Intramolecular nucleophilic deselenenylation reactions promoted by benzeneselenenyl triflate. Stereospecific synthesis of vicinal amino alcohol precursors

Article abstract of DOI:10.1021/jo960866g

After activation with electrophilic selenenylating agents, the phenylseleno group of vicinal azido selenides, containing internal oxygen or nitrogen nucleophilic substituents, readily undergoes intramolecular nucleophilic displacement to afford azido-substituted heterocyclic compounds. This intramolecular substitution occurs with inversion of configuration at the carbon atom bearing the selenium atom. Starting from acetamido selenides and carbamato selenides, a stereocontrolled synthesis of the vicinal amino alcohol precursor oxazolines and oxazolidin-2-ones has been developed.

Full text of DOI:10.1021/jo960866g

J . Org. Chem. 1996, 61, 7085-7091
7085
In tr a m olecu la r Nu cleop h ilic Deselen en yla tion Rea ction s
P r om oted by Ben zen eselen en yl Tr ifla te. Ster eosp ecific Syn th esis
of Vicin a l Am in o Alcoh ol P r ecu r sor s
Marco Tingoli,*,† Lorenzo Testaferri, Andrea Temperini, and Marcello Tiecco
Istituto di Chimica Organica, Facolta` di Farmacia, Universita` di Perugia, 06100 - Perugia, Italy
Received May 13, 1996X
After activation with electrophilic selenenylating agents, the phenylseleno group of vicinal azido
selenides, containing internal oxygen or nitrogen nucleophilic substituents, readily undergoes
intramolecular nucleophilic displacement to afford azido-substituted heterocyclic compounds. This
intramolecular substitution occurs with inversion of configuration at the carbon atom bearing the
selenium atom. Starting from acetamido selenides and carbamato selenides, a stereocontrolled
synthesis of the vicinal amino alcohol precursor oxazolines and oxazolidin-2-ones has been developed.
Sch em e 1
In tr od u ction
Organoselenium reagents are now largely used in
organic synthesis since they allow several important
chemo-, regio-, and stereoselective reactions to be effected
under mild experimental conditions.1-4 Very few sele-
nium-containing compounds find practical application,
and in most cases the selenium functionality, which in
general is a phenylselenenyl group, must therefore be
removed at the end of the conversion. Owing to the
versatility of this function, one can use this final step to
further elaborate the organic molecule. Deselenenylation
reactions can be effected directly on the selenides or after
transformation into selenoxides, selenones, or selenonium
salts. Simple replacement of the PhSe group by hydrogen
can be effected with Raney nickel, nickel boride,5 or with
tri-n-butyltin hydride6 in the presence of AIBN. This
represents a convenient way to produce carbon radicals.
The PhSe group can be replaced by an allyl group using
allyltributyltin.7 Interesting conversions can be per-
formed by electron transfer reactions. The dissociative
reduction of an aryl alkyl selenide produces an arylse-
lenium anion and a carbanion.8 Similarly, the dissocia-
tive oxidation produces an arylselenium cation and a
carbocation.4 The best known and most widely used
deselenenylation reaction is the syn-elimination of sele-
noxides which represents the mildest general olefin-
forming reaction.9-11 When the selenoxide is allylic, the
equilibrium lies largely toward the selenenic ester which
is readily hydrolyzed to the allylic alcohol.12 Selenoxides
which cannot give rise to one of these two processes
readily undergo nucleophilic substitution reactions.13 The
selenonyl group of selenones is an even better leaving
group.14 Finally, substitution reactions can be effected
on the selenonium salts which form as intermediates
when an alkyl phenyl selenide is treated with halogens
or with an electrophilic selenenylating agent.15,16 In a
recent communication we reported that selenonium salt
intermediates can be used to effect a mild and very
simple synthesis of substituted azides by deselenenyla-
tion of vicinal azido selenides.17
As indicated in Scheme 1, after treatment with elec-
trophilic selenenylating agents, the vicinal azido se-
lenides 1 can easily give rise to nucleophilic substitution
reactions to afford a variety of substituted azides 3. The
attack of the electrophilic selenenylating agents on the
selenium atom of the selenides 1 generates the sele-
nonium ion 2 in which the diphenyl diselenide acts as a
very good leaving group.17
† Present address: Dipartimento di Scienza degli Alimenti, Univer-
sita` di Napoli Federico II, Via Universita` 100, I - 80055 Portici, Napoli,
Italy.
We now report that this procedure can be applied to
phenyl alkyl selenides containing an internal nucleophile
so that an intramolecular displacement of the phenylse-
X Abstract published in Advance ACS Abstracts, September 1, 1996.
(1) Paulmier, C. Selenium Reagents and Intermediates in Organic
Synthesis; Pergamon Press: Oxford, 1986.
(2) Liotta, D. Organoselenium Chemistry; Wiley: New York, 1987.
(3) Patai, S. The Chemistry of Organic Selenium and Tellurium
Compounds; Wiley: New York, 1987, Vol. 1 and 2.
(4) Tiecco, M.; Tingoli, M.; Testaferri, L. Pure Appl. Chem. 1993,
65, 715.
(5) Barton, D. H. R.; Lusinchi, X.; Milliet, P. Tetrahedron Lett. 1982,
23, 4949. For a detailed study: Back, T. G.; Birss, V. I.; Edwards, M.;
Krishna, M. V. J . Org. Chem. 1988, 53, 3815.
(10) Nicolaou, K. C.; Magolda, R. L.; Sipio, W. J .;Barnette, W. E.;
Lysenko, Z.; J oullie, M. M. J . Am. Chem. Soc. 1980, 102, 3784. For
detailed studies: Reich, H. J .; Wollowitz, S.; Trend, J . E.; Chow, F.;
Wendelborn, D. F. J . Org. Chem. 1978, 43, 1697; Hori, T.; Sharpless,
K. B. J . Org. Chem. 1978, 43, 1689.
(11) Tiecco, M.; Testaferri, L.; Tingoli, M.; Marini, F. J . Org. Chem.
1993, 58, 1349.
(6) Clive, D. L. J .; Chittattu, G.; Wong, G. K. J . Chem. Soc., Chem.
Commun. 1978, 41. For a detailed study with the related PhSn3H:
Clive, D. L. J .; Chittattu, G. J .; Farina, V.; Kiel, W. A.; Menchen, S.
M.; Russel, C. G.; Singh, A.; Wong, C. K.; Curtis, N. J . J . Am. Chem.
Soc. 1980, 102, 4438.
(7) Keck, G. E.; J ates, J . B. J . Am. Chem. Soc. 1982, 104, 5829.
(8) Tiecco, M. Synthesis 1988, 10, 749.
(9) Sharpless, K. B.; Lauer, R. F. J . Am. Chem. Soc. 1973, 95, 2697.
Other early reports are: Reich, H. J .; Reich, I. L.; Renga, J . M. J . Am.
Chem. Soc. 1973, 95, 5813; Clive, D. L. J . J . Chem. Soc., Chem.
Commun. 1973, 695.
(12) Sharpless, K. B.; Lauer, R. F. J . Am. Chem. Soc. 1972, 94, 7154.
(13) Tiecco, M.; Chianelli, D.; Testaferri, L.; Tingoli, M.; Bartoli, D.
Tetrahedron 1986, 42, 4889.
(14) Krief, A.; Dumont, W.; Denis, J . N. J . Chem. Soc., Chem.
