and upon homoallylic participation of the second double bond depend on
solvent polarity, the nature of the halogen, the substituents in the sulfenamide benzene ring,
and on the reaction time. In addition, the formation of mixed adducts was proven for the
reaction carried out in acetonitrile and the formation of disulfenylation products was found
in the reaction with excess sulfenylating reagent. Isomerization of exoꢀ3ꢀarylthioꢀendoꢀ2ꢀhaloꢀ
bicyclo[2.2.1]heptꢀ5ꢀenes to the products formed with homoallylic participation of the secꢀ
ond double bond, exoꢀ5ꢀarylthioꢀendoꢀ3ꢀhalotricyclo[2.2.1.02,6]heptanes, was shown to be
possible.
Key words: arenesulfenamides, phosphorus(V) oxohalides, bicyclo[2.2.1]heptaꢀ2,5ꢀdiene,
sulfenylation, isomerization.
The new method of halosulfenylation of unsaturated
compounds with the arenesulfenamide—phosphorus oxoꢀ
halide system proposed in our previous study1 gave good
results for alkenes1 and alkynes.2 Owing to high yields
and ready availability and stability of the initial reacꢀ
tants, this method may be regarded as an alternative to
the existing methods of chloroꢀ and bromosulfenylation
of unsaturated compounds (see, for example, Refs. 3—12).
To continue our research, we studied the reaction of
arenesulfenamides activated by phosphorus(V) oxohalides
with bicyclo[2.2.1]heptaꢀ2,5ꢀdiene (norbornadiene),
which is a convenient substrate for elucidation of the
reaction mechanisms.
Arenesulfenamides as such are weak electrophiles unꢀ
able to add to multiple bonds; however, on treatment
with POCl3 or POBr3, they form active complexes, which
we identify conventionally as having structure 10 where
the positive charge on sulfur is higher than in the initial
sulfenamide1 (Scheme 2).
The 1H and 13C NMR spectra recorded for a mixture
of Nꢀ(pꢀnitrophenylthio)morpholine (2a)—phosphorus
oxochloride (3a) (1 : 1) in CDCl3 contain signals of the
initial sulfenamide 2a and an additional set of signals for
the aromatic system and the morpholine ring, which we
attribute to the formation of complex 10 (Table 2). After
addition of the olefin, the signals assigned to complex 10
disappear over a period of several minutes being replaced
by sets of signals due to the product of addition at the
C=C bond and phosphorous acid monoamide dichloꢀ
ride 11 (see Table 2 and Experimental).
Results and Discussion
We studied reactions of norbornadiene (1) with
Nꢀ(pꢀnitrophenylthio)morpholine (2a), Nꢀ(oꢀnitroꢀ
phenylthio)morpholine (2b), and Nꢀphenylthiomorꢀ
pholine (2c) in the presence of phosphorus oxochloride
(3a) and oxobromide (3b) in various solvents (Scheme 1).
These reactions in CH2Cl2 and AcOEt give isomeric
βꢀ (4, 5) and γꢀhalosulfides (6, 7). In MeCN, γꢀNꢀacetꢀ
amidosulfides 8 and 9 are formed apart from halosulfides.
Data on the product yields and ratios are listed in
Table 1.
Previously,15 it was shown that in the case of thiobisꢀ
morpholine, phosphorus oxohalide is coordinated to one
N atom; the 1H and 13C NMR spectra exhibit signals for
two nonequivalent morpholine rings, one exhibiting spinꢀ
spin coupling constants with the phosphorus nucleus.
1
The absence of spinꢀspin coupling constants for the H
or 13C nuclei of the morpholine ring with the 31P nuclei
in this particular case of sulfenamide activation is an
argument for the assumption that in complex 10, phosꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1356—1364, August, 2002.
1066ꢀ5285/02/5108ꢀ1468 $27.00 © 2002 Plenum Publishing Corporation

Sulfenylation of bicyclo[2.2.1]heptꢀ2,5ꢀdiene
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1469
Scheme 1
Scheme 2
phorus oxohalide is coordinated to the sulfenamide S
atom (Fig. 1) rather than to the N atom. Data of PM3
semiempirical quantumꢀmechanical calculations are conꢀ
sistent with the assumption that phosphorus oxohalide is
coordinated to the S atom of sulfenamide. The optiꢀ
mized geometry of complex 10 is shown in Fig. 1.
The addition of complex 10 to norbornadiene (1)
yields an intermediate that can be successfully described
in terms of the ionꢀpair mechanism concept, which has
been widely discussed previously.16,17
2: Ar = 4ꢀNO2C6H4 (a), 2ꢀNO2C6H4 (b), Ph (c)
3: Hal = Cl (a), Br (b)
4—7: Hal = Cl (a—c), Br (d—f);
Ar = 4ꢀNO2C6H4 (a, d), 2ꢀNO2C6H4 (b, e), Ph (c, f)
8, 9: Ar = 2ꢀNO2C6H4
Table 1. Product yields in the reactions of arenesulfenamides 2a—c activated by phosphorus(V) oxohalides with bicyclo[2.2.1]heptaꢀ
2,5ꢀdiene (1) (the yields of similar products obtained in the sulfenylation of the same olefin with arylsulfenyl chloride are given for
comparison13
)
Sulfenꢀ POHal3
amide
Solvent
t a/h
Productsb (%)
of the exoꢀattack
7
Overall
yield (%)
of the
endoꢀattack
4
Ar2S
5
6
8
9
2a
2b
2c
2a
2b
2c
2b
2c
2b
2b
2b
3a
3a
3a
3b
3b
3b
3a
3a
3a
3a
3a
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
AcOEt
2
2
3
1.5
1.5
4
48
120
2
30
20
23
20
22
23
18
23
31
17
39
20
11
24
47
40
43
57
14
—
44
—
—
70
59
56
30
40
35
19
47
57
25
2
—
—
—
—
—
—
19
20
—
—
—
—
—
—
—
—
—
—
—
—
—
21
13
—
—
—
—
—
—
—
—
—
—
49
30
—
—
—
—
—
—
—
—
—
—
78
78
34
100
76
43
78
34
57
47
50
81
c
MeCN
MeCN d
CCl4
2
2
11
14
—
c
4
10
2ꢀNO2ꢀC6H4SCl
a Reaction time.
