Synthesis of allylic alcohols from oxazolinyloxiranes

Article abstract of DOI:10.1021/jo026234d

Lithium diisopropylamide (LDA) (or s-BuLi/TMEDA) in diethyl ether promotes smooth ring opening of oxazolinyl alkyl oxiranes to give oxazolinyl allylic alcohols, which are masked Baylis-Hillman adducts, in good to excellent yields. An E₂-E₁cb-like syn-β-elimination is proposed to explain the easy base-promoted isomerization of the studied oxiranes.

Full text of DOI:10.1021/jo026234d

Syn th esis of Allylic Alcoh ols fr om Oxa zolin yloxir a n es
Filippo M. Perna, Vito Capriati, Saverio Florio,* and Renzo Luisi
C.N.R., Istituto di Chimica dei Composti OrganoMetallici “ICCOM”, Sezione di Bari,
Dipartimento Farmaco-Chimico, Universita` di Bari, Via E. Orabona 4, I-70126 Bari, Italy
florio@farmchim.uniba.it
Received J uly 24, 2002
Lithium diisopropylamide (LDA) (or s-BuLi/TMEDA) in diethyl ether promotes smooth ring opening
of oxazolinyl alkyl oxiranes to give oxazolinyl allylic alcohols, which are masked Baylis-Hillman
adducts, in good to excellent yields. An E2-E1cb-like syn-â-elimination is proposed to explain the
easy base-promoted isomerization of the studied oxiranes.
In tr od u ction
synthesis of numerous commercially and biologically
important substances such as carbovir,6 lasiol,7 faranal,8
leukotrienes,9 and prostaglandin precursors.10
The Baylis-Hillman (BH) reaction, which combines
the Michael addition of a tertiary amine, usually 1,4-
diazabicyclo[2.2.2]octane (DABCO), and an aldehyde to
an R,â-unsaturated carbonyl compound, is a useful
method of preparation of allylic alcohols.1 However, at
least in the classical version, the BH reaction presents
some drawbacks: (a) it is too slow; some reactions take
days and even weeks to occur; (b) it works well only with
particularly electrophilic R,â-unsaturated carbonyl com-
pounds; (c) it does not take place when a ketone is used
instead of an aldehyde; and (d) it works almost exclu-
sively with â-unsubstituted R,â-unsaturated carbonyl
compounds and cyclic enones. A number of physical and
chemical methods have been developed to accelerate the
notoriously slow BH reaction.2 Lewis acids have also been
used to this end, but extremely delicate experimental
conditions must be used.3 Alternative routes planned to
make the BH reaction reasonably fast use the “MAC”
procedure (Michael addition-aldol reaction-Cope elimi-
nation).4 The base-promoted rearrangement of oxiranes,
on the other hand, often provides a convenient method
of preparation of allylic alcohols, which are useful inter-
mediates in synthetic organic chemistry.5 Asymmetric
variants of this reaction have been the subject of recent
investigations and have been used as the key step in the
Resu lts a n d Discu ssion
In this paper, we report a quite simple route to
oxazolinyl allylic alcohols based on the isomerization
reaction of oxazolinyl alkyl oxiranes. The leading idea
was that lithiated 2-(1-chloroalkyl)oxazolines D11 (Scheme
1) can be considered synthetic equivalents of the BH
reagent (the electron-withdrawing oxazolinyl system is
a well-known masked form of the carbonyl functional-
ity),12 and their reaction with carbonyl compounds leads
to alkyl oxazolinyloxiranes that are the precursors of the
BH reaction adducts A as shown in the following ret-
rosynthetic approach (Scheme 1). According to such an
approach, the BH reaction product A would be afforded
upon deblocking of the oxazolinyl moiety of the allylic
alcohol B, which in turn could derive from the isomer-
ization of the oxazolinyloxirane C on its turn obtainable
by the coupling reaction of a carbonyl compound with the
oxazolinyl-R-chloroalkyl anion D, a Darzens-type re-
agent.11
(5) (a) So¨dergren, M. J .; Andersson, P. G. J . Am. Chem. Soc. 1998,
120, 10760-10761. (b) Nilsson Lill, S. O.; Arvidsson, P. I.; Ahlberg, P.
Tetrahedron: Asymmetry 1999, 10, 265-279. (c) Asami, M.; Ogawa,
M.; Inoue, S. Tetrahedron Lett. 1999, 40, 1563-1564. (d) O¢Brien, P.
J . Chem. Soc., Perkin Trans. 1 1998, 1439-1457. (e) Hodgson, D. M.;
Gibbs, A. R.; Lee, G. P. Tetrahedron 1996, 52, 14361-14384. (f) Cox,
P. J .; Simpkins, N. S. Tetrahedron: Asymmetry 1991, 2, 1-26.
(6) (a) Hodgson, D. M.; Witherington, J .; Moloney, B. A. J . Chem.
Soc., Perkin Trans. 1 1994, 3373. (b) Hodgson, D. M.; Gibbs, A. R.
Synlett 1997, 657-658. (c) Asami, M.; Takahashi, J .; Inoue, S.
Tetrahedron: Asymmetry 1994, 5, 1649-1652. (d) Saravanan, P.; Singh,
V. K. Tetrahedron Lett. 1998, 39, 167-170.
* To whom correspondence should be addressed. Phone: +39-080-
5442749. Fax: +39-080-5442231.
(1) For a review, see: (a) Basavaiah, D.; Rao, P. D.; Hyma, R. S.
Tetrahedron 1996, 52, 8001-8062. (b) Drewes, S. E.; Roos, G. H. P.
Tetrahedron 1988, 44, 4653-4670. (c) Ciganek, E. Org. React. 1997,
51, 201-350. (d) Langer, P. Angew. Chem., Int. Ed. 2000, 39, 3049-
3052.
(7) Kasai, T.; Watanabe, H.; Mori, K. Bioorg. Med. Chem. 1993, 1,
67-70.
(2) (a) Aggarwal, V. K.; Dean, D. K.; Mereu, A., Williams, R. J . Org.
Chem. 2002, 67, 510-514. (b) Aggarwal, V. K.; Mereu, A.; Tarver, G.
J .; McCague, R. J . Org. Chem. 1998, 63, 7183-7189. (c) Basavaiah,
D.; Satyanarayana, T. Org. Lett. 2001, 3, 3619-3622. (d) Yu, C.; Hu,
L. J . Org. Chem. 2002, 67, 219-223.
(3) (a) Uehira, S.; Han, Z.; Shinokubo, H.; Oshima, K. Org. Lett.