Commun. 1985, 571. Nearly simultaneous work: Uemura, S.; Fuku-
zawa, S.-I. J . Chem Soc., Perkin Trans. 1 1985, 471.
(15) Sevrin, M.; Krief, A. J . Chem. Soc., Chem. Commun. 1980, 656.
(16) Tiecco, M.; Testaferri, L.; Tingoli, M.; Chianelli, D.; Bartoli, D.
Tetrahedron 1988, 44, 2261.
(17) Tingoli, M.; Tiecco, M.; Testaferri, L.; Temperini, A. J . Chem.
Soc., Chem. Commun. 1994, 1883.
S0022-3263(96)00866-3 CCC: $12.00 © 1996 American Chemical Society

7086 J . Org. Chem., Vol. 61, No. 20, 1996
Tingoli et al.
Ta ble 1. Con ver sion of Vicin a l Azid o Selen id es 4 in to
Heter ocyclic Com p ou n d s 5 P r om oted by P h SeOTf in
MeCN a t Room Tem p er a tu r e
Sch em e 2
lenenyl group can occur (Scheme 1). This represents a
new kind of ring-closure reaction which leads to the
formation of interesting heterocyclic compounds. We
describe in this paper the conversion of vicinal azido
selenides, containing a suitably positioned oxygen or
nitrogen nucleophile, into azido-substituted heterocyclic
compounds and those of vicinal acetamido and carbamato
selenides into oxazolines and oxazolidin-2-ones, respec-
tively.
Resu lts a n d Discu ssion
The selenium-induced deselenenylation reactions were
simply carried out by stirring for a few hours at room
temperature a solution of the selenides (1.0 mmol) and
benzeneselenenyl triflate18 (1.1 mmol) in acetonitrile or
in methylene chloride. After the usual workup, the
reaction mixtures were chromatographed through a silica
gel column to afford pure diphenyl diselenide and the
cyclization products.
The first experiments which were carried out con-
cerned the intramolecular nucleophilic deselenenylation
of the hydroxy, carboxy, and sulfonamido azido selenides
4 which were easily obtained, starting from alkenols,
alkenoic acids, and alkenyl sulfonamides, using our
recently reported procedure19 for the radical azido phe-
nylselenenylation of alkenes (Scheme 2). The reactions
of compounds 4 with PhSeOTf afforded the azido-
substituted heterocyclic compounds 5 (Scheme 2). The
results of these experiments are collected in Table 1. The
hydroxy azido selenides 4a and 4b (entries 1 and 2) gave
the 2-(azidomethyl)tetrahydrofurans 5a and 5b very
rapidly and in satisfactory yield. Compound 5b was
obtained as a mixture of two diastereoisomers which
could not be separated. Compound 4c (entry 3) required
longer reaction times to afford the pyran derivative 5c.
The carboxy derivatives 4d and 4f presented a similar
behavior. The formation of the δ-lactone 5f required
longer reaction time than that of the γ-lactone 4d . The
radical azido selenenylation of trans-styrylacetic acid
should afford the two diastereoisomeric azido selenides
4e. As a matter of fact this reaction gave rise to a
mixture of the trans azido lactone 5e and of one of the
two isomeric azido selenides of 4e. This latter isomer,
when treated with benzeneselenenyl triflate, gave the cis
azido lactone 5e (Table 1, entry 5). The structures of the
two isomers were demonstrated by differential NOE
experiments. The formation of the trans azido lactone
from the azido selenenylation of the trans-styrylacetic
acid cannot be easily explained. Nevertheless, the results
described above seem to indicate that the ring-closure
reaction is a stereospecific process. This seems to be
confirmed by the results obtained with the methyl ester
of styrylacetic acid. In this case the azido selenenylation
reaction gave the expected mixture of the two isomeric
methyl esters of 4e in a 1:1 ratio. This mixture was
directly deselenenylated with PhSeOTf and afforded a
1:1 mixture of the cis and trans azido lactones 5e which
were easily separated by column chromatography.
The last two examples reported in Table 1 (entries 7
and 8) concern the cyclization reactions which are effected
by nitrogen nucleophiles. The starting products em-
ployed for these experiments, 4g and 4h , were the azido
selenides of the alkenyl sulfonamides. The deseleneny-
lation of these two products afforded the 2-(azidomethyl)
N-methyl and N-phenylsulfonamido pyrrolidines 5g and
5h . On the contrary, when the same reaction was
effected starting from the seleno azide of 5-alkenyl amine,
(18) Murata, S.; Suzuki, T. Chem. Lett. 1987, 849. Nearly simulta-
neous work: Okazaki, R.; Itoh, Y. Chem. Lett. 1987, 1575.
(19) Tingoli, M.; Tiecco, M.; Chianelli, D.; Balducci, R.; Temperini,
A. J . Org. Chem. 1991, 56, 6809.

Intramolecular Nucleophilic Deselenenylation Reactions
J . Org. Chem., Vol. 61, No. 20, 1996 7087
Ta ble 2. Con ver sion of Vicin a l Azid o Selen id es 6 in to
Heter ocyclic Com p ou n d s 7 P r om oted by P h SeOTf in
Meth ylen e Ch lor id e a t Room Tem p er a tu r e
Sch em e 3
We have then used the intramolecular deselenenyla-
tion of selenides promoted by benzeneselenenyl triflate
to develop a simple approach to the stereocontrolled
synthesis of oxazolines and oxazolidin-2-ones. These
compounds have considerable synthetic relevance since
they can be easily converted into vicinal amino alco-
hols.27,28 The experiments described below not only
demonstrated that these syntheses can be easily effected
but they also gave useful information about the stereo-
chemical course of the deselenenylation process. Owing
to the structure of the substrates employed, this impor-
tant aspect of the process could not be investigated in
the case of the reactions of the azido selenides described
above, although some indications arose from the reactions
leading to the formation of the two isomers of 5e.
The synthesis of oxazolines was realized starting from
vicinal acetamido selenides. In this case the nucleophile
which effects the displacement reaction is the oxygen
atom of the acetamido group. Acetamido selenides were
prepared in two different and complementary ways. As
indicated in Scheme 3, in the case of terminal alkenes
the two methods afford the two regioisomeric acetamido
selenides.
The first method is the electrophilic amido seleneny-
lation of alkenes which is effected with PhSeCl, aceto-
nitrile, and water in the presence of trifluoromethane-
sulfonic acid.29 We have sligthly modified this procedure
by replacing PhSeCl with benzeneselenenyl sulfate (eas-
ily obtained from PhSeSePh by oxidation with am-
monium persulfate) which is a much stronger electro-
philic reagent.4,30 These reactions are both regiospecific
(Markovnikov orientation) and stereospecific (anti addi-
tion). This method was employed for the synthesis of
compounds 8c, 8d , erythro-8f, and trans-8h (Table 3). The
synthesis of the other acetamido selenides reported in
Table 3 was instead effected starting from the corre-
sponding azido selenides. The azido group was first
reduced to the amino group, using triphenylphosphine
and water,31 and this was then converted into the
acetamido group by treatment with acetyl chloride. The
radical azido selenenylation of alkenes occurs with an
anti-Markovnikov orientation, and therefore compounds
8a , 8b, and 8e were obtained starting from styrene,
1-octene, and allyl benzamide, respectively. In the case
of acenaphthylene the azido selenenylation afforded a
no cyclization products could be obtained. These results
were not completely unexpected since a similar behavior
is presented by the alkenyl amines in respect to the
related cyclization reactions induced by electrophilic
reagents. It is in fact well documented that in the
presence of electrophilic reagents primary alkenyl amines
do not give cyclization products20 whereas good results
are obtained starting from alkenyl amines N-substituted
with electron-withdrawing substituents.21-25
Further examples of the versatility of the presently
described deselenenylation reaction are reported in Table
2. In these cases the nucleophile which effects the
displacement reaction is the oxygen atom of an enolizable
carbonyl compound. Good results were obtained from the
reactions of the azido selenides of the allyl â-keto ester
6a and of the allyl â-diketone 6b which afforded dihy-
drofuran derivatives. In the first case (entry 1) a single
product, 7a , was obtained. The reaction of the â-diketone
6b (entry 2) gave instead a 1:1 mixture of the two possible
cyclization products 7b and 7c. These two products could
be easily separated by column chromatography.