b Approximate contents of products in the reaction mixture determined from H NMR spectroscopy data are given.
c Rf 0.33 (AcOEt—petroleum ether, 1 : 3), m.p. 119—121 °C (cf. Ref. 14: m.p. 122—123 °C).
d The reaction was carried out in the presence of LiClO4 (doping conditions).
1

1470
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Zyk et al.
Table 2. 1H and 13C NMR spectra of compounds 2a, 11 and sulfenylating reagents 10, 14 in CDCl3 (for comꢀ
pounds 2a, 10, 11) or CD3CN (for compound 14)
Comꢀ
pound
δ
H (JH,H/Hz)
δ
C
2a
10
11
8.15, 7.42 (J = 9.0)
8.22, 7.58 (J = 9.1)

3.79, 3.10 (J = 4.7)
149.9, 145.0, 123.7, 122.4
146.6, 144.4, 125.6, 123.9

67.5, 56.0
63.5, 43.3
65.1 (d, JC,P = 7.4);
44.2 (d, JC,P = 1.4)
3.96, 3.21 (J = 4.3)
3.68 (dt, 4 H, J = 4.9,
JH,P = 2.1);
3.28 (dt, 4 H, J = 4.9,
JH,P = 4.9)

14
8.12, 7.74 (J = 9.1)


1
Note. The H NMR spectra of the 4ꢀNO2C6H4S fragment exhibit an AA´BB´ system; the JA,B constant is given. The
1H NMR spectra of the morpholine fragment represent an A2B2 system; the JA,B constant is given.
The reactions carried out in solvents with different
more electronegative chlorine is better solvated by solꢀ
vent molecules, which shifts equilibrium toward the solꢀ
ventꢀseparated ion pair and increases the yield of norꢀ
tricyclane products.
It was found that the proportion of 1,2ꢀadduct 5 in
the reaction mixture decreases with time, while the proꢀ
portion of compound 6 increases, and in some cases,
initially missing 3,5ꢀdiꢀexoꢀsubstituted nortricyclane 7 is
also formed. Probably, the formation of product 5
(1,2ꢀexoꢀaddition) is reversible, and over a period of two
days, thermodynamic equilibrium is established in the
reaction mixture, resulting in the set of products we
observe.
The possibility of 5 → 6 isomerisation is also conꢀ
firmed by experiment: on stirring of a 22 : 43 : 35 mixꢀ
ture of 4e, 5e, and 6e with a solution of Nꢀ(оꢀnitroꢀ
phenylthio)morpholine (2b) activated by POBr3 (3b),
di(arylthio)dihalonorbornanes 12 and 13, resulting from
addition of the second equivalent of the reagent to the
second double bond, were isolated together with comꢀ
pound 6e (the 6e : 12 : 13 ratio was 55 : 37 : 8). It is
evident that the increase in the content of product 6e in
the mixture is due to transformation of some of alkene
5e into nortricyclane 6e.
polarities result in different ratios of the products resultꢀ
ing from exoꢀ and endoꢀattacks of the diene system (see
Table 1). This can be explained as follows: the endoꢀattack
is preferred from the standpoint of electronic factors
because in this case, the electrophile can be coordinated
simultaneously to two double bonds, while the exoꢀatꢀ
tack is better for steric reasons. Thus, in less polar solꢀ
vents in which the electrophilic species is less solvated
and, hence, less bulky, the reaction should yield a greater
amount of the endoꢀattack product than in more polar
solvents. Indeed, in AcOEt (ε = 6.02),18 the endoꢀ to
exoꢀattack product ratio is 31 : 69, that in CH2Cl2
(ε = 8.9)18 is 20 : 80, while in MeCN (ε = 36.2),18 this
ratio is 17 : 83.
The amount of nortricyclane products formed in the
reaction depends also on the nature of the halogen in
POHal3. Indeed, when POCl3 is used for activation, the
proportion of products 6 is substantially higher than that
obtained in the presence of POBr3 (cf. rows 1 and 4, 2
and 5, 3 and 6 in Table 1). Apparently, the less bulky and
It should be noted that product 13 could have formed
from compound 5e only in the case of exoꢀattack by the
electrophilic species at the second double bond. If 5e → 4e
isomerization is considered impossible, compound 12
can be formed both from 5e due to endoꢀattack of the
sulfenylating reagent and from 4e due to exoꢀaddition of
ArS+ (Scheme 3).
The use of strong electrolytes (for example, LiClO4)
as polar additives in olefin sulfenylation increases the
medium polarity and, as a consequence, increases the
proportion of rearranged products (doping effect).17 Inꢀ
deed, when MeCN is used as the solvent in POHal3ꢀacꢀ
tivated sulfenylation of norbornadiene, 3ꢀarylthioꢀ5ꢀNꢀ
acetamidotricyclo[2.2.1.02,6]heptanes 8 and 9 are formed
Fig. 1. Structure of the Nꢀ(pꢀnitrophenylthio)morphoꢀ
line—phosphorus(V) oxochloride complex from the data of PM3
semiempirical quantumꢀmechanical calculations.