1999, 1, 1383-1385. (b) Shi, M.; Feng Y. S. J . Org. Chem. 2001, 66,
406-411. (c) Li, G.; Gao, J .; Wei, H. X.; Enright, M. Org. Lett. 2000, 2,
617-620.
(4) Sammelson, R. E.; Gurusinghe, C. D.; Kurth, J . M.; Olmstead,
M. M.; Kurth, M. J . J . Org. Chem. 2002, 67, 876-882.
(8) Mori, K.; Murata, N. Liebigs Ann. Chem. 1995, 2089-2092.
(9) (a) Sabol, J . S.; Cregge, R. J . Tetrahedron Lett. 1989, 30, 3377-
3380. (b) Hayes, R.; Wallace, T. W. Tetrahedron Lett. 1990, 31, 3355-
3356.
(10) (a) Asami, M. Chem. Lett. 1985, 5803. (b) Asami, M. Bull. Chem.
Soc. J pn. 1990, 63, 721-727. (c) Asami, M.; Inoue. S. Tetrahedron
1995, 51, 11725-11730. (d) Bhuniya, D.; DattaGupta, A.; Singh, V.
K. J . Org. Chem. 1996, 61, 6108-6113.
(11) Capriati, V.; Degennaro, L.; Florio, S.; Luisi, R.; Tralli, C.; Troisi,
L. Synthesis 2001, 15, 2299-2306 and Ref. therein.
(12) Meyers, A. I. J . Heterocycl. Chem. 1998, 35, 991-1002.
10.1021/jo026234d CCC: $22.00 © 2002 American Chemical Society
Published on Web 10/31/2002
J . Org. Chem. 2002, 67, 8351-8359
8351

Perna et al.
TABLE 2. Syn th esis of Oxa zolin yloxir a n es 4a -e a n d
5a -e
SCHEME 1
oxirane
R
R1
yielda (%)
4a
4b
4c
4d
4e
5a
5b
5c
5d
5e
Ph
Et
Me
Ph
Et
Me
78b
86c
84b
64d
62d
70
H (t-Bu)
H (cyclohexyl)
Ph
Et
Me
t-Bu (H)
cyclohexyl (H)
Ph
Et
Me
85
TABLE 1. Syn th esis of Oxa zolin yloxir a n es 2a -k by
Lith ia tion of 2-(1-Ch lor oeth yl)-2-oxa zolin e 1
85
H (t-Bu)
H (cyclohexyl)
t-Bu (H)
cyclohexyl (H)
55e
55e
a
b
Isolated yields. As preliminarly reported in ref 15a. c Opti-
mized yield with respect to that preliminarly reported in ref 15b.
d
Overall isolated yield in both cis and trans isomers (42% cis and
22% trans for 4d , 40% cis and 22% trans for 4e); a 1.2/1
diastereomeric mixture separable by column chromatography
(silica gel, petroleum ether/AcOEt 7-8/3-2) in favor of the trans
isomer formed in the crude reaction mixture for both 4d and 4e.
e Overall isolated yield in both (R*,R*) and (R*,S*) isomers not
separable by column chromatography (R*,S*/R*,R* ratio ) 5.7/1
for 5d ; R*,S*/R*,R* ratio ) 2.3/1 for 5e).
oxirane
R
R1
yielda (%)
2a
2b
2c
2d
2e
2f
2g
2h
2i
Ph
Ph
-(CH2)5-
Et
66b
76b
80
Et
H
cyclohexyl
42c
41c
45c
43c
39c
39c
87d
83b
TABLE 3. Syn th esis of Allylic Alcoh ols 6a -e
cyclohexyl
H
i-Pr
H
Ph
H
i-Pr
Me
Ph
Me
2j
2k
Me (n-Pr)
Me
n-Pr (Me)
Me
a
b
Isolated yields. As reported in ref 11. c A 1:1 diastereomeric
mixture of separable (silica gel, petroleum ether/AcOEt 6-7/4-3)
oxirane
R
R1
allylic alcohol 6 (yield, %)a
d
diastereoisomers formed. Combined isolated yield; an inseparable
mixture of diastereomeric oxiranes 2j (dr 1/1 by 1H NMR) formed.
2a
2b
2c
2d
2e
2f
Ph
Ph
-(CH2)5-
Et
6a (76)
6b (86)
6c (78)
6d (71)
6d (70)
6e (72)
6e (71)
Et
H
Oxiranes 2a -k 13 were prepared by the Darzens reac-
tion of R-lithiated 2-(1-chloroethyl)oxazoline14 1a and the
appropriate carbonyl compound (Table 1) according to a
procedure recently reported from our laboratory,11 while
oxiranes 4a -e (Table 2) were synthesized from 2-chlo-
romethyl-2-oxazoline 3 by lithiation in the presence of
the appropriate carbonyl compound by using the Barbier
technique.15 Compounds 5a -e could be prepared from
cyclohexyl
cyclohexyl
H
i-Pr
H
H
i-Pr
2g
a
Isolated yields.
4a -e by a procedure based on lithiation of the oxazo-
linyloxirane and reaction with the appropriate electro-
phile (Table 2).16
(13) Oxiranes 2d , 2f, and (R*,S*)-5d were assigned the configuration
Treatment of 2a with lithium diisopropylamide (LDA)
in Et2O at -98 °C followed by warming to room temper-
ature and quenching with aqueous NH4Cl resulted in the
formation of the allylic alcohol 6a (Table 3). Comparable
results were achieved when oxiranes 2b-g were treated
with LDA leading to allylic alcohols 6b -e in a regio-
selective manner. The same allylic alcohol 6d was obvi-
ously obtained from oxiranes 2d and 2e and the alcohol
6e formed from oxiranes 2f and 2g.
3
on the basis of the very small long-range J CH coupling constant
(3J CH2-H ∼ 0 Hz) between the oxirane â-hydrogen and the carbon of
the methylene group (or of the methyl group) of the substituent on
the R-carbon, as reported: Kingsbury, C. A.; Durham, D. L.; Hutton,
R. J . Org. Chem. 1978, 43, 4696-4700. The configuration to 2h /2i and
5e was assigned either by analogy to similar trisubstituted aryl methyl
oxazolinyloxiranes as reported in ref 16 or by analogy to 5d , respec-
tively. The configuration to the inseparable diastereomers 2j could not
be assigned.