The examples reported above indicate that the present
deselenenylation procedure, together with the regiose-
lective radical azido selenenylation of alkenes, can be
very useful to synthesize several azido-substituted het-
erocyclic compounds. These compounds are interesting
intermediates since the azido group can be used to effect
several conversions leading to the formation of more
complex molecules.26
(20) Clive, D. L. J .; Farina, V.; Sinigh, A.; Wong, C. K.; Kiel, W. A.;
Menchen, S. M. J . Chem. Soc., Chem. Commun. 1978, 379.
(21) Tiecco, M.; Testaferri, L.; Tingoli, M.; Bartoli, D.; Balducci, R.
J . Org. Chem. 1990, 55, 429.
(22) Clive, D. L. J .; Farina, V.; Sinigh, A.; Wong, C. K.; Kiel, W. A.;
Menchen, S. M. J . Org. Chem. 1980, 45, 2120.
(23) Webb II, R. R.; Danishefsky, S. Tetrahedron Lett. 1983, 24,
1357.
(24) Toshimitsu, A.; Terao, K.; Uemura, S. J . Org. Chem. 1986, 51,
1724.
(25) Cooper, M. A.; Ward, A. D. Tetrahedron Lett. 1994, 35, 5065.
(26) Tingoli, M.; Tiecco, M.; Testaferri, L.; Andrenacci, R.; Balducci,
R. J . Org. Chem. 1993, 58, 6097. There are more general references
on how “the azido group can be used to effect several conversions
leading to the formation of more complex molecules”. For example,
Patai, S. The Chemistry of the Azido Group, Wiley: London, 1971.
(27) Cardillo, G.; Orena, M. Tetrahedron 1990, 46, 3321.
(28) (a) Giuliano, R. M.; Bigos, C. Synth. Commun. 1995, 25, 1145.
(b) Li, C.; Fuchs, P. L. Synlett 1994, 629. (c) Kano, S.; Yokomatsu, T.;
Iwasawa, H.; Shibuya, S. Tetrahedron Lett. 1987, 28, 6331. (d) Hassner,
A.; Lorber, M. E.; Heathcock, C. J . Org. Chem. 1967, 32, 540.
(29) Toshimitsu, A.; Aoai, T.; Owada, H.; Uemura, S.; Okano, M. J .
Org. Chem. 1981, 46, 4727.
(30) Tiecco, M.; Testaferri, L.; Tingoli, M.; Chianelli, D.; Bartoli, D.
Tetrahedron Lett. 1989, 30, 1417.
(31) Gololobov, Y. G.; Kasukhin, L. F. Tetrahedron 1992, 48, 1353.

7088 J . Org. Chem., Vol. 61, No. 20, 1996
Tingoli et al.
Ta ble 3. Con ver sion of Vicin a l Aceta m id o Selen id es 8
in to Oxa zolin es 9 P r om oted by P h SeOTf in Meth ylen e
Ch lor id e a t Room Tem p er a tu r e
Ta ble 4. Con ver sion of Vicin a l Ca r ba m a to Selen id es 10
in to Oxa zolid in -2-on es 11 P r om oted by P h SeOTf in
Meth ylen e Ch lor id e a t Room Tem p er a tu r e
the acetamido selenides having a defined stereochemistry
(Table 3, entries 6, 8, and 9). A single oxazoline was
obtained in every case. erythro-8f gave the trans oxazo-
line 9f and the trans compounds 8h and 8i gave the cis
oxazolines 9h and 9i, respectively. In agreement with
these results, the 1:1 mixture of the erythro- and threo-
8g gave a 1:1 mixture of the trans and cis oxazolines 9g.
Similar results were obtained from the above described
cyclization reaction of the 1:1 mixture of the methyl
esters of 4e. Thus, the whole of these experimental data
clearly indicates that the presently reported intramo-
lecular substitution on the selenonium ion intermediates
is a stereospecific process which occurs with inversion of
configuration at the carbon atom bearing the phenylse-
leno group.
Further evidence came from the reactions carried out
on carbamato selenides 10 which afforded the oxazolidin-
2-ones 11 (Table 4). The starting products were prepared
from the corresponding azido selenides which were
reduced to the amines and then treated with benzyl
chloroformate. The radical azido selenenylation of cy-
clohexene gave a 3:1 mixture of the two stereoisomers
which were directly transformed into the two isomeric
carbamato selenides 10b and 10c. These were easily
separated by column chromatography. The structures
of the two isomers were assigned on the basis of their
NMR spectra and were also confirmed by an independent
synthesis of 10b starting from the known33 trans-1-azido-
2-(phenylseleno)cyclohexane. Under the usual condi-
tions, 10a gave 11a in good yield. The trans isomer 10b
was easily converted into the cis oxazolidin-2-one 11b,
whereas the cis isomer 10c, in which the intramolecular
displacement with inversion of configuration cannot
occur, was recovered unchanged even after prolonged
reaction times. The results obtained from the reactions
of the acetamido and carbamato selenides demonstrate
that the presently described deselenenylation reaction
represents a convenient procedure to effect the stereospe-
cific synthesis of oxazoline and oxazolidin-2-one deriva-
single stereoisomer which was transformed into the
acetamido selenide. The small value of the vicinal
coupling constant32 indicates that this is the trans isomer
8i. As expected, the radical azido selenenylation of trans-
4-octene gave instead a 1:1 mixture of two stereoisomers.
These were transformed into a 1:1 mixture of the ben-
zamido selenides 8g which could not be separated.
The results of the reactions of the amido selenides 8a -i
with PhSeOTf are collected in Table 3. The cyclization
reactions proceeded smoothly in every case and afforded
the expected oxazolines 9a -i in good yield. Also included
in Table 3 is the reaction of the azido selenide 8e which
gave rise to the interesting 5-(azidomethyl)oxazoline 9e.
Of particular importance were the results obtained from
(33) (a) Denis, J . N.; Vicens, J .; Krief, A. Tetrahedron Lett. 1979,
2697. (b) Hassner, A.; Amarasekara, A. S. Tetrahedron Lett. 1987, 28,
5185.
(32) Dewar, M. J . S.; Fahey, R. C. J . Am. Chem. Soc. 1963, 85, 2245.

Intramolecular Nucleophilic Deselenenylation Reactions
J . Org. Chem., Vol. 61, No. 20, 1996 7089
Anal. Calcd for C16H15N3O2Se: C, 53.34; H, 4.20; N, 11.66.