Sulfenylation of bicyclo[2.2.1]heptꢀ2,5ꢀdiene
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1471
Scheme 3
as the major products. However, the formation of subꢀ
stantial amounts (11—14%) of diaryl sulfide (which is
not observed when the reaction is carried out in other
solvents) and the unexpected ratio of products obtained
in the presence of LiClO4 (see Table 1) suggest that in
MeCN, the reaction of the arenesulfenamide—phosphoꢀ
rus oxohalide system with norbornadiene (1) proceeds
via the formation of sulfenylating reagent of a different
structure. Probably, new sulfenylating complex 14 is
formed when complex 10 reacts with MeCN molecule
(Scheme 4).
from these signals, the spectrum contains signals for comꢀ
pound 11 and an additional set of signals, which may be
attributed to a new electrophilic complex 14.
The structures of the reaction products were estabꢀ
1
lished by H and 13C NMR spectroscopy (Tables 3—5).
Analysis of the spectra and the subsequent structural
assignments were based on published data on the influꢀ
ence of substituents on the chemical shifts, on the
1H—1H spinꢀspin coupling constants, and on the nuclear
Overhauser effect (NOE) data.
The 1H NMR spectra of products 4 and 5 (see Table 3)
contain signals of olefinic protons, and the magnitude of
the spinꢀspin coupling constant for the protons at subꢀ
stituents (J2,3 = 2.6—3.4 Hz) indicates that these comꢀ
pounds result from 1,2ꢀaddition to one double bond and
attests to transꢀpositions of the arylthio group and the
halogen atom, because transꢀvicinal derivatives of norꢀ
bornane are normally characterized by J2,3 = 2.5—5.0 Hz,
while for cisꢀderivatives, J2,3 = 6—10 Hz.18 The spectroꢀ
scopic characteristics of compounds 4 and 5 correspond
to those reported previously.16
Scheme 4
Products 6b and 7b were isolated as a mixture. The
signals for the H(3) and H(5) protons in the major isoꢀ
mer 6b occur at δ 4.12 and 4.08, respectively. In the case
of isomer 7b, these signals are at about δ 4.04 and 3.36. As
shown previously,19 a substantial upfield shift of the H(5)
signal is due to a change in the orientation (endo→exo)
of the substituent at C(3). This suggests that comꢀ
pound 6b is exoꢀ5ꢀ(оꢀnitrophenylthio)ꢀendoꢀ3ꢀchloroꢀ
tricyclo[2.2.1.02,6]heptane, and 7b is exoꢀ5ꢀ(oꢀnitroꢀ
phenylthio)ꢀexoꢀ3ꢀchlorotricyclo[2.2.1.02,6]heptane.
1
Thus the H and 13C NMR spectra of a Nꢀ(pꢀnitroꢀ
phenylthio)morpholine (2a)—phosphorus oxochloride
(3a) mixture in CDCl3 exhibit signals for the initial
sulfenamide and complex 10, whereas in CD3CN, apart

1472
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Zyk et al.
1
Table 3. H NMR spectra of compounds 4—13 in CDCl3
Comꢀ
pound
δ (JH,H/Hz)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7), H(7´)
2.10 (dt, J7,7´
Other
signals
4a
3.17
(br.s)
3.81 (t,
3.71 (t,
3.13
(br.s)
6.23 (dd,
J5,6 = 5.7,
J5,4 = 3.3)
6.31 (dd,
J6,5 = 5.7, 9.4, J7,1 =
J6,1 = 2.9) J7,4 = 1.3);
=
8.12, 7.48 a
J2,3
≈
J3,2
≈
J
2,7´ = 2.8)
J3,4 = 2.3)
1.85 (dq,
J
7,7´ = 9.4,
J7´,1 = J7´,4
J7´,2 = 1.9)
2.11 (d,
