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Endo addition of chlorosulfonyl isocyanate to norbornadienes
Letters No. 52, pp 2953 - 2956. @Pergamon Press Ltd. 1979. Printed in Great Britain.
Tetrahedron
END0 ADDITION
OF CHLOROSULFONYL
ISOCYANATE
TO NORBORNADIENES
Paul H. Mazzocchi*, Theodore Halchak and Herman Department of Chemistry University of Maryland College Park, Maryland 20742
L. Ammon
SUMMARY The addition of chlorosulfonyl isocyanate to several bornadienes affords endo and -exo addition products. Recently
has been 1 norbornadienes. With
tuted
additions,
there
the preponderance
a great
deal of interest
respect
to inverse
of s-end0
substituents
(i.e. 3b) has been explained -_ la bond by the sllbstituent.
double
obtained
by specific
nor-
in additions
electron
adducts
7-substituted
to 7-substila-c Diels-Alder
demand with
certain
activation
7-
of the syn
R +
&
i
“6
b RIO+
4
C R- OCOC6H5
The addition diene
has been
adducts
of chlorosulfonyl
shown
in 86% and 94% yield
of 7-substituents our initial
results.
to norbornadienes.
NMR(CDC13)
63.3
with
(m, 3H),
1770 cm-1.4,5
phase
(CSI) to norbornene
by exo addition 2 respectively. We initiated on the mode
constitute
the exo
a study
of the effects
of CSI addition
the first
and norborna-
to give
case of endo
and we now report addition
of CSI
Addition
treatment
IR(CHC13)
These
isocyanate
exclusively
in norbornadiene
subsequent
aqueous
to occur
of 7-phenylnorbornadiene (la) __ to CSI in CHC13 3 Na SO -KOH gave a 37% yield of the exo-8-lactam 2 3 3.75 (m, 2H), 6.2 (m, 2H), and 7.2-7.4 (m, 5H),
A second
and was preliminarily
crystalline
product
characterized
2955
was
isolated
as the amide
from the
alcohol
8a: __
and 6a:
No. 32
H5C20C0
OH 10
NMR(DMSO-d6)
61.3-2.1
(m, 3H), 2.2-2.4
4.8-6.7
(broad, exchangeable, -1 ; mass spectral and 1460 cm 167 respectively.
The yield
Confirmation was provided smooth
(m, 2H),
3.4
parent after
3650,
(s, lH),
3490,
ion and base peaks
several
of the structure
by brief
conversion
(m, 2), 3.0
3H), IR(KBr)
(s, 5H), and
3200,
at m/e
recrystallizations
and endo orientation
7.4
3360,
1690
229 and m/e (H20) was
l58.
of the amide-alcohol
treatment
of 8a with HCl-EtOH which resulted in its *-_ 9a: 6 NMR(CDC13) l-7-2.0 (m, 3H), 2.55-2.75 (m, HB); 7.35 (s, 5H); IR(CDC13) 1785 cm -1 .
to the lactone
(s, lH), 4.95
Treatment
of lc with CSI and aqueous workup afforded the corresponding __ 9c (IR(CDC13) 1785 and 1725 cm -1) , 7 in addition to the B-lactam 5c. __ __ A tentative assignment of the orientation of the bridge substituent with relactone
spect
to the lactone
carbonyl in 9a and 9c was made by comparing the chemical -.__ of Ha in 9a vs 9c. Proton HA is deshielded by the bridge carbonyl group __ I_ by approximately 0.2 ppm in 9c (62.9) vs 9a (6-2.65) whereas the HB chemical __ __ shifts are quite similar. shifts
This
assignment
9a _-. (Fig. 1). phite crystal are:
(2)O; 2 = 4.
ground.
R
Data were
collected
monochromatized
monoclinic,P21/n;
20 of 500.
matrix
was confirmed
Intensities
were
radiation
squares
([xw(~_-~~)~/Zw&~]%
solved
technique.
f actors
FACS-I
with
by direct The final
were
methods R
determination
diffractometer 2
with
gradata
c = 20.769(4) _
more
than
and refined
(CIFo-Fcl/CFo)
and 0.037.