Found: C, 53.40; H, 4.28; N, 11.54. Meth yl ester : (1:1
mixture of two isomers) (72% yield): oil; 1H NMR δ 7.49-7.35
(m, 4 H), 7.34-7.1 (m, 16 H), 4.45-4.22 (m, 4 H), 3.7 (s, 3 H),
3.66 (s, 3H), 2.85 (dd, 1 H, J ) 16.5, 3.8 Hz), 2.53-2.38 (m, 2
H), 2.43 (dd, 1 H, J ) 16.5, 8.9 Hz); 13C NMR δ 170.8, 170.7,
139.1, 138.5, 135.4, 135.3, 129.1, 128.9, 128.8, 128.6, 128.4,
128.2, 128.1, 127.7, 127.2, 63.7, 62.6, 53.3, 52.2, 51.9, 38.5, 38.2.
Anal. Calcd for C17H17N3O2Se: C, 54.55; H, 4.58; N, 11.23.
Found: C, 54.49; H, 4.65; N, 11.33.
6-Azid o-5-(p h en ylselen o)h exa n oic a cid (4f) (60%
yield): oil; 1H NMR δ 10.5 (br s, 1 H), 7.7-7.5 (m, 2 H), 7.5-
7.18 (m, 3 H), 3.7-3.32 (m, 2 H), 3.3-3.1 (m, 1 H), 2.58-2.24
(m, 2 H), 2.14-1.46 (m, 4 H); 13C NMR δ 179.3, 135.3, 129.1,
128.0, 127.4, 55.7, 44.0, 33.4, 31.7, 22.6. Anal. Calcd for
C12H15N3O2Se: C, 46.16; H, 4.84; N, 13.46. Found: C, 46.08;
H, 4.85; N, 13.41.
N -[ 5 -Az i d o -4 -( p h e n y l s e l e n o ) p e n t y l ] m e t h a n e -
su lfon a m id e (4g) (56% yield): oil; 1H NMR δ 7.64-7.5 (m, 2
H), 7.4-7.32 (m, 3 H), 4.61 (t, 1 H, J ) 6.0 Hz), 3.58 (dd, 1 H,
J ) 12.5, 5.2 Hz), 3.42 (dd, 1 H, J ) 12.5, 7.5 Hz), 3.26-3.16
(m, 3 H), 2.9 (s, 3 H), 2.0-1.48 (m, 4 H); 13C NMR δ 135.0,
129.0, 127.9, 127.1, 55.5, 43.8, 42.5, 39.7, 29.2, 27.8. Anal.
Calcd for C12H18N4O2SSe: C, 39.89; H, 5.02; N, 15.51.
Found: C, 39.86; H, 5.08; N, 15.39.
N -[ 5 -Az i d o -4 -( p h e n y l s e l e n o ) p e n t y l ] b e n z e n e -
su lfon a m id e (4h ) (49% yield): oil; 1H NMR δ 7.94-7.78 (m,
2 H), 7.68-7.4 (m, 5 H), 7.36-7.16 (m, 3 H), 4.72 (t, 1 H, J )
6.3 Hz), 3.54 (dd, 1 H, J ) 12.5, 5.2 Hz), 3.35 (dd, 1 H, J )
12.5, 7.5 Hz), 3.16-2.84 (m, 3 H), 1.88-1.36 (m, 4 H); 13C NMR
δ 139.6, 135.1, 132.4, 129.0, 128.9, 127.9, 126.8, 55.5, 43.8, 42.5,
29.2, 27.4. Anal. Calcd for C17H20N4O2SSe: C, 48.23; H, 4.76;
N, 13.23. Found: C, 48.15; H, 4.84; N. 13.31.
tives. These reactions therefore can be usefully employed
for the synthesis of stereodefined vicinal amino alcohols.
All the cyclization reactions described above were
effected with PhSeOTf in methylene chloride at room
temperature. However, other selenenylating agents with
a non-nucleophilic counterion can be employed. Indeed,
compounds 9a and 9c were obtained in good yield from
8a and 8c (Table 3, entries 1 and 3) when the PhSeOTf
was replaced by the less expensive benzeneselenenyl
sulfate which can be easily prepared from diphenyl
diselenide.4,30
In conclusion, from the results described in this paper
it can be anticipated that the stereospecific deseleneny-
lation of selenides promoted by electrophilic seleneny-
lating agents can find a more general application and
that it can also be applied to the synthesis of complex
molecules.
Exp er im en ta l Section
Product identification was effected by 1H and 13C NMR
spectroscopy, mass spectrometry, and elemental analyses.21
Physical and spectral data of compounds 5d ,34 6a ,26 8c,29
8d ,35 8h ,29 9a ,36 9c,37 9f,38 9h ,37,38 and 11b39 have already been
reported in the literature.
P r ep a r a tion of Azid o Selen id es. These compounds were
prepared according to the recently reported procedure.19
5-Azid o-4-(p h en ylselen o)-1-p en ta n ol (4a ) (56% yield):
oil; 1H NMR δ 7.7-7.4 (m, 2 H), 7.4-7.2 (m, 3 H), 3.7-3.1 (m,
5 H), 2.0-1.5 (m, 5 H); 13C NMR δ 135.3, 133.2, 129.2, 128.1,
62.3, 56.0, 44.4, 30.7, 28.9; MS m/ z (relative intensity) 285
(6), 157 (42), 91 (15), 78 (52), 77 (42), 71 (100). Anal. Calcd
for C11H15N3OSe: C, 46.49; H, 5.32; N, 14.78. Found: C, 46.40;
H, 5.32; N, 14.78.
6-Azid o-5-(p h en ylselen o)-3-b en zoylh exa n -2-on e (6b )
1
(70% yield): oil; H NMR δ 8.15-7.91 (m, 4 H), 7.7-7.14 (m,
16 H), 5.1-4.9 (m, 2 H), 3.75-3.4 (m, 4 H), 3.37-3.18 (m, 1
H), 3.18-2.98 (m, 1 H), 2.72-2.42 (m, 2 H), 2.3-1.94 (m, 2
H), 2.14 (s, 3 H), 2.04 (s, 3 H); 13C NMR δ 202.6, 202.5, 195.8,
195.6, 136.3, 135.0, 134.7, 133.7, 129.2, 129.1, 128.8, 128.7,
128.6, 128.5, 128.1, 127.5, 60.9, 60.5, 56.2, 56.1, 43.4, 42.6, 31.9,
31.5, 28.5, 28.2. Anal. Calcd for C19H19N3O2Se: C, 57.00; H,
4.78; N, 10.50. Found: C, 57.02; H, 4.70; N, 10.61.
5-Azido-4-(ph en ylselen o)-1-ph en yl-1-pen tan ol (4b) (47%
1
yield): oil; H NMR δ 7.6-7.43 (m, 2 H), 7.4-7.16 (m, 8 H),
4.78-4.6 (m, 1 H), 3.54 (dd, 1 H, J ) 12.5, 5.5 Hz), 3.45-3.28
(m, 1 H), 3.25-3.18 (m, 1 H), 2.2-1.72 (m, 5 H); 13C NMR δ
135.4, 129.1, 128.5, 128.1, 127.7, 125.8, 125.7, 74.3, 73.8, 55.9,
44.5, 44.3, 36.9, 36.7, 28.8, 28.5; MS m/ z (relative intensity)
315 (14), 184 (20), 158 (100), 157 (20), 104 (93), 91 (45), 77
(38), 55 (77). Anal. Calcd for C17H19N3OSe: C, 56.67; H, 5.31;
N, 11.66. Found: C, 56.80; H, 5.42; N, 11.48.