=
=
=
=
4b
4c
4d
3.19
(br.s)
3.79 (t,
J2,3
2,7´ = 2.9)
3.75 (t,
3.14
(br.s)
6.22 (dd,
J5,6 = 5.6,
J5,4 = 3.2)
6.37 (dd,
J6,5 = 5.6,
8.14, 7.82,
7.59, 7.25 b
≈
J3,2
≈
J7,7´ = 9.3);
J
J3,4 = 2.1)
J6,1 = 2.7) 1.85 (dq,
7,7´ = 9.3,
J
J7´,1 = J7´,4
J7´,2 = 1.8)
1.97 (d,
3.05
(br.s)
3.66 (t,
J2,3
2,7´ = 2.1)
3.64 (t,
3.02
(br.s)
6.16 (dd,
J5,6 = 5.3,
J5,4 = 3.0)
6.29 (dd,
J6,5 = 5.3,
7.44—7.25
(m)c
≈
J3,2
≈
J7,7´ = 9.3);
J
J3,4 = 2.9)
J6,1 = 3.0) 1.75 (dq,
7,7´ = 9.2,
J
J7´,1 = J7´,4
J7´,2 = 1.8)
2.14 (d,
3.20
(br.s)
3.97 (t,
J2,3
2,7´ = 3.0)
3.66 (t,
3.16
(br.s)
6.22 (dd,
J5,6 = 5.6,
J5,4 = 3.3)
6.28 (dd,
J6,5 = 5.6,
8.12, 7.48 a
≈
J3,2
≈
J7,7´ = 9.5);
J
J3,4 = 2.4)
J6,1 = 2.7) 1.87 (dq,
7,7´ = 9.5,
J
J7´,1 = J7´,4
J7´,2 = 1.9)
2.17 (d,
4e
4f
3.24
(br.s)
3.95 (t,
J2,3
2,7´ = 2.9)
3.72 (t,
3.19
(br.s)
6.22 (dd,
J5,6 = 5.4,
J5,4 = 3.0)
6.36 (dd,
J6,5 = 5.4,
8.13, 7.84
7.57, 7.26 b
≈
J3,2
≈
J
7,7´ = 9.4);
J
J3,4 = 2.4)
J6,1 = 2.8) 1.88 (d,
J
7,7´ = 9.4)
3.14
(br.s)
3.82 (t,
J2,3
2,7´ = 3.2)
3.64 (t,
3.05
(br.s)
5.95 (dd,
J5,6 = 5.6,
J5,4 = 3.1)
6.18 (dd,
J6,5 = 5.6,
2.05 (d,
J7,7´ = 9.2);
7.50—7.15
(m)c
≈
J3,2
≈
J
J3,4 = 2.7)
J6,1 = 3.4) 1.80 (dq,
7,7´ = 9.2,
J
J7´,1 = J7´,4
J7´,2 = 2.0)
1.83 (d,
=
=
=
=
5a
5b
5c
3.22
(br.s)
4.20 (t,
J2,3
J2,1 = 3.4)
3.19 (t,
2.94
(br.s)
6.28 (dd,
J5,6 = 5.6,
J5,4 = 2.9)
6.41 (dd,
J6,5 = 5.6,
8.12, 7.43 a
≈
J3,2
≈
J7,7´ = 9.6);
J3,7´ = 3.0)
J6,1 = 3.1) 1.76 (dq,
7,7´ = 9.6,
J
J7´,1 = J7´,4
J7´,3 = 1.9)
1.88 (d,
3.22
(br.s)
4.24 (t,
3.16 (t,
J3,2
3,7´ = 3.0)
2.97
(br.s)
6.29 (dd,
J5,6 = 5.7,
J5,4 = 2.7)
6.44 (dd,
J6,5 = 5.7,
8.18, 7.62,
7.56, 7.28 b
J2,3
≈
≈
J7,7´ = 10.2);
J2,1 = 3.2)
J
J6,1 = 3.2) 1.74 (dq,
J
7,7´ = 10.2,
J7´,1 = J7´,4
J7´,3 = 1.9)
1.84 (d,
3.11
(br.s)
4.16 (t,
3.05 (t,
J3,2
3,7´ = 3.1)
2.83
(br.s)
6.17 (dd,
J5,6 = 5.7,
J5,4 = 2.8)
6.29 (dd,
J6,5 = 5.7,
7.44—7.25
(m)c
J2,3
≈
≈
J7,7´ = 9.3);
J2,1 = 3.2)
J
J6,1 = 3.0) 1.66 (dq,
7,7´ = 9.3,
J
J7´,1 = J7´,4
J7´,3 = 2.6)
(to be continued)

Sulfenylation of bicyclo[2.2.1]heptꢀ2,5ꢀdiene
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1473
Table 3 (continued)
Comꢀ
pound
δ (JH,H/Hz)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7), H(7´)
Other
signals
5d
5e
3.24
(br.s)
4.13 (t,
3.28 (t,
2.92
(br.s)
6.23 (dd,
J5,6 = 5.6,
J5,4 = 2.9)
6.27 (dd,
J5,6 = 5.7,
J5,4 = 2.9)
6.39 (dd,
J6,5 = 5.6,
J6,1 = 3.2) 1.73 (m)
6.43 (dd,
J6,5 = 5.7,
J6,1 = 3.2) 1.74 (dq,
7,7´ = 9.4,
1.82 (d,
J7,7´ = 9.5);
8.12, 7.42 a
J2,3
≈
J3,2
3,7´ = 2.8)
3.26 (t,
J3,2
3,7´ = 2.8)
≈
J2,1 = 3.2)
4.19 (t,
J
3.26
(br.s)
2.96
(br.s)
1.88 (d,
7,7´ = 9.4);
8.18, 7.63,
7.57, 7.27 b
J2,3
≈
≈
J
J2,1 = 3.3)
J
J
J7´,1 = J7´,4
J7´,3 = 2.3)
1.85 (d,
=
=
5f
3.18
(br.s)
4.12 (t,
3.16 (t,
J3,2
2.84
(br.s)
6.16 (dd,
J5,6 = 5.7,
J5,4 = 2.7)
6.31 (dd,
J6,5 = 5.7,
7.50—7.15
(m)c
J2,3
≈
≈
J7,7´ = 9.5);
J2,1 = 3.4)
J3,7´ = 3.0)
J6,1 = 3.2) 1.66 (dq,
7,7´ = 9.5,
J
J7´,1 = J7´,4
J7´,3 = 2.2)
6a
6b
1.53 (tq,
1.66 (tt,
4.15
(br.s)
2.26
(br.s)
4.10 (t,
1.62 (tt,
J6,1
J6,2 = 5.2, J7,4 = 1.5);
J6,5 1.52 (dt, J7,7´
J6,4 = 1.1) 11.5, J7´,1