on
The crystal
the O-28 scan method
reflections
are 0.038
x-ray
(X = 0.71069)
b = 8.402(l),
measured
1276 of the 1822 unique was
crystal
on a Picker
MoK
5 = 5.967(l),
The structure least
by a single
8,g
= 93.66-
to a maximum
3a above
back-
by the full
and weighted
No. 32
2955
Figure Evidence frared
for the intermediacy
spectrum
(C=N) and 1820 appear
ORTEP
I
of the reaction
immediately
of lactone
of 7 was provided
mixture
absorption
(C=O) cm-l
Drawing
on CSI addition
9a __
by examination
(la + CSI) which __
showed
of the in-
strong
from 7a and 5a respectively. _,.. Iand their relative intensities
1610
These
bands
do not change
on standing. Speculation must
on the nature
of the transition
states
leading to 7a and 5a *_ __ of 2 is essentially
be consistent
with the fact that the 5a/7a ratio __ _.. invariant 8 in solvents of widely different dielectric
EtBr,
CH3CN)
These
(kCH5CN'kCClq=10)' in these reactions leading
results
and that
to 7 and 5 are quite
similar.
mechanistic
by the electron
and would
result
ance of lactone
hypothesis
deficient
addition
the isomeric
l-substitution products.
in the rate of endo hope
to be able
gations
results
This
addition
to answer
norbornadienes
with
could
that
7-phenyl
state.
lactone
The preponder-
which
would
result
is some preference
increase
from either
for
in the yield
a significant
we have
finished
of CSI additions substituents
of
increase
in the rate of exo addition.
when
and kinetics
states
either initial -exo or endo of CSI at a double bond,
these
in a dramatic result
or a decrease
p-substituted -
of the transition
transition
(unisolated)
this question
on the stereochemistry
carbon
polarized
anti-end0 attack, indicates -___ la over -anti-end0 attack.
endo
involves
carbonyl
in the required 9 over
the polarities
from initial syn-endo -Clearly
(CC14, CHC12,
to la is quite solvent dependent __ that the transition states involved
suggest
are polar
A reasonable attack
constants
but the rate of CSI addition
We
our investito a series
(F, H, CH8,
of
OCH5).
2956
No.
37
Acknowledgement We thank the Computer Science Center of the University of Maryland and the National Science Foundation (CHE-7823808) for partial support of this work. References and Footnotes 1.
(a) Battiste, M-A., Timberlake, J.F., Malkus, H., Tetrahedron E., 2529 (1976); (b) Byrne, L.T., Rye, A.R., Wege, D., Aust. J. Chem., 22, 1961 (1974); (c) Astin, K.B., Mackenzie, K., J. Chem. Sot-, Perkin Trans. G, 1005 (1975); (d) McLean, S., Findlay,D.M.,%trahedron E., 2219 (1969); (e) Wilt, J.W., Malloy, T.P., 2. Org. Chem., 38, 277 (1973); (f) Wilt, J.W., Sullivan, D.R., J. Org. Checc, 1036 (1975); (g) Wilt, J.W., Roberts, W.N., 2. Org. Chem., 43, 170 (1978); (h) FranckNeumann, M., Sedrati, M., Angew. Chem., Int. Ed. a., LI_, 606 (1974); (i) Jefford, C.W., Mareda, J., Gehret, J>. E, Kabengele, nT., Graham, 98, 2585 (1976); (j) Jefford, C.W. W.D., Burger, U., J. Am. Chem. e., 703 (1976); (k) de 10s Heros, V., andBurger, U., Tetrahedron s., 707 (1976); Klumpp, G.W., Kwantes, P.M., Klumpp, G.W., Tetrahedron e., Veefkind, A.H., deGraaf, W.L., Bickelhaupt, F., Ann. Chem., 706, 47 -(1967).
2.
Moriconi, E.J., and Crawford, W.C., IL. Org. Chem., 33, 370
3.
Durst, T., and O'Sullivan, M.J., J. Org. Chem., 35, 2043 (1970).
4.
All new compounds gave acceptable elemental analysis (C,H,N).
5.
The exo stereochemistry follows from the analysis of the NMR couplings. See ref. 2.
6.
Prolonged treatment of 9a __ __ with EtOH-EICl afforded the alcohol ester 10.
7.
This material was originally isolated by Moriconi and Crawford (ref. 2) but its structure was not assigned. They reported an 11% yield of 5c __ and we have isolated 9~ in 10% yield.
8.
Determined by NMR using the olefin proton and HB resonance in 5 and z respectively. HB was assigned to a resonance at 5.26. An additional peak (l/3 the intensity of the 5.26 peak) at 5.06 was observed in all cases and was tentatively assigned to the isomeric imino lactone formed via initial anti-end0 attack. This material may have been lost during work-up. Inxportof this hypothesis preliminary experiments with 7-(p-methoxyphenyl)norbornadiene indicate that in this case we isolate a mixture of isomeric lactones in a 3:l ratio. We are presently working on the separation of these materials.