N-[3-Azido-2-(ph en ylselen o)pr opyl]ben zam ide (8e) (52%
1
yield): oil; H NMR δ 7.8-7.66 (m, 2 H), 7.66-7.19 (m, 8 H),
6.93-6.72 (m, 1 H), 3.97-3.38 (m, 5 H); 13C NMR δ 167.6,
134.9, 131.4, 129.2, 128.3, 128.1, 127.3, 126.8, 53.8, 43.6, 42.2.
Anal. Calcd for C16H16N4OSe: C, 53.49; H, 4.49; N, 15.59.
Found: C, 53.55; H, 4.41; N, 15.62.
6-Azid o-5-(p h en ylselen o)-1-h exa n ol (4c) (56% yield): oil;
1H NMR δ 7.66-7.5 (m, 2 H), 7.47-7.22 (m, 3 H), 3.8-3.34
(m, 5 H), 3.31-3.12 (m, 1 H), 1.95-1.21 (m, 6 H); 13C NMR δ
135.0, 128.9, 127.8, 127.2, 62.1, 55.6, 44.4, 32.1, 23.7; MS m/ z
(relative intensity) 299 (13), 157 (89), 85 (100), 78 (85), 77 (72),
56 (55), 41 (98). Anal. Calcd for C12H17N3OSe: C, 48.33; H,
5.75; N, 14.09. Found: C, 48.24; H, 5.69; N, 14.17.
5-Azid o-4-(p h en ylselen o)p en t a n oic a cid (4d ) (71%
yield): oil; 1H NMR δ 9.5 (br s, 1 H), 7.65-7.5 (m, 2 H), 7.48-
7.21 (m, 3 H), 3.62 (dd, 1 H, J ) 12.5, 5.4 Hz), 3.42 (dd, 1 H,
J ) 12.5, 7.6 Hz), 3.31-3.14 (m, 1 H), 2.8-2.6 (m, 2 H), 2.28-
2.04 (m, 1 H), 1.95-1.7 (m, 1 H); 13C NMR δ 179.1, 135.5, 129.3,
128.3, 126.9, 55.9, 43.6, 32.1, 27.3. Anal. Calcd for C11H13N3O2-
Se: C, 44.31; H, 4.39; N, 14.09. Found: C, 44.22; H, 4.49; N,
14.01.
P r ep a r a tion of Aceta m id o Selen id es. Meth od A. A
solution of trifluoromethanesulfonic acid (1 mmol) in water (1
mL) and acetonitrile (5 mL) was added to a mixture of the
olefin (1 mmol), diphenyl diselenide (0.55 mmol), and am-
monium persulfate (0.6 mmol) in acetonitrile (20 mL). The
mixture was refluxed for 2 h and then poured on 10% aqueous
Na2CO3 and extracted with Et2O. The organic layer was
washed with brine, dried (Na2SO4), and evaporated. The
reaction products were obtained in pure form after chroma-
tography on silica gel using Et2O as eluant. Reaction yields
and physical and spectral data of the reaction products are
reported below.
N-[[1-P r op yl-2-(p h en ylselen o)]p en tyl]a ceta m id e (8f)
(80% yield): oil; 1H NMR δ 7.6-7.45 (m, 2 H), 7.3-7.15 (m, 3
H), 5.6 (d, 1 H, J ) 8.3 Hz), 4.25-4.0 (m, 1 H), 3.45-3.3 (m,
1 H), 2.0-1.3 (m, 11 H), 0.9 (t, 6 H, J ) 7.0 Hz); 13C NMR δ
169.3, 133.3, 130.6, 128.9, 126.9, 54.2, 52.2, 36.1, 32.4, 22.8,
21.2, 19.1, 13.7, 13.5; MS m/ z (relative intensity) 327 (6), 268
(44), 170 (53), 157 (13), 128 (43), 114 (41), 72 (100). Anal. Calcd
for C16H25NOSe: C, 58.89; H, 7.72; N, 4.29. Found: C, 58.96;
H, 7.69; N, 4.18.
Meth od B. A solution of triphenylphosphine (1.1 mmol)
in THF (3 mL) was slowly added at rt to a solution of seleno
azide (1 mmol) in THF (5 mL). The progress of the reaction
was monitored by TLC. When the starting product was
consumed, water (1 mL) was added and the mixture was
warmed at 40 °C for 20 h. The solvent was evaporated, and
the residue was dried over P2O5. The crude product was
3-Azid o-4-p h en yl-4-(p h en ylselen o)bu ta n oic a cid (4e)
(26% yield): oil; 1H NMR δ 9.4 (br s, 1 H), 7.52-7.35 (m, 2 H),
7.35-7.08 (m, 8 H), 4.44-4.18 (m, 2 H), 2.95 (dd, 1 H, J )
16.9, 3.5 Hz), 2.46 (dd, 1H, J ) 16.9, 8.9 Hz); 13C NMR δ 176.5,
138.4, 135.3, 129.2, 128.6, 128.5, 128.3, 127.8, 62.3, 52.3, 38.6.
(34) Olsen, R. K.; Bhat, K. L.; Wardle, R. B.; Hennen, W. J .; Kini,
G. D. J . Org. Chem. 1985, 50, 896.
(35) Yoshida, M.; Satoh, N.; Kamigata, N. Chem. Lett. 1989, 1433.
(36) Padwa, A.; Gasdaska, J . R.; Tomas, M.; Turro, N. J .; Cha, Y.;
Gould, I. R. J . Am. Chem. Soc. 1986, 108, 6739.
(37) Bellucci, G.; Bianchini, R.; Chiappe, C. J . Org. Chem. 1991, 56,
3067.
(38) Hu, N. X.; Aso, Y.; Otsubo, T.; Ogura, F. Tetrahedron Lett. 1988,
29, 1049.
(39) Hu, N. X.; Aso, Y.; Otsubo, T.; Ogura, F. J . Chem. Soc., Chem.
Commun. 1987, 1447.

7090 J . Org. Chem., Vol. 61, No. 20, 1996
Tingoli et al.
dissolved in THF (10 mL) and cooled at 0° C. Triethylamine
(2 mmol) and acetyl chloride (1.1 mmol) were added, and the
mixture was stirred for 4 h. The mixture was then treated
with hydrochloric acid (3% solution in water) and extracted
with Et2O. The organic layer was washed with brine and dried
(Na2SO4). The reaction products were obtained in pure form
after chromatography on silica gel using Et2O as eluant.
Reaction yields and physical and spectral data of the reaction
products are reported below.
24.0, 22.3; MS m/ z (relative intensity) 281 (26), 158 (25), 157
(11), 81 (100), 77 (11). Anal. Calcd for C20H23NO2Se: C, 61.85;
H, 5.97; N, 3.61. Found: C, 61.81; H, 6.04; N, 3.70.
Deselen en yla tion Rea ction s. Gen er a l P r oced u r e. The
selenide (1 mmol) was added to a solution of PhSeOTf18 (1.1
mmol) in acetonitrile or in methylene chloride (10 mL) stirred
under nitrogen at 0° C. The progress of the reaction was
monitored by TLC and GLC. The crude mixture was filtered
over Al2O3(Grade III)/Na2CO3. The filtrate was dried (Na2-
SO4) and evaporated. The reaction products were obtained
in pure form after column chromatography on silica gel using
petroleum ether/Et2O (70/30) as eluant. Reaction yields of
isolated products are indicated in Tables 1-4. Physical and
spectral data of the reaction products are reported below.