1.96 (dt, J7,7´
=
=
=
=
=
8.12, 7.38 a
J1,2
=
J2,1
J2,6 = 5.2,
J2,3
=
J5,4
=
=
11.5, J7,1
=
J1,6 = 5.2,
J1,7 = J1,7´
J1,4 = 1.0)
J5,6 = 1.6)
=
=
=
=
J2,4 = 1.1)
=
J7´,4 = 1.2)
2.02 (dt, J7,7´
11.3, J7,1 =
J7,4 = 1.3);
1.54 (tq,
1.62
(m)
4.12 (t,
2.30
(br.s)
4.08
(br.s)
1.65
(m)
8.18, 7.57,
7.56, 7.24 b
J1,2
=
J3,2
J3,4
1.6)
=
=
J1,6 = 5.0,
J1,7 = J1,7´
J1,4 = 1.9)
1.50 (dt, J7,7´
11.3, J7´,1
=
J7´,4 = 1.4)
2.03 (dt, J7,7´
6c
6d
6e
6f
1.47 (m)
1.57 (d,
J2,1 = 5.1)
4.00
(br.s)
2.14
(br.s)
3.96
(br.s)
1.57 (d,
7.44—7.25
(m)c
J6,1 = 5.1) 11.3, J7,1 =
J7,4 = 1.5);
1.44 (d,
J
7,7´ = 11.3)
1.91 (dt,
7,7´ = 11.6,
1.46 (t,
1.73 (t,
4.13
(br.s)
2.29
(br.s)
4.10 (t,
1.62 (t,
J6,1
8.12, 7.48 a
J1,2
=
J2,1
=
J5,4
=
=
J
J1,6 = 5.2)
J2,6 = 5.2)
J5,6 = 1.4)
J6,2 = 5.2) J7,1 = J7,4 = 1.4);
1.51 (d,
J
7,7´ = 11.6)
1.97 (dt,
7,7´ = 11.2,
1.64 (tq,
1.47 (t,
4.11
(br.s)
2.33
(br.s)
4.09
(br.s)
1.72 (t,
J6,1
8.18, 7.60
7.57, 7.25 b
J1,2
=
J2,1
=
=
J
J1,6 = 5.4,
J1,7 = J1,7´
J1,4 = 1.1)
1.40 (tq,
J2,6 = 5.4)
J6,2 = 5.4) J7,1 = J7,4 = 1.4);
=
=
1.50 (d,
J
7,7´ = 11.3)
2.00 (dt,
7,7´ = 11.1,
J7,1 = J7,4 = 1.6);
1.44 (dt, J7,7´
11.3, J7´,1
1.57 (tt,
4.04 (t,
2.20
(br.s)
4.04
(br.s)
1.64 (m)
7.50—7.15
(m)c
J1,2
=
J2,1
J2,6 = 5.2,
J2,3
=
J3,2
≈
J
J1,6 = 5.2,
J1,7 = J1,7´
J1,4 = 1.1)
J3,4 = 1.6)
=
=
J2,4 = 1.1)
=
J7´,4 = 1.4)
7b
1.54 (tq,
1.59 (d,
J2,1 = 5.0)
4.04 (t,
2.40
(br.s)
3.36
(br.s)
1.59 (d,
J6,1 = 5.0)
2.02 (m, 2 H)
8.15, 7.48,
7.55, 7.25 b
J1,2
=
J3,2
=
J1,6 = 5.0,
J1,7 = J1,7´
J1,4 = 1.9)
J3,4 = 1.7)
=
(to be continued)

1474
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Zyk et al.
Table 3 (continued)
Comꢀ
δ (JH,H/Hz)
pound
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7), H(7´)
Other
signals
7c
8
1.51 (tt,
J1,2 = J1,6
1.53 (d,
J1,2 = 5.1)
3.89 (t,
2.14
(br.s)
3.22
(br.s)
1.53 (d,
J6,1 = 5.1) (m, 2 H)
2.00
7.44—7.25
(m)c
=
J3,2
≈
5.0, J1,7
1,7´ = 1.2
1.45 (tq,
J1,2
=
J3,4 = 1.6)
J
1.37 (tt,
3.63 (s)
2.45
(br.s)
3.99 (d,
J5,NH
6.3)
1.51 (m)d
1.98 (m)
1.52 (m)d
8.14, 7.54,
7.54, 7.24 b
6.44 (d, 1 H,
=
J2,1
J2,6 = 5.0,
J2,3
=
=
J1,6 = 5.0,
J1,7 = J1,7´
J1,4 = 1.0)
=
=
NH, J5,NH =
J2,4 = 1.2)
5.7); 2.05 (s,
3 H, Me)
8.14, 7.54,
7.54, 7.24 b
5.56 (d,
1 H, NH,
J5,NH = 6.9);
1.93 (s,
9
1.45 (tq,
1.39 (tt,
3.42 (s)
2.32
(br.s)
4.00 (dt,
J5,NH = 7.4,
1.48 (m)d
1.91 (dt,
J1,2
=
J2,1
J2,6 = 5.0,
J2,3
=
J
7,7´ = 11.5,
J1,6 = 5.0,
J1,7 = J1,7´
J1,4 = 1.0)
J5,4
=
J7,1
=
=
=
J5,6 = 1.5)
J7,4 = 1.3);
1.45 (m)d
J2,4 = 1.2)
3 H, Me)
8.03—7.00
(m)b
12
13
2.94 (d,
J1,6 = 4.8)
4.58 (dd,
J2,3 = 4.3,
J2,7 = 2.1)
4.11 (m)e
4.11 (m)e
2.66 (d,
4.02 (dd,
J5,6 = 4.8,
4.15 (t,
2.28 (d,
J7,7´ = 11.8);
J4,3
=
J6,5
J6,1 = 4.3) 2.17 (d,
J7´,7 = 11.8)
1.98 (br.s,
2 H)d
=
2.9)
J5,7´ = 2.6)
2.63 (d,
J1,6 = 5.0)
4.24 (t,
2.63 (d,
J4,3
5.0)
4.24 (t,
J5,6
J5,4 = 4.5)
4.11 (m)e
8.03—7.00
(m)b
J2,3
≈
=
≈
J2,1 = 4.5)
a Signals of the 4ꢀNO2C6H4S fragment.
b Signals of the 2ꢀNO2C6H4S fragment.
c Signals of the C6H5S fragment.
d The signals in the spectrum overlap.
e The signals overlap with the signals of compound 6e.