(14) Abbotto, A.; Bradamante, S.; Florio, S.; Capriati, V. J . Org.
Chem. 1997, 62, 8937-8940.
(15) (a) Florio, S.; Capriati, V.; Luisi, R. Tetrahedron Lett. 1996, 37,
4781-4784. (b) Capriati, V.; Florio, S.; Luisi, R.; Russo, V.; Salomone,
A. Tetrahedron Lett. 2000, 41, 8835-8838. (c) Florio, S.; Capriati, V.;
Di Martino, S.; Abbotto, A. Eur. J . Org. Chem. 1999, 409-417. (d)
Lithiated 2-chloromethyl-2-oxazoline is an extremely reactive inter-
mediate for undergoing smooth homocoupling reaction to give trans-
bis(oxazolinyl)ethene and trans-1,2,3-tris(oxazolinyl)cyclopropane, as
reported: Capriati, V.; Florio, S.; Luisi, R.; Rocchetti, M. T. J . Org.
Chem. 2002, 67, 759-763.
Allylic alcohols 6a -e are likely the result of a â-elim-
ination reaction involving the methyl group and the
oxygen of the oxirane ring, the R-elimination being
impossible for the absence of oxirane ring hydrogens. The
(16) Abbotto, A.; Capriati, V.; Degennaro, L.; Florio, S.; Luisi, R.;
Pierrot, M.; Salomone, A. J . Org. Chem. 2001, 66, 3049-3058.
8352 J . Org. Chem., Vol. 67, No. 24, 2002

Synthesis of Allylic Alcohols
TABLE 4. Com p etitive Elim in a tion in
â-Meth yl-Su bstitu ted Oxa zolin yloxir a n es 2h -k
SCHEME 2
allylic
allylic
alcohol 7
relief of the ring strain of the oxirane, which provides
sufficient driving force to overcome the reluctance of the
ether oxygen atom to act as a leaving group in the
â-elimination reaction, and the strength of the base used
(LDA) do not suffice to explain the ease with which the
above isomerization takes place. Indeed, it has been
reported17a that, even by using very strong bases, the
â-elimination of epoxides not carrying electron-withdraw-
ing groups capable of enhancing the acidity on the
â-carbon takes hours or days to occur. In some cases, a
cosolvent or a ligand is needed and superbases are
used.17b We believe that the oxazoline system, jointly with
the oxirane ring, plays a crucial role providing coordina-
tion to the lithium cation of LDA in a sort of complex
such as the one shown below (Scheme 2), thus exalting
the LDA basicity and driving the elimination reaction to
occur. An E2-E1cb like mechanism with a syn stereo-
chemical course could be invoked, as reported for other
base-promoted isomerization reactions of alkyl oxi-
ranes.3d,17c,d
LDA
alcohol 6
oxirane
R
R1
(equiv) (yield, %)a (yield, %)a
2h
2i
2j
2j
2k
2k
Ph
Me
Me
Ph
1.5
1.5
1.5
2.5
1.5
2.5
7a (89)
7a (42)
7b (76)c
7b (68)c
7c (81)
7c (75)
6f (42)
6g (10)d
6h (13)
n-Pr(Me)b Me(n-Pr)b
n-Pr(Me)b Me(n-Pr)b
Me
Me
Me
Me
Isolated yields. 1:1 mixture of (R*,R)- and (R*,S*)-2j. c R )
n-Pr. This product could not be isolated as it tends to decompose
with the time and during column chromatography.
a
b
d
SCHEME 3
It was proposed18 that, especially in the presence of
bad leaving groups and strong bases, as in our case, the
syn elimination is favored by the cation coordination
provided by the oxirane oxygen. The regioselectivity of
the isomerization reaction of oxiranes 2b-g, involving
the methyl and not the other alkyl groups of the oxirane
ring, can be explained with the Hofmann rule according
to which the abstraction of protons from methyl proceeds
faster than from methylene (or methynic) groups espe-
cially with a poor leaving group and a strong base. It is
also worth noting that compounds 6a -e resemble the BH
adducts that would derive from the reaction involving
ketones, which, as mentioned above, do not react in the
classic BH reaction. The inspection of results listed in
Table 3 allows us to say that the reaction tolerates
several different substituents in the â position (with
respect to the oxazolinyl ring). However, the presence of
a â-methyl group, as in epoxides 2h -k (Table 4), has
been found to cause an alternative or competitive â-
elimination reaction. When the epoxide (R*,R*)-2i was
treated with LDA under the standard experimental
conditions, a 1:1 mixture of allylic alcohols 6f and 7a
(Table 4) formed in quite good yields. The approach of
the base to the two methyl groups of oxirane 2i, which
are cis each other, seems to be equally feasible. In
contrast, the reaction of the epoxide (R*,S*)-2h gave
compound 7a as the sole product. Such a regioselectivity
could be accounted for by considering that in compound
2h the â-methyl group, being cis with respect to the
oxazolinyl group, can be more easily approached by the
base (LDA) via a preliminary coordination of lithium of
LDA by the aza group of the oxazoline system and the
oxygen of the oxirane ring, thus promoting the syn
â-elimination as visualized in Scheme 3.
As expected, lithiation of the trimethyl oxazolinyl
oxirane 2k afforded allylic alcohol 7c; a small amount
(13%) of allylic alcohol 6h also formed when 2.5 equiv of
LDA were used. Allylic alcohol 7b formed in the reaction
of a 1:1 mixture of cis- and trans-oxiranes 2j with 1.5
equiv of LDA, whereas the use of 2.5 equiv produced also
about 10% of the alcohol 6g.
Treatment of benzyl oxazolinyloxiranes 5a -c with
19
LDA furnished good yields of allylic alcohols 8a -c as
Z and E diastereomeric mixtures (Table 5). Of course,
here, the eliminative ring fission of the oxirane system
is facilitated by the enhancing acidity effect of the phenyl
group attached to the exocyclic methylene group. Inter-
estingly, Z isomers of allylic alcohols 8a and 8b formed
exclusively when oxiranes 5a and 5b were reacted with
s-BuLi/TMEDA, while oxirane 5c afforded allylic alcohol
8c with a good diastereoselectivity (Z/E ratio: 84/16).