2-(Azid om eth yl)tetr a h yd r ofu r a n (5a ): oil; 1H NMR δ
4.16-4.0 (m, 1 H), 3.99-3.73 (m, 2 H), 3.37 (dd, 1 H, J ) 12.7,
4.0 Hz), 3.22 (dd, 1 H, J ) 15.8, 12.7 Hz), 2.1-1.85 (m, 3 H),
1.77-1.6 (m, 1 H); 13C NMR δ 77.7, 68.4, 54.5, 28.7, 25.8; MS
m/ z (relative intensity) 99 (1), 71 (100), 43 (77), 41 (53). Anal.
Calcd for C5H9N3O: C, 47.23; H, 7.13; N, 33.05. Found: C,
47.16; H, 7.03; N, 33.12.
N-[2-P h en yl-2-(ph en ylselen o)eth yl]acetam ide (8a) (84%
1
yield): oil; H NMR δ 7.5-7.38 (m, 2 H), 7.36-7.04 (m, 8 H),
6.2 (t, 1 H, J ) 5.7 Hz), 4.44 (dd, 1 H, J ) 8.2, 7.9 Hz), 3.82
(dd, 1 H, J ) 13.8, 7.9 Hz), 3.7 (dd, 1 H, J ) 13.8, 8.2 Hz),
1.75 (s, 3 H); 13C NMR δ 169.9, 139.4, 134.7, 128.8, 128.3,
127.7, 127.5, 127.2, 46.4, 44.0, 22.7; MS m/ z (relative intensity)
260 (1), 162 (48), 120 (100), 103 (12), 77 (10), 43 (14). Anal.
Calcd for C16H17NOSe: C, 60.38; H, 5.38; N, 4.40. Found: C,
60.43; H, 5.35; N, 4.29.
N-[2-(P h en ylselen o)octyl]a ceta m id e (8b) (64% yield):
oil; 1H NMR δ 7.62-7.48 (m, 2 H), 7.36-7.2 (m, 3 H), 5.95 (br
s, 1 H), 3.59 (ddt, 1 H, J ) 9.4, 7.7, 6.4 Hz), 3.35-3.17 (m, 2
H), 1.9 (s, 3 H), 1.68-1.4 (m, 4 H), 1.36-1.16 (m, 6 H), 0.88 (t,
3 H, J ) 7.0 Hz); 13C NMR δ 169.9, 134.7, 128.9, 128.0, 127.5,
46.0, 43.7, 32.8, 31.4, 28.8, 27.5, 22.9, 22.3, 13.8; MS m/ z
(relative intensity) 327 (7), 198 (31), 170 (100), 157 (21), 128
(51), 43 (76). Anal. Calcd for C16H25NOSe: C, 58.89; H, 7.72;
N, 4.29. Found: C, 58.80; H, 7.75; N, 4.36.
2-(Azid om eth yl)-5-p h en yltetr a h yd r ofu r a n (5b). Isomer
1
A: oil; H NMR δ 7.4-7.15 (m, 5 H), 5.07 (dd, 1 H, J ) 7.2,
6.2 Hz), 4.51-4.36 (m, 1 H), 3.48 (dd, 1 H, J ) 12.7, 4.1 Hz),
3.31 (dd, 1 H, J ) 12.7, 5.3 Hz), 2.5-2.3 (m, 1 H), 2.22-2.05
(m, 1 H), 2.02-1.8 (m, 2 H); 13C NMR δ 128.3, 127.3, 125.5,
1
81.0, 78.3, 54.7, 35.0, 29.4. Isomer B: oil; H NMR δ 7.42-
N-[[1-P r op yl-2-(p h en ylselen o)]p en tyl]ben za m id e (8g)
(1:1 mixture of two isomers) (77% yield): oil; 1H NMR δ 8.22-
8.08 (m, 2 H), 7.76-7.22 (m, 16 H), 7.2-7.08 (m, 2 H), 6.38 (d,
1H, J ) 9.2 Hz), 6.3 (d, 1 H, J ) 9.5 Hz), 4.54-4.32 (m, 2 H),
3.52 (dt, 1 H, J ) 7.6, 3.3 Hz), 3.39 (ddd, 1 H, J ) 7.9, 5.8, 2.6
Hz), 1.82-1.12 (m, 16 H), 1.04-0.74 (m, 12 H); 13C NMR δ
167.0, 166.9, 134.4, 133.3, 132.9, 131.2, 131.1, 130.3, 129.8,
129.0, 128.6, 128.3, 128.1, 127.4, 126.9, 126.7, 126.6, 54.5, 53.1,
52.6, 52.5, 36.3, 35.3, 32.8, 21.2, 21.1, 19.2, 13.8, 13.6; MS m/ z
(relative intensity) 389 (1), 268 (14), 176 (12), 105 (100), 77
(28). Anal. Calcd for C21H27NOSe: C, 64.94; H, 7.01; N, 3.61.
Found: C, 65.02; H, 7.12; N, 3.58.
trans-1-Aceta m id o-2-(p h en ylselen o)a cen a p h th en e (8i)
(76% yield): oil; 1H NMR 7.8-7.05 (m, 11 H), 6.03 (dd, 1 H, J
) 8.8, 1.1 Hz), 5.76 (d, 1 H, J ) 8.8 Hz), 4.88 (d, 1 H, J ) 1.1
Hz), 1.94 (s, 3 H); 13C NMR δ 169.2, 142.3, 142.0, 135.4, 130.8,
128.6, 128.1, 128.0, 124.5, 123.8, 120.9, 120.5, 62.0, 50.4, 23.0.
Anal. Calcd for C20H17NOSe: C, 65.58; H, 4.68; N, 3.82.
Found: C, 65.54; H, 4.79; N, 3.88.
P r ep a r a tion of Ca r ba m a to Selen id es. The carbamato
selenides were prepared according to the procedure described
above (method B) for the synthesis of the acetamido selenides
using benzyl chloroformate (1.1 mmol) instead of acetyl
chloride. Reaction yields and physical and spectral data of
the reaction products are reported below.
O-Ben zyl N-[2-(P h en ylselen o)-2-p h en yleth yl]ca r ba m -
a te (10a ) (83% yield): oil; 1H NMR δ 7.52-7.06 (m, 15 H),
5.02 (s, 2 H), 5.0 (br s, 1 H), 4.4 (t, 1 H, J ) 7.9 Hz), 3.9-3.58
(m, 2 H); 13C NMR δ 155.9, 139.4, 136.3, 135.0, 128.9, 128.5,
128.3, 127.9, 127.7, 127.4, 66.5, 47.0, 45.6; MS m/ z (relative
intensity) 304 (1), 157 (13), 146 (68), 128 (100), 91 (17), 77 (27).
Anal. Calcd for C22H21NO2Se: C, 64.39; H, 5.16; N, 3.41.
Found: C, 64.32; H, 5.28; N, 3.51.
7.2 (m, 5 H), 4.91 (dd, 1 H, J ) 7.8, 6.4 Hz), 4.34-4.18 (m, 1
H), 3.55-3.33 (m, 2 H), 2.43-2.04 (m, 2 H), 1.99-1.78 (m, 2
H); 13C NMR δ 128.3, 127.3, 125.7, 81.6, 78.0, 54.9, 34.1, 28.8.
MS m/ z (relative intensity) (Isomers A and B) 147 (94), 129
(43), 105 (27), 91 (100), 77 (20), 41 (29). Anal. Calcd for
C11H13N3O: C, 65.01; H, 6.45; N, 20.67. Found: C, 64.90; H,
6.36; N, 20.81.