Nuclear Overhauser effect experiments confirm this
assignment. In product 6b, irradiation of the signal with
δ 4.12 does not induce NOE at the arylꢀgroup protons,
which permits this signal to be assigned to the H—C—Cl
fragment (see below, for 7b and 9). The ηH(5)(H(3))
effect is missing either, but the intensity of the signal of
the H(7) proton changes (ηH(7)(H(3)) = 2.3%). This is
possible only in the case of endoꢀorientation of the
Cl atom.
The assignment of 1H NMR signals of product 7b
was based on the NOE data (see Table 5) and on comꢀ
parison with published data.19 The great effect (5%) at
the orthoꢀproton of the aryl group induced by irradiation
of the proton with δ 3.36 allows this signal to be assigned
unambiguously to the H—C—SAr fragment. The lowerꢀ
field signal (δ 4.04) was assigned to the H—C—Cl fragꢀ
ment. As has been shown previously,20 the absence of
NOE at H(7) and H(7´) on irradiation of H(3) and H(5)
Table 4. 13C NMR spectra of compounds 6b, 7b, 8, and 9 in CDCl3
Comꢀ
pound
δ
C(1)
15.0
C(2)
C(3)
C(4)
C(5)
C(6)
15.9
C(7)
C arom.
6b
7b
8*
9**
20.0
19.9
15.7
16.4
64.8
62.7
47.6
48.6
41.5
41.8
38.5
38.6
47.9
48.3
56.4
54.5
29.4
27.7
29.4
27.0
137.4, 133.5, 127.0, 126.1, 124.5
133.3, 127.4, 126.0, 124.9
146.0, 137.4, 133.3, 127.3, 125.9, 124.5
146.0, 136.9, 133.4, 127.5, 125.8, 124.6
13.2
11.7
16.5
16.7
* 171.0 (CO), 23.2 (Me).
** 170.0 (CO), 23.2 (Me).

Sulfenylation of bicyclo[2.2.1]heptꢀ2,5ꢀdiene
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1475
Table 5. NOE data (η) for compounds 7b and 9 (in CDCl3)
Comꢀ
pound
Irradiated
protons
Observed protons, η (%)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7)
NH 2ꢀNO2C6H4
7b
9
H(3)CCl
H(5)CS
H(3)CS
H(5)CN
NH
2.9
—
5.4
—
—
10.4
—
9.3
—
2.8
1.7
2.4
2.5
—
8.1
—
10.3
—
—
3.3
—
4.5
2.3
—
—
—
—
4.1
—
—
—
0.9
—
—
5.0
5.6
—
—
1.6
—
respectively, using CDCl3 and CD3CN as solvents. Nuclear
Overhauser effect measurements were carried out in the differꢀ
ence spectroscopy mode (NOEDIF program). The melting
points of substances were determined on a hot stage in an open
capillary and were not corrected.
Arenesulfenamides were synthesized using a known proceꢀ
dure.21 The formation of the monoamide dichloride of phosꢀ
phorous acid (11) was confirmed by an alternative synthesis
from POCl3 and morpholine by a published procedure.22 The
course of the reaction was monitored by TLC on a fixed silica
gel layer (Silufol).
and the high ηH(3)(H(5)) and ηH(5)(H(3)) values (∼9%)
imply a spatial proximity of these protons and conꢀ
firm unambiguously the diꢀexoꢀconfiguration of comꢀ
pound 7b.
A similar change in the chemical shifts of H(3) and
H(5) observed for the whole series of products 6 and 7
(see Table 3) makes it possible to identify products 6
as exoꢀ5ꢀarylthioꢀendoꢀ3ꢀhalotricyclo[2.2.1.02,6]hepꢀ
tanes and 7, as exoꢀ5ꢀarylthioꢀexoꢀ3ꢀhalotricycꢀ
lo[2.2.1.02,6]heptanes.
Reactions of sulfenamides 2 with bicyclo[2.2.1]heptaꢀ2,5ꢀ
diеne (1) in the presence of phosphorus(V) oxohalides in CH2Cl2
and AcOEt (general procedure). A solution of phosphorus(V)
oxohalide (2 mmol) in the anhydrous solvent was slowly added
with intense stirring at ∼20 °C to a solution of sulfenamide 2
(2 mmol) in the same anhydrous solvent, and the mixture was
stirred for 10 min. Then a solution of diene 1 (2 mmol) in the
anhydrous solvent was slowly added, and the mixture was stirred
until the reaction was over (1.5—4 h, TLC monitoring). The
solvent was evaporated on a rotary evaporator and the residue
was separated on a chromatographic column with SiO2.
Reaction of sulfenamide 2b with bicyclo[2.2.1]heptaꢀ2,5ꢀdiꢀ
ene (1) in the presence of POCl3 in MeCN. A solution of POCl3
(2 mmol) in the anhydrous solvent was slowly added with inꢀ
tense stirring at ∼20 °C to a solution of sulfenamide 2b (2 mmol)
in the same solvent, and the mixture was stirred for 10 min.