The formation of allylic alcohols 8a -c can be accounted
for by assuming that treatment of oxiranes 5a -c with
the base (LDA or s-BuLi/TMEDA) promotes an elimina-
tive oxirane ring fission involving the R-alkyl substituent.
Here, an E2-E1cb-like mechanism, more shifted toward
(19) Configuration to allylic alcohols 8a -e could be assigned on the
basis of the 3J (CN,H) coupling constants between the iminic carbon
and the olefinic proton. In the case of the E isomers (having a cis-type
arrangement between the above groups) couplings have been found to
be always smaller (7.5-8.5 Hz) than those of the Z ones (10.6-11.5
Hz) as reported for similar π-bonded systems: Kalinowski, H.-O.;
Berger, S.; Braun, S. Carbon-13 NMR Spectroscopy; Wiley: New York,
1988; Chapter 4, pp 526-543.
(17) (a) Crandall, J . K.; Apparu, M. Org. React. 1983, 29, 345-443.
(b) Mordini, A.; Ben Rayana, E:, Margot, C.; Schlosser, M. Tetrahedron
1990, 46, 2401-2410. (c) Margot, C.; Rizzolio, M.; Schlosser, M.
Tetrahedron 1990, 46, 2411-2424. (d) Bertilsson, S. K.; So¨dergren,
M. J .; Andersson, P. G. J . Org. Chem. 2002, 67, 1567-1573 and ref
therein.
(18) Sicher, J . Angew. Chem., Int. Ed. Engl. 1972, 11, 200-214.
J . Org. Chem, Vol. 67, No. 24, 2002 8353

Perna et al.
TABLE 5. Dep r oton a tion of Oxa zolin yloxir a n es 5a -c
SCHEME 5
oxirane
R
base
allylic alcohol 8 (yield, %)a Z/ E ratiob
5a
5a
5b
5b
5c
5c
Ph LDA
8a (91)
8a (80)
8b (92)
8b (85)
8c (40)d
8c (91)
64/36
>99/1
77/23
>99/1
50/50
84/16
Ph s-BuLic
Et
Et
LDA
TABLE 6. Dep r oton a tion of Oxa zolin yloxir a n es 5d ,e
s-BuLic
Me LDA
Me s-BuLic
a
Combined isolated yields; isomers Z and E could be separated
b
by column chromatography. Diastereomeric ratio determined by
1H NMR on the crude reaction mixture. c TMEDA was always
d
employed in stoichiometric amount with respect to s-BuLi. The
major product of this reaction was allylic alcohol 9 as shown in
Scheme 4.
allylic
oxir-
ane
alcohol 8 Z/ E
R
R1
base (yield, %)a ratiob
SCHEME 4
5d t-Bu (H)c
5d t-Bu (H)c
(H) t-Buc
(H) t-Buc
LDA
s-BuLi 8d (90)d 87/13
8d (90)d 87/13
5e cyclohexyl (H)e (H) cyclohexyle LDA
8e (89)f
85/15
85/15
5e cyclohexyl (H)e (H) cyclohexyle s-BuLi 8e (89)f
a
b
Isolated yields. Diastereomeric ratio determined by 1H NMR
on the crude reaction mixture. Isomers Z and E could be separated
by column chromatography. c 85/15 mixture of (R*,S)- and (R*,R*)-
d
5d . R ) t-Bu. e 70/30 mixture of (R*,R)- and (R*,S*)-5e. f R )
cyclohexyl.
the E1cb mechanism for involving benzylic hydrogens,
might be proposed as reported for ring opening reactions
of other oxiranes.3d Coordination offered to the lithium
base by the oxazolinyl group and the oxirane oxygen
should facilitate the syn-â-elimination reaction. Two
competitive syn-â-eliminations occur when a methyl
group is present on the â-carbon atom (with respect to
the oxazoline ring) of benzyl oxiranes. In the case of
oxirane 5c (Table 5 and Scheme 4), indeed, treatment
with LDA affords the expected allylic alcohol 8c (40%,
Z/E ratio: 1/1) together with the isomeric allylic alcohol
9 (48%). This is probably the result of a balance between
steric and electronic effects. The coordinative assistance
of the oxazoline ring to the â-elimination involving the
methyl group cis to it must also be taken into consider-
ation. Concerning the isomerization reactions of 5a -c
promoted by LDA, an appreciable increase of the Z/E
ratio was observed on going from 5c to 5a and 5b; this
could be tentatively explained with the different steric
hindrance of the R groups.
of the starting oxirane. There are two conformers E and
F (Scheme 5) that permit the syn-â-elimination. Con-
former E, which is of higher energy with respect to F for
experiencing a higher steric compression that originates
from the interaction of the R groups on the oxirane ring
and the phenyl group, would lead to the E stereoisomer
while conformer F would give the Z isomer. The role of
the ligand TMEDA, which on the other hand exalts the
basicity of s-BuLi, could be that of enlarging the energy
difference between the transition states leading to the Z
and E isomers.
When a diastereomeric mixture of oxirane 5d (R*,S*/
R*,R* ratio: 85/15)22 was reacted with LDA (or s-BuLi/
TMEDA) in Et2O, a regioselective eliminative ring fission
reaction involving the benzyl group occurred leading to
a diastereomeric mixture (Z/E ratio: 87/13) of allylic
alcohol 8d (Table 6). It is useful to note that there is no
change in stereoselection passing from LDA to s-BuLi/
TMEDA. Such an absence of the base effect on the
stereoselection could be accounted for by assuming that
in the case of the reactions of 5d the interactions between
the phenyl and â-R groups are playing the major role.
The Z/E ratio in the final product, which substantially
parallels the diastereomeric ratio of the starting oxirane,
seems to indicate a stereospecificity in the elimination
reaction of the diastereomers of 5d .
The Z-stereoselectivity observed when s-BuLi was used
as the base can be accounted for by considering the
possible different aggregation state of s-BuLi in Et2O
with respect to LDA20,21 and the reactive conformations
(20) LDA is recognized to exist as a disolvated dimer in ethereal
solvents (Sun, X.; Collum, D. B. J . Am. Chem. Soc. 2000, 122, 2452-
2458), while s-BuLi complexed by TMEDA is usually monomeric going
towards an endothermic disproportionation from a 1:1 complex to a
1:2 complex according to the temperature (Catala, J . M.; Clouet, G.;
Brossas, J . J . Organomet. Chem. 1981, 219, 139-143).