2-(Azid om eth yl)tetr a h yd r op yr a n (5c): oil; 1H NMR δ
4.16-3.92 (m, 1 H), 3.62-3.1 (m, 4 H), 2.0-1.32 (m, 6 H); 13
C
NMR δ 77.9, 69.6, 56.9, 30.2, 27.0, 24.2; MS m/ z (relative
intensity) 85 (100), 67 (26), 57 (29), 43 (40), 41 (63). Anal.
Calcd for C6H11N3O: C, 51.05; H, 7.85; N, 29.77. Found: C,
51.15; H, 7.99; N, 29.80.
4-Azid o-5-p h en yl-4,5-d ih yd r o-3H -fu r a n -2-on e
(5e).
cis-Isomer: oil; 1H NMR δ 7.48-7.28 (m, 5 H), 5.62 (d, 1 H, J
) 4.3 Hz), 4.5 (ddd, 1 H, J ) 6.2, 4.3, 1.3 Hz), 2.97 (dd, 1 H, J
) 17.6, 6.2 Hz), 2.66 (dd, 1 H, J ) 17.6, 1.3 Hz); 13C NMR δ
173.6, 128.9, 128.6, 126.1, 125.1, 83.3, 61.5, 36.2. Anal. Calcd
for C10H9N3O2: C, 59.11; H, 4.46; N, 20.68. Found: C, 59.19;
H, 4.33; N, 20.78. trans-Isomer: oil; 1H NMR δ 7.55-7.25 (m,
5 H), 5.33 (d, 1 H, J ) 5.0 Hz), 4.23 (ddd, 1 H, J ) 7.5, 6.0, 5.0
Hz), 2.97 (dd, 1 H, J ) 17.7, 7.5 Hz), 2.66 (dd, 1 H, J ) 17.7,
6.0 Hz); 13C NMR δ 171.7, 129.2, 125.1, 84.7, 64.0, 34.4; MS
m/ z (relative intensity) 203 (1), 148 (18), 105 (100), 77 (41),
42 (50). Anal. Calcd for C10H9N3O2: C, 59.11; H, 4.46; N,
20.68. Found: C, 59.07; H, 4.52; N, 20.55.
6-(Azidom eth yl)tetr ah ydr opyr an -2-on e (5f): oil; 1H NMR
δ 4.57-4.32 (m, 1 H), 3.64-3.32 (m, 2 H), 2.75-2.28 (m, 2 H),
2.12-1.54 (m, 4 H);
18.0; MS m/ z (relative intensity) 155 (1), 99 (100), 71 (43), 55
H9N3O2: C,
13C NMR δ 170.1, 78.3, 54.2, 29.1, 24.7,
(50), 43 (46), 42 (25), 41 (29). Anal. Calcd for C6
46.45; H, 5.85; N, 27.08. Found: C, 46.54; H, 5.93; N, 27.02.
1-(Meth ylsu lfon yl)-2-(a zid om eth yl)pyr r olid in e (5g): oil;
1H NMR δ 3.97-3.79 (m, 1 H), 3.6-3.28 (m, 4 H), 2.88 (s, 3
H), 2.16-1.84 (m, 4 H); 13C NMR δ 58.7, 54.7, 49.1, 35.0, 29.3,
24.3; MS m/ z (relative intensity) 148 (87), 70 (100), 41 (20).
Anal. Calcd for C6H12N4O2S: C, 35.28; H, 5.92; N, 27.43.
Found: C, 35.21; H, 6.03; N, 27.40.
1-(Ben zen esu lfon yl)-2-(a zid om eth yl)p yr r olid in e (5h ):
oil; 1H NMR δ 7.9-7.78 (m, 2 H), 7.68-7.46 (m, 3 H), 3.8-
3.63 (m, 1 H), 3.6-3.38 (m, 3 H), 3.28-3.08 (m, 1 H), 1.96-
1.43 (m, 4 H); 13C NMR δ 134.3, 132.8, 129.0, 127.3, 58.8, 55.0,
49.3, 29.1, 23.8; MS m/ z (relative intensity) 210 (79), 141 (49),
77 (100), 51 (17), 41 (14). Anal. Calcd for C11H14N4O2S: C,
49.61; H, 5.30; N, 21.04. Found: C, 49.72; H, 5.25; N, 21.01.
2-P h en yl-3-(eth oxyca r bon yl)-5-(a zid om eth yl)-4,5-d ih y-
d r ofu r a n (7a ): oil; 1H NMR δ 7.88-7.72 (m, 2 H), 7.46-7.31
(m, 3 H), 4.97-4.79 (m, 1 H), 4.14 (q, 2 H, J ) 7.0 Hz), 3.56-
3.36 (m, 2 H), 3.22 (dd, 1 H, J ) 15.3, 10.5 Hz), 2.89 (dd, 1 H,
O-Ben zyl tr a n s-N-[2-(P h en ylselen o)cycloh exyl]ca r -
ba m a te (10b) (66% yield): mp 88-90 °C; 1H NMR δ 7.6-7.5
(m, 2 H), 7.4-7.1 (m, 8 H), 5.16 (s, 2 H), 5.06 (d, 1 H, J ) 8.7
Hz), 3.52 (ddt, 1 H, J ) 10.1, 8.7, 4.2 Hz), 2.99 (dt, 1 H, J )
10.1, 3.9 Hz), 2.2-2.0 (m, 2 H), 1.7-1.1 (m, 6 H); 13C NMR δ
155.6, 136.6, 135.6, 128.8, 128.3, 127.9, 127.7, 66.5, 54.4, 48.2,
33.8, 33.7, 26.3, 24.4; MS m/ z (relative intensity) 281 (19),
158 (37), 157 (11), 81 (100), 77 (14). Anal. Calcd for C20H23
-
NO2Se: C, 61.85; H, 5.97; N, 3.61. Found: C, 61.93; H, 5.88;
N, 3.74.
O-Ben zyl cis-N-[2-(P h en ylselen o)cycloh exyl]ca r ba m -
1
a te (10c) (22% yield): mp 90-92 °C; H NMR δ 7.6-7.4 (m,
2 H), 7.4-7.1 (m, 8 H), 5.24 (d, 1 H, J ) 8.7 Hz), 5.02 (AB
system, 2 H), 3.85-3.65 (m, 2 H), 2.2-2.0 (m, 1 H), 2.0-1.8
(m, 1 H), 1.8-1.2 (m, 6 H); 13C NMR δ 155.3, 136.5, 133.7,
130.0, 128.9, 128.3, 127.8, 127.1, 66.4, 52.3, 52.1, 32.2, 30.3,

Intramolecular Nucleophilic Deselenenylation Reactions
J . Org. Chem., Vol. 61, No. 20, 1996 7091
J ) 15.3, 7.6 Hz), 1.22 (t, 3 H, J ) 7.0 Hz); 13C NMR δ 164.7,
164.1, 130.3, 129.4, 129.1, 127.5, 102.2, 79.5, 59.7, 54.2, 34.4,
14.0; MS m/ z (relative intensity) 273 (1), 216 (14), 171 (22),
122 (17), 115 (18), 105 (100), 77 (37). Anal. Calcd for
C14H15N3O3: C, 61.53; H, 5.53; N, 15.38. Found: C, 61.39; H,
5.62; N, 15.26.