Then a solution of diene 1 (2 mmol) in the anhydrous solvent
was slowly added, and the mixture was stirred until the reacꢀ
tion was over (2 h). The solvent was evaporated using a rotary
evaporator and the residue was dissolved in CHCl3, the soluꢀ
tion was washed three times with water, and the washings were
extracted with CHCl3. The organic fraction was dried with
Na2SO4, the solvent was evaporated, and the residue was sepaꢀ
rated on a chromatographic column with SiO2.
Reaction of POCl3ꢀactivated sulfenamide 2b with bicycꢀ
lo[2.2.1]heptaꢀ2,5ꢀdiene (1) in MeCN in the presence of LiClO4.
A solution of POCl3 (2 mmol) in the anhydrous solvent and
LiClO4 (4 mmol) were slowly added with intense stirring at
∼20 °C to a solution of sulfenamide 2b (2 mmol) in the same
solvent, and the mixture was stirred for 10 min. Then a solution
of diene 1 (2 mmol) in the anhydrous solvent was slowly added,
and the mixture was stirred until the reaction was over (TLC
monitoring). The solvent was evaporated on a rotary evaporaꢀ
tor, the residue was dissolved in CHCl3, the solution was washed
three times with water, and the washings were extracted with
CHCl3. The organic fraction was dried with Na2SO4, the CHCl3
was evaporated, and the residue was separated on a chromatoꢀ
graphic column with SiO2.
Compounds 8 and 9 were also isolated and characꢀ
terized as a mixture. The chemical shifts of protons at
substituents correspond to correlations reported previꢀ
ously.19 Structure 9 is additionally confirmed by NOE
experiment (see Table 5); these data provided unamꢀ
1
biguous assignment of signals in the H NMR spectrum
and a proof for the diꢀexoꢀconfiguration of product 9.
The structure of compound 12 was established using
analysis of the chemical shifts and spinꢀspin coupling
constants in the 1H NMR spectrum. Thus the J2,3
=
4.3 Hz and J5,6 = 4.8 Hz values correspond to transꢀpoꢀ
sitions of the H(2) and H(3), H(5) and H(6) protons.
The exoꢀorientation of the H—C(6)—Br proton (δ 4.16)
is indicated by the presence of rather large vicinal constant
(J1,6 = 4.8 Hz). The endoꢀprotons of the H—C(2)—Br
(δ 4.58) and H—C(5)—S (δ 4.02) groups show no interꢀ
actions with the bridgehead protons but a Wꢀcoupling
constant is observed, J2,7 = 2.1 Hz and J5,7´ = 2.6 Hz.
Compound 13 is a stereoisomer of compound 12 but
1
the former is responsible for only four H NMR signals,
as it is highly symmetric. The structure containing exoꢀ
arylthio groups and endoꢀbromine atoms was chosen reꢀ
lying on calculations performed using the correlations
proposed previously.19,20
Thus, the arenesulfenamide—phosphorus oxohalide
system appears promising as a reagent for sulfenylation
of dienes. The results of reactions with norbornadiene
(1) attest that the reactions carried out in MeCN and
CH2Cl2 involve different sulfenylating species.
Experimental
1
H and 13C NMR spectra were recorded at 28 °C on a
Varian VXRꢀ400 instrument operating at 400 and 100 МHz,

1476
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Zyk et al.
Table 6. Chromatographic data and results of elemental analysis of the products of haloꢀ
sulfenylation of bicyclo[2.2.1]heptaꢀ2,5ꢀdiene (1)
Comꢀ
pound
Rf
Found
Calculated
Molecular formula
(%)
(system)
C
H
N
4a
4b
4c
4d
4e
4f
0.20
55.36 b
55.42
54.83 c
55.42
—
4.16 b
4.26
4.39 c
4.26
—
4.70 b
4.97
4.72 c
4.97
—
C13H12ClNO2S
(CHCl3—PEa, 1 : 3)
0.54
C13H12ClNO2S
(CHCl3—PE, 1 : 1)
0.28
(PE)
0.13
—
47.85 d
47.85
47.60 e
47.85
—
3.72 d
3.68
3.97 e
3.68
—
4.09 d
4.29
4.06 e
4.29
—
C13H12BrNO2S
(CHCl3—PE, 1 : 3)
0.19
C13H12BrNO2S
(CHCl3—PE, 1 : 3)
0.41
—
(PE)
0.20
5a
5b
5c
5d
5e
5f
55.36 b
55.42
54.83 c
55.42
—
4.16 b
4.26
4.39 c
4.26
—
4.70 b
4.97
4.72 c
4.97
—
C13H12ClNO2S
(CHCl3—PE, 1 : 3)
0.54
C13H12ClNO2S
(CHCl3—PE, 1 : 1)
0.28
—
(PE)
0.13
47.85 d
47.85
47.60 e
47.85
—
3.72 d
3.68
3.97 e
3.68
—
4.09 d
4.29
4.06 e
4.29
—
C13H12BrNO2S
(CHCl3—PE, 1 : 3)
0.19
C13H12BrNO2S
(CHCl3—PE, 1 : 3)
0.41
—
(PE)
0.20
6a
6b
6c
6d
6e
6f
55.36 b
55.42
54.83 c
55.42
—
4.16 b
4.26
4.39 c
4.26
—
4.70 b
4.97
4.72 c
4.97
—
C13H12ClNO2S
(CHCl3—PE, 1 : 3)
0.54
C13H12ClNO2S
(CHCl3—PE, 1 : 1)
0.28
—
(PE)
0.13
47.85 d
47.85
—
3.72 d
3.68
—
4.09 d
4.29
—
C13H12BrNO2S
(CHCl3—PE, 1 : 3)
0.18
—
(CHCl3—PE, 1 : 3)
0.41
(PE)
0.46
—
—
—
—
—
—
—
—
—
—
7b
7c
8
—
(CHCl3—PE, 1:1)
0.28
—
(PE)
0.44
(CHCl3)
0.44
(CHCl3)
59.31 f
59.21
59.31 f
59.21
5.28 f
5.26
5.28 f
5.26
9.01 f
9.21
9.01 f
9.21
C15H16N2O3S
C15H16N2O3S
9
a PE is petroleum ether.