(21) The possibility that the lower stereoselection of reactions
promoted by LDA could be attributed to an isomerization reaction of
Z isomers into E isomers promoted by the formed diisopropylamine
can be ruled out. Indeed, Z-8a , Z-8b, and Z-8d do not isomerize to the
corresponding E isomers when treated with diisopropylamine and E-8d
does not isomerize to Z-8d .
To go in more detail, we presume that base-epoxide
complexes are involved in the â-elimination as in base-
mediated isomerizations of other epoxides.17a Steric
interactions between the phenyl and the â-substituents
(22) All efforts made in order to separate diastereomers 5d and 5e
failed so far.
8354 J . Org. Chem., Vol. 67, No. 24, 2002

Synthesis of Allylic Alcohols
SCHEME 6
reaction of the above oxazolinyl alkyl oxiranes is under
way in our lab and results will be reported in due course.
Exp er im en ta l Section
Gen er a l Meth od s. Tetrahydrofuran (THF) and diethyl
ether (Et2O) were freshly distilled under a nitrogen atmo-
sphere over sodium/benzophenone ketyl. N,N,N′,N′-Tetra-
methylethylenediamine (TMEDA) was distilled over finely
powdered calcium hydride. All other chemicals were of com-
mercial grade and used without further purification. Petroleum
ether refers to the 40-60 °C boiling fraction. Commercial
solutions of n-BuLi (2.5 M solution in hexanes) and s-BuLi
(1.3 M solution in cyclohexane) were titrated by using N-
pivaloyl-o-toluidine prior to use.23 For the 1H and 13C NMR
spectra (1H NMR 200, 300, 500 MHz; 13C NMR 75.4, 125 MHz),
CDCl3 was used as the solvent. GC-MS spectrometry analyses
were performed on a gas chromatograph HP 6890 (HP-5 MS
capillary column, 30 m, 0.25 mm i.d. × 0.25 µm) equipped with
a 5973 mass selective detector operating at 70 eV (EI). Melting
points were uncorrected. TLC was performed on Merck silica
gel plates with F-254 indicator; visualization was accomplished
by UV light (254 nm) or by exposure to I2 vapor. All reactions
involving air-sensitive reagents were performed under nitrogen
in oven-dried glassware using the syringe-septum cap tech-
on the oxirane ring will dictate which conformers will be
predominating. Accordingly, the complex derived from
diastereomer (R*,S*)-5d (having the t-Bu and benzyl
group cis with respect to the oxirane ring) and placing
the phenyl group synclinal to the oxazoline ring (con-
former H, Scheme 6), which experiences a lower steric
compression with respect to conformer G (Scheme 6),
would furnish Z allylic alcohol 8d , while complex J
(prevailing in the equilibrium with complex I), derived
from diastereomer (R*,R*)-5d , would lead to the E allylic
alcohol 8d .
LDA- or s-BuLi-promoted isomerization of a diastere-
omeric mixture (R*,S*/R*,R* ratio: 70/30) of oxirane 5e
generated a diastereomeric mixture (Z/E ratio: 85/15) of
allylic alcohol 8e. This result could be accounted for by
considering the steric interactions occurring between the
phenyl and the cyclohexyl groups in the complexes
preceding the formation of the final product. Considering
the (R*,S*)-5e, this would react in a stereospecific
manner passing through conformer L (Scheme 7) (pre-
ferred with respect to conformer K) to give the Z isomer,
while the (R*,R*)-5e would produce a mixture of Z,
which, therefore, adds to that obtained from the (R*,S*)-
5e, and E allylic alcohol 8e, going through base-oxirane
complexes M and N, which should be of comparable
energy.
11
nique. Spectroscopic data of oxazolinyloxiranes 2a ,11 2b,
2k ,11 and 4a 15c have been reported.
3-Eth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-2,3-ep oxyp en -
ta n e (2c): colorless oil; 80%; 1H NMR (300 MHz) δ 0.89 (t, J
) 7.5 Hz, 3 H), 0.93 (t, J ) 7.5 Hz, 3 H), 1.20 (s, 3 H), 1.21 (s,
3 H), 1.47 (s, 3 H), 1.49-1.53 (m, 3 H), 1.64-1.66 (m, 1 H),
3.85 and 3.92 (2 × d, AB system, J ) 8.2 Hz, 2 H); 13C NMR
(75.4 MHz) δ 8.6, 8.7, 16.7, 22.0, 22.9, 27.7, 27.8, 60.5, 67.0,
68.7, 78.7, 164.0; GC-MS (70 eV) m/z 196 (M+-15, 2), 168 (10),
156 (15), 142 (19), 112 (100), 86 (21), 70 (46), 69 (37), 55 (19),
43 (29), 41 (17); FT-IR (film, cm-1) 2964, 2877, 1671 (s, CdN),
1463, 1299, 1186, 1097, 961, 733, 547.
(1R*,2S*)-1-Cycloh exyl-2-(4,4-d im et h yl-2-oxa zolin -2-
yl)-1,2-ep oxyp r op a n e (2d ): colorless oil; 42%; 1H NMR (500
MHz) δ 1.12-1.24 (m, 6 H), 1.23 (s, 3 H), 1.24 (s, 3 H), 1.52 (s,
3 H), 1.58-1.71 (m, 4 H), 1.89-1.92 (m, 1 H), 2.94 (d, J ) 9.0
Hz, 1 H), 3.91 (s, 2 H); 13C NMR (125 MHz) δ 14.4, 25.2, 28.1,
28.5, 30.4, 37.1, 55.0, 66.4, 67.5, 79.3, 164.9; GC-MS (70 eV)
m/z 237 (M+, 4), 194 (20), 192 (38), 182 (21), 142 (26), 138 (36),
127 (25), 95 (100), 55 (26), 43 (54); FT-IR (film, cm-1) 2927,
2852, 1670 (s, CdN), 1450, 1366, 1117, 1079, 974, 856. Anal.
Calcd for C14H23NO2: C, 70.85; H, 9.77; N, 5.90. Found: C,
71.15; H, 10.03; N, 5.69.