2-P h en yl-5-(a zid om eth yl)-4,5-d ih yd r ooxa zole (9e): oil;
1H NMR δ 8.06-7.9 (m, 2 H), 7.58-7.35 (m, 3 H), 4.96-4.82
(m, 1 H), 4.15 (dd, 1 H, J ) 15.0, 9.8 Hz), 3.82 (dd, 1 H, J )
15.0, 7.0 Hz), 3.46 (d, 2 H, J ) 5.2 Hz); 13C NMR δ 163.5, 131.3,
128.2, 128.1, 127.2, 78.0, 57.6, 53.8. Anal. Calcd for
C10H10N4O: C, 59.40; H, 4.98; N, 27.71. Found: C, 59.49; H,
4.87; N, 27.63.
2-P h en yl-4,5-d ip r op yl-4,5-d ih yd r ooxa zole (9g): oil; 1H
NMR δ 8.2-7.85 (m, 4 H), 7.52-7.39 (m, 6 H), 4.74-4.55 (m,
1 H), 4.36-4.08 (m, 2 H), 3.9-3.74 (m, 1 H), 1.82-1.41 (m, 16
H), 1.05-0.85 (m, 12 H); 13C NMR δ 162.3, 130.7, 128.3, 128.2,
127.9, 84.6, 82.5, 71.6, 67.9, 38.0, 32.5, 31.3, 20.3, 19.8, 18.7,
18.3, 14.0, 13.9, 13.7; MS m/ z (relative intensity) (isomer A):
231 (5), 188 (100), 130 (43), 104 (48), 77 (28); (isomer B): 231
(8), 188 (100), 130 (91), 104 (74), 77 (45). Anal. Calcd for
C15H21NO: C, 77.88; H, 9.15; N, 6.05. Found: C, 77.83; H,
9.09; N, 6.12.
2-P h en yl-3-a cet yl-5-(a zid om et h yl)-4,5-d ih yd r ofu r a n
1
(7b): oil; H NMR δ 7.67-7.48 (m, 5 H), 5.02-4.84 (m, 1 H),
3.54 (dd, 1 H, J ) 13.3, 4.1 Hz), 3.48 (dd, 1 H, J ) 13.3, 5.6
Hz), 3.25 (dd, 1 H, J ) 15.1, 10.6 Hz), 2.93 (dd, 1 H, J ) 15.1,
7.5 Hz), 1.98 (s, 3 H); 13C NMR δ 193.8, 164.9, 130.4, 130.3,
128.9, 128.1, 114.3, 80.0, 54.1, 34.2, 28.6; MS m/ z (relative
intensity) 243 (1), 171 (22), 105 (94), 77 (34), 43 (100). Anal.
Calcd for C13H13N3O2: C, 64.19; H, 5.39; N, 17.27. Found: C,
64.16; H, 5.45; N, 17.37.
2-Me t h yl-3-b e n zoyl-5-(a zid om e t h yl)-4,5-d ih yd r ofu -
1
r a n (7c): oil; H NMR δ 7.65-7.3 (m, 5 H), 4.92-4.76 (m, 1
H), 3.52 (dd, 1 H, J ) 13.1, 3.7 Hz), 3.41 (dd, 1 H, J ) 13.1,
6.0 Hz), 3.19 (dd, 1 H, J ) 14.8, 10.4 Hz), 2.89 (dd, 1 H, J )
14.8, 7.4 Hz), 1.83 (s, 3H); 13C NMR δ 192.5, 167.5, 140.5,
130.9, 128.1, 127.5, 112.2, 80.2, 54.1, 34.0, 15.0; MS m/ z
(relative intensity) 243 (6), 185 (27), 105 (100), 77 (64), 43 (52).
Anal. Calcd for C13H13N3O2: C, 64.19; H, 5.39; N, 17.27.
Found: C, 64.16; H, 5.45; N, 17.37.
cis-(()-8-Me t h yl-6b ,9a -d ih yd r oa ce n a p h t h [1,2-d ]ox-
1
a zole (9i): mp 125-126 °C; H NMR δ 7.85-7.69 (m, 2 H),
7.64-7.49 (m, 4 H), 6.18 (d, 1 H, J ) 7.5 Hz), 5.91 (dq, 1 H, J
) 7.5, 1.1 Hz), 1.94, (d, 3 H, J ) 1.1 Hz); 13C NMR δ 165.3,
142.9, 140.5, 131.7, 128.5, 128.0, 125.9, 124.3, 122.0, 120.8,
84.4, 75.3, 14.1; MS m/ z (relative intensity) 209 (77), 168 (100),
140 (67), 84 (31), 43 (27). Anal. Calcd for C14H11NO: C, 80.36;
H, 5.30; N, 6.69. Found: C, 80.27; H, 5.38; N, 6.76.
5-P h en yl-4,5-d ih yd r ooxa zol-2-on e (11a ): oil; 1H NMR δ
7.46-7.3 (m, 5 H), 6.64 (br s, 1 H), 5.6 (dd, 1 H, J ) 8.8, 8.2
Hz), 3.98 (dd, 1 H, J ) 8.8, 8.2 Hz), 3.54 (t, 1 H, J ) 8.2 Hz);
13C NMR δ 160.0, 138.5, 128.8, 125.6, 77.8, 48.2; MS m/ z
(relative intensity) 163 (19), 107 (100), 79 (30), 77 (11). Anal.
Calcd for C9H9NO2: C, 66.25; H, 5.56; N, 8.58. Found: C,
66.29; H, 5.61; N, 8.49.
2-Meth yl-5-h exyl-4,5-d ih yd r ooxa zole (9b): oil; 1H NMR
δ 4.58-4.41 (m, 1 H), 3.86 (ddq, 1 H, J ) 13.8, 9.5, 1.4 Hz),
3.4 (ddq, 1 H, J ) 13.8, 7.5, 1.4 Hz), 1.94 (t, 3 H, J ) 1.4 Hz),
1.72-1.19 (m, 10 H), 0.9 (t, 3 H, J ) 6.6 Hz); 13C NMR δ 164.6,
79.6, 59.4, 35.2, 31.4, 28.8, 24.8, 22.2, 13.7; MS m/ z (relative
intensity) 169 (2), 84 (34), 55 (100), 43 (30). Anal. Calcd for
C10H19NO: C, 70.96; H, 11.31; N, 8.27. Found: C, 71.04; H,
11.20; N, 8.38.
2-Meth yl-4-h exyl-4,5-d ih yd r ooxa zole (9d ): mp 77-78 °C;
1H NMR δ 4.3 (dd, 1 H, J ) 9.2, 7.8 Hz), 4.12-3.9 (m, 1 H),
3.81 (t, 1 H, J ) 7.8 Hz), 1.98 (s, 3 H), 1.72-1.12 (m, 10 H),
0.88 (t, 3 H, J ) 7.0 Hz); 13C NMR δ 164.0, 72.2, 66.0, 35.7,
31.4, 28.9, 25.6, 22.2, 13.6, 13.4; MS m/ z (relative intensity)
169 (1), 140 (15), 99 (33), 84 (100), 56 (72), 43 (57). Anal. Calcd
for C10H19NO: C, 70.96; H, 11.31; N, 8.27. Found: C, 71.04;
H, 11.20; N, 8.38.
Ackn owledgm en t. Financial support from the CNR,
Rome, and Ministero dell’Universita` e della Ricerca
Scientifica e Tecnologica, Italy, is gratefully acknowl-
edged.
J O960866G