b For a mixture of isomers 4a, 5a, and 6a.
c For a mixture of isomers 4b, 5b, and 6b.
d For a mixture of isomers 4d, 5d, and 6d.
e For a mixture of isomers 4e and 5e.
f For a mixture of isomers 8 and 9.

Sulfenylation of bicyclo[2.2.1]heptꢀ2,5ꢀdiene
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1477
The product yields are listed in Table 1, and the physicoꢀ
chemical characteristics of the products are given in Tables 3—6.
11. H. G. Viehe and S. Y. Delavarenn, Chem. Ber., 1970,
103, 1216.
12. V. Calo, G. Melloni, and G. Scorrano, J. Chem. Soc. C,
1968, 1339.
This work was supported by the Russian Foundation
for Basic Research (Projects No. 99ꢀ03ꢀ33093 and
No. 02ꢀ03ꢀ33347) and the Foundation "Universities of
Russia." (Project No. 990879).
13. N. S. Zefirov, N. K. Sadovaya, R. Sh. Akhmedova, I. V.
Bodrikov, T. S. Morrill, A. M. Nersisyan, V. B. Rybakov,
N. D. Saratseno, and Yu. T. Struchkov, Zh. Org. Khim.,
1980, 16, 580 [J. Org. Chem. USSR, 1980, 16 (Engl. Transl.)].
14. Svoistva organicheskikh soedinenii [Properties of Organic Comꢀ
pounds], Ed. A. A. Potekhin, Khimiya, Leningrad, 1984,
520 pp. (in Russian).
References
15. I. D. Titanyuk, Ph.D Thesis (Chem.), M. V. Lomonosov
Moscow State University, Moscow, 1999, 137 pp. (in
Russian).
16. N. S. Zefirov, N. K. Sadovaya, R. Sh. Akhmedova, I. V.
Bodrikov, T. S. Morrill, A. N. Nersisyan, V. B. Rybakov,
N. D. Saratseno, and Yu. D. Struchkov, Zh. Org. Khim.,
1980, 16, 580 [J. Org. Chem. USSR, 1980, 16 (Engl. Transl.)].
17. N. S. Zefirov, V. A. Smit, I. V. Bodrikov, and M. Z. Krimer,
Dokl. Akad. Nauk SSSR, 1978, 240, 858 [Dokl. Chem., 1978
(Engl. Transl.)].
1. E. K. Beloglazkina, N. V. Zyk, V. S. Tyurin, I. D. Titanyuk,
and N. S. Zefirov, Dokl. Akad. Nauk, 1994, 344, 487 [Dokl.
Chem., 1994 (Engl. Transl.)].
2. N. V. Zyk, E. K. Beloglazkina, M. A. Belova, and N. S.
Zefirov, Izv. Akad. Nauk, Ser. Khim., 2000, 1874 [Russ.
Chem. Bull., Int. Ed., 2000, 49, 1846].
3. M. Z. Krimer, V. A. Smit, and A. A. Shamurshin, Dokl.
Akad. Nauk SSSR, 1973, 208, 864 [Dokl. Chem., 1973 (Engl.
Transl.)].
4. N. Kharasch, C. M. Buess, and S. I. Strashun, J. Am.
Chem. Soc., 1952, 74, 3422.
5. N. Kharasch and A. J. Havlik, J. Am. Chem. Soc., 1953,
75, 3734.
18. A. J. Gordon and R. A. Ford, The Chemist´s Companion,
Wiley and Sons, New York, 1972, 293 pp.
19. A. O. Chizhov, N. S. Zefirov, N. V. Zyk, and T. C. Morrill,
J. Org. Chem., 1987, 52, 5647.
6. A. J. Heiba and R. M. Dessau, J. Org. Chem., 1967, 32, 3837.
7. I. V. Bodrikov, L. I. Kovaleva, and N. S. Zefirov, Zh. Org.
Khim., 1976, 12, 2476 [J. Org. Chem. USSR, 1976, 12 (Engl.
Transl.)].
8. W. H. Mueller, Angew. Chem., 1969, 81, 475.
9. N. Kharasch and S. J. Accony, J. Am. Chem. Soc., 1953,
75, 1081.
20. I. D. Gridnev, I. F. Leshcheva, N. M. Sergeyev, and V. A.
Chertkov, Magn. Reson. Chem., 1992, 30, 817.
21. J. H. Billman and E. J. O´Mahony, J. Am. Chem. Soc.,
1939, 61, 2340.
22. K. Issleib and W. Seidel, Chem. Ber., 1959, 92, 2681.
Received April 20, 2001
10. F. Montanari, Gazz. Chim. Ital., 1956, 86, 406.
in revised form March 14, 2002