In conclusion, we have developed a simple method of
preparation of oxazolinyl allylic alcohols based on the
base-promoted isomerization of alkyl epoxides. The ob-
tained allylic alcohols seem to be promising in synthetic
organic chemistry for the possible elaboration of their
oxazoline system. The chiral version of the isomerization
(1R*,2R*)-1-Cycloh exyl-2-(4,4-d im et h yl-2-oxa zolin -2-
yl)-1,2-ep oxyp r op a n e (2e): colorless oil; 41%; 1H NMR (500
MHz) δ 1.05-1.29 (m, 6 H), 1.25 (s, 3 H), 1.27 (s, 3 H), 1.51 (s,
3 H),1.60-1.75 (m, 4 H), 1.89-1.93 (m, 1 H), 2.61 (d, J ) 9.2
Hz, 1 H), 3.90 and 3.96 (2 × d, AB system, J ) 8.2 Hz, 2 H);
13C NMR (125 MHz) δ 20.5, 25.1, 25.5, 28.1, 28.2, 30.3, 37.1,
SCHEME 7
J . Org. Chem, Vol. 67, No. 24, 2002 8355

Perna et al.
56.3, 67.5, 68.8, 79.4, 163.3; GC-MS (70 eV) m/z 237 (M+, 4),
194 (28), 192 (41), 182 (21), 142 (31), 138 (34), 127 (25), 95
(100), 55 (31), 43 (57); FT-IR (film, cm-1): 2927, 2853, 1656
(s, CdN), 1523, 1450, 1364, 1070, 974, 856. Anal. Calcd for
2-Meth yl-1-(4,4-dim eth yl-2-oxazolin -2-yl)-1,2-epoxypr o-
p a n e (4c): colorless oil; 84%; 1H NMR (300 MHz) δ 1.30 (s, 6
H), 1.40 (s, 6 H), 3.35 (s, 1 H), 4.01 (s, 2 H); 13C NMR (75.4
MHz) δ 18.0, 23.8, 28.0, 56.5, 59.2, 67.2, 79.0, 161.1; GC-MS
(70 eV) m/z 169 (M+, 1), 114 (56), 84 (100), 56 (45), 41 (66);
FT-IR (film, cm-1): 2971, 2920, 1653 (s, CdN), 1380, 1184,
976, 807.
C
14H23NO2: C, 70.85; H, 9.77; N, 5.90. Found: C, 70.90; H,
10.06; N, 5.73.
(2R*,3S*)-4-Meth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-2,3-
ep oxyp en ta n e (2f): colorless oil; 45%; 1H NMR (300 MHz) δ
0.84 (d, J ) 6.8 Hz, 3 H), 0.99 (d, J ) 6.8 Hz, 3 H), 1.23 (s, 3
H), 1.25 (s, 3 H), 2.86 (d, J ) 9.3 Hz, 1 H), 3.45-3.60 (m, 1 H),
3.88 (s, 2 H); 13C NMR (125 MHz) δ 18.2, 20.0, 20.6, 27.7, 28.1,
28.2, 56.8, 67.5, 70.2, 79.3, 163.3; GC-MS (70 eV) m/z 197 (M+,
4), 182 (7), 154 (43), 142 (38), 124 (15), 98 (49), 83 (13), 72
(40), 55 (46), 43 (100); FT-IR (film, cm-1) 2964, 2877, 1660 (s,
3,3-Dim et h yl-1-(4,4-d im et h yl-2-oxa zolin -2-yl)-1,2-ep -
1
oxybu ta n e (4d ) (1R*,2S*): colorless oil; 22%; H NMR (300
MHz) δ 0.94 (s, 9 H), 1.28 (s, 3 H), 1.29 (s, 3 H), 3.03 (d, J )
2.2 Hz, 1 H), 3.41 (d, J ) 2.2 Hz, 1 H), 3.97 (s, 2 H); 13C NMR
(75.4 MHz) δ 25.4, 28.1, 28.2, 30.8, 48.2, 65.5, 67.4, 79.3, 162.4;
GC-MS (70 eV) m/z 182 (M+ - 15, 12), 142 (28), 140 (100),
128 (21), 112 (44), 95 (21),70 (46), 55 (45), 41 (35); FT-IR (film,
cm-1) 2966, 2871, 1665 (s, CdN), 1482, 1464, 1365, 1302, 993,
896. (1R*,2R*): colorless oil; 42%; 1H NMR (500 MHz) δ 0.97
(s, 9 H), 1.23 (s, 3 H), 1.27 (s, 3 H), 2.86 (d, J ) 4.7 Hz, 1 H),
3.45 (d, J ) 4.7 Hz, 1 H), 3.91 and 3.98 (2 × d, AB system, J
) 8.2 Hz, 2 H); 13C NMR (75.4 MHz) δ 26.4, 27.6, 28.1, 31.7,
50.8, 65.6, 67.5, 79.2, 160.5; GC-MS (70 eV) m/z 182 (6), 142
(21), 140 (49), 128 (20), 113 (100), 98 (47), 95 (23), 70 (53), 55
(60), 41 (40). FT-IR (film, cm-1); 2966, 2871, 1679 (s, CdN),
1483, 1464, 1365, 1241, 1193, 981, 934, 838.
CdN), 1465, 1366, 1163, 1068, 864. Anal. Calcd for C11H19
-
NO2: C, 66.97; H, 9.71; N, 7.10. Found: C, 66.75; H, 9.53; N,
6.91.
(2R*,3R*)-4-Meth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-2,3-
1
ep oxyp en ta n e (2g): colorless oil; 43%. H NMR (300 MHz)
δ 0.90 (d, J ) 6.7 Hz, 3 H), 1.05 (d, J ) 6.7 Hz, 3 H), 1.24 (s,
3 H), 1.25 (s, 3 H), 1.53 (s, 3 H), 2.58 (d, J ) 9.4 Hz, 1 H),
3.45-3.60 (m, 1 H), 3.93 (s, 2 H); 13C NMR (125 MHz) δ 18.1,
20.0, 27.6, 28.0, 60.5, 67.6, 70.1, 79.3, 164.8; GC-MS (70 eV)
m/z 197 (M+, 3), 182 (17), 154 (28), 142 (40), 126 (14), 98 (48),
83 (18), 72 (44), 55 (50), 43 (100); FT-IR (film, cm-1) 2964, 2869,
1671 (s, CdN), 1522, 1463, 1191, 972, 547. Anal. Calcd for
C11H19NO2: C, 66.97; H, 9.71; N, 7.10. Found: C,66.70; H, 9.80;
N, 7.00.