(Receivedin USb 26 kpril 1979)
(1966).
Tetrahedron
END0 ADDITION
OF CHLOROSULFONYL
ISOCYANATE
TO NORBORNADIENES
Paul H. Mazzocchi*, Theodore Halchak and Herman Department of Chemistry University of Maryland College Park, Maryland 20742
L. Ammon
SUMMARY The addition of chlorosulfonyl isocyanate to several bornadienes affords endo and -exo addition products. Recently
has been 1 norbornadienes. With
tuted
additions,
there
the preponderance
a great
deal of interest
respect
to inverse
of s-end0
substituents
(i.e. 3b) has been explained -_ la bond by the sllbstituent.
double
obtained
by specific
nor-
in additions
electron
adducts
7-substituted
to 7-substila-c Diels-Alder
demand with
certain
activation
7-
of the syn
R +
&
i
“6
b RIO+
4
C R- OCOC6H5
The addition diene
has been
adducts
of chlorosulfonyl
shown
in 86% and 94% yield
of 7-substituents our initial
results.
to norbornadienes.
NMR(CDC13)
63.3
with
(m, 3H),
1770 cm-1.4,5
phase
(CSI) to norbornene
by exo addition 2 respectively. We initiated on the mode
constitute
the exo
a study
of the effects
of CSI addition
the first
and norborna-
to give
case of endo
and we now report addition
of CSI
Addition
treatment
IR(CHC13)
These
isocyanate
exclusively
in norbornadiene
subsequent
aqueous
to occur
of 7-phenylnorbornadiene (la) __ to CSI in CHC13 3 Na SO -KOH gave a 37% yield of the exo-8-lactam 2 3 3.75 (m, 2H), 6.2 (m, 2H), and 7.2-7.4 (m, 5H),
A second
and was preliminarily
crystalline
product
characterized
2955
was
isolated
as the amide
from the
alcohol
8a: __
and 6a:
No. 32
H5C20C0
OH 10
NMR(DMSO-d6)
61.3-2.1
(m, 3H), 2.2-2.4
4.8-6.7
(broad, exchangeable, -1 ; mass spectral and 1460 cm 167 respectively.
The yield
Confirmation was provided smooth
(m, 2H),
3.4
parent after
3650,
(s, lH),
3490,
ion and base peaks
several
of the structure
by brief
conversion
(m, 2), 3.0
3H), IR(KBr)
(s, 5H), and
3200,
at m/e
recrystallizations
and endo orientation
7.4
3360,
1690
229 and m/e (H20) was
l58.
of the amide-alcohol
treatment
of 8a with HCl-EtOH which resulted in its *-_ 9a: 6 NMR(CDC13) l-7-2.0 (m, 3H), 2.55-2.75 (m, HB); 7.35 (s, 5H); IR(CDC13) 1785 cm -1 .
to the lactone
(s, lH), 4.95
Treatment
of lc with CSI and aqueous workup afforded the corresponding __ 9c (IR(CDC13) 1785 and 1725 cm -1) , 7 in addition to the B-lactam 5c. __ __ A tentative assignment of the orientation of the bridge substituent with relactone
spect
to the lactone
carbonyl in 9a and 9c was made by comparing the chemical -.__ of Ha in 9a vs 9c. Proton HA is deshielded by the bridge carbonyl group __ I_ by approximately 0.2 ppm in 9c (62.9) vs 9a (6-2.65) whereas the HB chemical __ __ shifts are quite similar. shifts
This
assignment
9a _-. (Fig. 1). phite crystal are:
(2)O; 2 = 4.
ground.
R
Data were
collected
monochromatized
monoclinic,P21/n;
20 of 500.
matrix
was confirmed
Intensities
were
radiation
squares
([xw(~_-~~)~/Zw&~]%
solved
technique.
f actors
FACS-I
with
by direct The final
were
methods R
determination
diffractometer 2
with
gradata
c = 20.769(4) _
more
than
and refined
(CIFo-Fcl/CFo)
and 0.037.