(2R*,3S*)-2-(4,4-Dim eth yl-2-oxa zolin -2-yl)-3-p h en yl-2,3-
ep oxybu ta n e (2h ): colorless oil; 39%; 1H NMR (200 MHz) δ
1.16 (s, 3 H), 1.29 (s, 3 H), 1.30 (s, 3 H), 1.62 (s, 3 H), 3.94 and
4.02 (2 × d, AB system, J ) 8.1 Hz, 2 H), 7.22-7.31 (m, 5 H);
13C NMR (125 MHz) δ 17.5, 20.6, 28.3, 61.7, 66.8, 67.7, 79.3,
126.1, 127.4, 128.0, 139.4, 163.9; GC-MS (70 eV) m/z 245 (M+,
1), 228 (3), 202 (8), 146 (100), 120 (6), 103 (9), 77 (8), 43 (6);
FT-IR (film, cm-1): 3059, 2968, 2931, 1669 (s, CdN), 1450,
1091, 752, 700. Anal. Calcd for C15H19NO2: C, 73.44; H, 7.81;
N, 5.71. Found: C, 73.65; H, 7.92; N, 5.70.
(2R*,3R*)-2-(4,4-Dim et h yl-2-oxa zolin -2-yl)-3-p h en yl-
2,3-ep oxybu ta n e (2i): colorless oil; 39%; 1H NMR (200 MHz)
δ 0.74 (s, 3 H), 0.91 (s, 3 H), 1.66 (s, 3 H), 1.68 (s, 3 H), 3.42
and 3.56 (2 × d, AB system, J ) 8.0 Hz, 2H), 7.16-7.36 (m, 5
H); 13C NMR (125 MHz) δ 16.8, 20.2, 27.5, 27.6, 61.6, 66.1,
66.8, 78.9, 126.2, 127.1, 127.5, 139.6, 163.0; GC-MS (70 eV)
m/z 245 (M+, 1), 202 (13), 146 (100), 120 (9), 103 (14), 91 (4),
77 (12), 43 (10); FT-IR (film, cm-1) 3058, 3029, 2969, 1658 (s,
CdN), 1448, 1091, 764, 700, 566.
3-Met h yl-2-(4,4-d im et h yl-2-oxa zolin -2-yl)-2,3-ep oxy-
h exa n e (2j): inseparable mixture of two diastereoisomers, dr
(2R*,3R*)/(2R*,3S*) 1/1; colorless oil; 87%; 1H NMR (500 MHz)
δ 0.80 (t, J ) 6.5 Hz, 3 H), 0.87 (t, J ) 6.6 Hz, 3 H), 1.19 (s, 6
H), 1.22 (s, 3 H), 1.26 (s, 3 H), 1.45 (s, 3 H), 1.46 (s, 3 H), 1.30-
1.65 (m, 8 H), 3.85-3.93 (m, 4 H); 13C NMR (125 MHz) δ 14.3,
14.4, 17.2, 17.6, 18.1, 18.8, 28.4, 28.5, 36.0, 36.9, 60.5, 60.7,
65.3, 65.5, 67.6, 67.7, 79.4, 79.5, 164.6; GC-MS (70 eV) m/z
stereoisomer with a lower tR 211 (M+, 1), 168 (20), 156 (16),
142 (21), 127 (13), 112 (100), 86 (24), 70 (63), 69 (39), 55 (19),
43 (39); stereoisomer with a higher tR 211 (M+, 1), 168 (19),
156 (16), 142 (18), 127 (8), 112 (100), 86 (25), 70 (66), 69 (42),
55 (19), 43 (41); FT-IR (film, cm-1) 2964, 2877, 1673 (s, CdN),
1464, 1382, 1097, 978, 539.
2-Cycloh exyl-1-(4,4-d im et h yl-2-oxa zolin -2-yl)-1,2-ep -
1
oxyeth a n e (4e) (1R*,2S*): colorless oil; 22%; H NMR (300
MHz) δ 1.03-1.23 (m, 6 H), 1.24 (s, 3 H), 1.27 (s, 3 H), 1.56-
1.82 (m, 4 H), 1.98-2.04 (m, 1 H), 3.02 (dd, J ) 2.7, 6.4 Hz, 1
H), 3.36 (d, J ) 2.7 Hz, 1 H), 3.92 (s, 2 H); 13C NMR (75.4
MHz) δ 25.3, 25.4, 26.0, 28.1, 28.2, 28.6, 29.0, 39.3, 49.9, 62.2,
67.4, 79.2, 162.0; GC-MS (70 eV); m/z 223 (M+, 1), 192 (10),
140 (13), 95 (100), 81 (23), 67 (23), 56 (35), 55 (52), 41 (90);
FT-IR (film, cm-1) 2964, 2922, 2853, 1664 (s, CdN), 1450, 1302,
1188, 993, 801. Anal. Calcd for C13H21NO2: C, 69.92; H, 9.48;
N, 6.27. Found: C, 69.72; H, 9.75; N, 6.15. (1R*,2R*): colorless
1
oil; 40%; H NMR (300 MHz) δ 1.03-1.22 (m, 5 H), 1.25 (s, 3
H), 1.27 (s, 3 H), 1.43-1.52 (m, 2 H), 1.62-1.78 (m, 3 H), 1.96-
2.02 (m, 1 H), 2.85 (dd, J ) 4.4 Hz, J ) 8.9 Hz, 1 H), 3.53 (d,
J ) 4.4 Hz, 1 H), 3.96 (s, 2 H); 13C NMR (75.4 MHz) δ ) 25.1,
25.4, 26.0, 28.1, 28.2, 28.4, 30.5, 36.4, 50.0, 62.1, 67.4, 79.3,
161.1; GC-MS (70 eV) m/z 223 (M+, 1), 206 (18), 113 (27), 95
(100), 67 (22), 56 (33), 55 (54), 41 (90); FT-IR (film, cm-1) 2965,
2922, 2852, 1676, 1661 (s, CdN), 1450, 1161, 981, 870.