on
The crystal
the O-28 scan method
reflections
are 0.038
x-ray
(X = 0.71069)
b = 8.402(l),
measured
1276 of the 1822 unique was
crystal
on a Picker
MoK
5 = 5.967(l),
The structure least
by a single
8,g
= 93.66-
to a maximum
3a above
back-
by the full
and weighted
No. 32
2955
Figure Evidence frared
for the intermediacy
spectrum
(C=N) and 1820 appear
ORTEP
I
of the reaction
immediately
of lactone
of 7 was provided
mixture
absorption
(C=O) cm-l
Drawing
on CSI addition
9a __
by examination
(la + CSI) which __
showed
of the in-
strong
from 7a and 5a respectively. _,.. Iand their relative intensities
1610
These
bands
do not change
on standing. Speculation must
on the nature
of the transition
states
leading to 7a and 5a *_ __ of 2 is essentially
be consistent
with the fact that the 5a/7a ratio __ _.. invariant 8 in solvents of widely different dielectric
EtBr,
CH3CN)
These
(kCH5CN'kCClq=10)' in these reactions leading
results
and that
to 7 and 5 are quite
similar.
mechanistic
by the electron
and would
result
ance of lactone
hypothesis
deficient
addition
the isomeric
l-substitution products.
in the rate of endo hope
to be able
gations
results
This
addition
to answer
norbornadienes
with
could
that
7-phenyl
state.
lactone
The preponder-
which
would
result
is some preference
increase
from either
for
in the yield
a significant
we have
finished
of CSI additions substituents
of
increase
in the rate of exo addition.
when
and kinetics
states
either initial -exo or endo of CSI at a double bond,
these
in a dramatic result
or a decrease
p-substituted -
of the transition
transition
(unisolated)
this question
on the stereochemistry
carbon
polarized
anti-end0 attack, indicates -___ la over -anti-end0 attack.
endo
involves
carbonyl
in the required 9 over
the polarities
from initial syn-endo -Clearly
(CC14, CHC12,
to la is quite solvent dependent __ that the transition states involved
suggest
are polar
A reasonable attack
constants
but the rate of CSI addition
We
our investito a series
(F, H, CH8,
of
OCH5).
2956
No.
37
Acknowledgement We thank the Computer Science Center of the University of Maryland and the National Science Foundation (CHE-7823808) for partial support of this work. References and Footnotes 1.
(a) Battiste, M-A., Timberlake, J.F., Malkus, H., Tetrahedron E., 2529 (1976); (b) Byrne, L.T., Rye, A.R., Wege, D., Aust. J. Chem., 22, 1961 (1974); (c) Astin, K.B., Mackenzie, K., J. Chem. Sot-, Perkin Trans. G, 1005 (1975); (d) McLean, S., Findlay,D.M.,%trahedron E., 2219 (1969); (e) Wilt, J.W., Malloy, T.P., 2. Org. Chem., 38, 277 (1973); (f) Wilt, J.W., Sullivan, D.R., J. Org. Checc, 1036 (1975); (g) Wilt, J.W., Roberts, W.N., 2. Org. Chem., 43, 170 (1978); (h) FranckNeumann, M., Sedrati, M., Angew. Chem., Int. Ed. a., LI_, 606 (1974); (i) Jefford, C.W., Mareda, J., Gehret, J>. E, Kabengele, nT., Graham, 98, 2585 (1976); (j) Jefford, C.W. W.D., Burger, U., J. Am. Chem. e., 703 (1976); (k) de 10s Heros, V., andBurger, U., Tetrahedron s., 707 (1976); Klumpp, G.W., Kwantes, P.M., Klumpp, G.W., Tetrahedron e., Veefkind, A.H., deGraaf, W.L., Bickelhaupt, F., Ann. Chem., 706, 47 -(1967).
2.
Moriconi, E.J., and Crawford, W.C., IL. Org. Chem., 33, 370
3.
Durst, T., and O'Sullivan, M.J., J. Org. Chem., 35, 2043 (1970).
4.
All new compounds gave acceptable elemental analysis (C,H,N).
5.
The exo stereochemistry follows from the analysis of the NMR couplings. See ref. 2.
6.
Prolonged treatment of 9a __ __ with EtOH-EICl afforded the alcohol ester 10.
7.
This material was originally isolated by Moriconi and Crawford (ref. 2) but its structure was not assigned. They reported an 11% yield of 5c __ and we have isolated 9~ in 10% yield.
8.
Determined by NMR using the olefin proton and HB resonance in 5 and z respectively. HB was assigned to a resonance at 5.26. An additional peak (l/3 the intensity of the 5.26 peak) at 5.06 was observed in all cases and was tentatively assigned to the isomeric imino lactone formed via initial anti-end0 attack. This material may have been lost during work-up. Inxportof this hypothesis preliminary experiments with 7-(p-methoxyphenyl)norbornadiene indicate that in this case we isolate a mixture of isomeric lactones in a 3:l ratio. We are presently working on the separation of these materials.
(Receivedin USb 26 kpril 1979)
(1966).