2-(4,4-Dim eth yl-2-oxa zolin -2-yl)-1,1,3-tr ip h en yl-1,2-ep -
oxybu ta n e (5a ): white solid; mp 135 °C (Et2O); 70%; 1H NMR
(300 MHz) δ 0.76 (s, 3 H), 0.87 (s, 3 H), 2.52 (d, J ) 14.6 Hz,
1 H), 3.38-3.55 (2 × d, AB system, J ) 8.0 Hz, 2 H), 3.43 (d,
J ) 14.6 Hz, 1 H), 7.13-7.41 (m, 11 H), 7.56-7.65 (m, 4 H);
13C NMR (75.4 MHz) δ 27.4, 27.5, 37.5, 66.7, 67.1, 70.3, 79.0,
126.5, 127.1, 127.2, 127.5, 127.7, 127.9, 128.1, 128.4, 129.4,
136.2, 137.8, 138.2, 161.2; GC-MS (70 eV) m/z 383 (M+, 5),
292 (7), 209 (29), 208 (100), 165 (52), 105 (8), 91 (20), 77 (8);
FT-IR (film cm-1) 3058, 3029, 2967, 1656 (s, CdN), 1495, 1449,
1082, 750, 700. Anal. Calcd for C26H25NO2: C, 81.43; H, 6.57;
N, 3.65. Found: C, 81.61; H, 6.91; N, 3.63.
3-E t h yl-2-(4,4-d im et h yl-2-oxa zolin -2-yl)-1-p h en yl-2,3-
ep oxyp en ta n e (5b): colorless oil; 85%; 1H NMR (300 MHz) δ
0.95-1.00 (m, 6 H), 1.02-1.07 (m, 6 H), 1.53-1.61 (m, 2 H),
1.64-1.72 (m, 1 H), 1.75-1.79 (m, 1 H), 2.89 (d, J ) 14.4 Hz,
1 H), 3.34 (d, J ) 14.4 Hz, 1 H), 3.66 (s, 2 H), 7.11-7.29 (m,
5 H); 13C NMR (75.4 MHz) δ 9.3, 9.6, 23.1, 24.1, 28.2, 37.3,
65.5, 67.6, 69.4, 79.1, 126.7, 128.3, 129.8, 136.8, 162.8; GC-
MS (70 eV) m/z 287 (M+, 1), 258 (53), 201 (43), 200 (54), 186
(17), 112 (89), 103 (14), 91 (100), 70 (30), 55 (14); FT-IR (film,
cm-1) 3064 3031, 2971, 2884, 1658 (s, CdN), 1497, 1462, 1191,
1078, 967, 756, 699. Anal. Calcd for C18H25NO2: C, 75.22; H,
8.77; N, 4.87. Found: C, 75.11; H, 9.05; N, 4.98.
2-E t h yl-1-(4,4-d im et h yl-2-oxa zolin -2-yl)-1,2-ep oxyb u -
ta n e (4b): colorless oil; 86%; 1H NMR (300 MHz) δ 0.90 (t, J
) 7.7 Hz, 3 H), 0.93 (t, J ) 7.5 Hz, 3 H), 1.24 (s, 3 H), 1.25 (s,
3 H), 1.61-1.72 (m, 4 H), 3.36 (s, 1 H), 3.94 (s, 2 H); 13C NMR
(75.4 MHz) δ 8.5, 9.3, 22.8, 26.3, 28.2, 55.4, 66.8, 67.4, 79.3,
161.4; GC-MS (70 eV) m/z 197 (M+, 1), 180 (9), 168 (13), 142
(100), 128 (28), 112 (74), 86 (46),70 (74), 55 (45), 41 (52); FT-
IR (film, cm-1) 2969, 2926, 2882, 1659 (s, CdN), 1462, 1365,
1104, 975, 921.
3-Meth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-1-p h en yl-2,3-
ep oxybu ta n e (5c): colorless oil; 85%; 1H NMR (300 MHz) δ
1.01 (s, 3 H), 1.07 (s, 3 H), 1.34 (s, 3 H), 1.50 (s, 3 H), 2.90 (d,
J ) 14.5 Hz, 1 H), 3.35 (d, J ) 14.5 Hz, 1 H), 3.70 (s, 2 H),
7.15-7.30 (m, 5 H); 13C NMR (75.4 MHz) δ 20.5, 21.4, 28.2,
28.3, 37.6, 62.7, 64.6, 67.6, 79.2, 126.8, 128.3, 129.8, 136.8,
(23) Suffert, J . J . Org. Chem. 1989, 54, 509-512.
8356 J . Org. Chem., Vol. 67, No. 24, 2002

Synthesis of Allylic Alcohols
162.7; GC-MS (70 eV) m/z 259 (M+, 1), 244 (60), 200 (58), 186
(13), 172 (16), 119 (813), 91 (100), 84 (59), 41 (12); FT-IR (film,
cm-1) 3088, 3064, 3031, 2966, 2929, 1660 (s, CdN), 1497, 146,
1299, 1192, 1136, 1058, 967, 755, 700.
970, 759, 702. Anal. Calcd for C20H21NO2: C, 78.15; H, 6.89;
N, 4.56. Found: C, 78.25; H, 7.19; N 4.56.
1-[1-(4,4-Dim e t h yl-2-oxa zolin -2-yl)vin yl]cycloh e x-
a n ol (6b): colorless oil; 86%; 1H NMR (300 MHz) δ 1.27 (s, 6
H), 1.42-1.53 (m, 6 H), 1.64-1.93 (m, 4 H), 3.90 (s, 2 H), 5.53
(s, 1 H), 5.74 (br. s, 1 H, exchanges with D2O), 5.86 (s, 1 H);
13C NMR (75.4 MHz) δ 22.0, 26.1, 28.4, 37.0, 68.0, 72.1, 77.9,
119.6, 143.7, 161.8; GC-MS (70 eV) m/z 235 (M+, 1), 206 (11),
195 (47), 194 (26), 181 (55), 180 (100), 168 (19), 166 (44), 152
(31), 139 (34), 126 (80), 55 (29), 41 (21); FT-IR (film, cm-1) 3382,
2934, 2856, 1648 (s, CdN), 1599, 1364, 1191, 1121, 976, 935.
Anal. Calcd for C13H21NO2: C, 69.92; H, 9.48; N, 6.27. Found:
C, 70.20; H, 9.80; N 5.95.
4,4-Dim eth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-1-p h en yl-
2,3-ep oxyp en ta n e (5d ): inseparable mixture of two diaste-
reoisomers, dr (2R*,3R*)/(2R*,3S*) ) 85/15; colorless oil; 55%;
1H NMR (500 MHz) δ 0.99 (s, 9 H, minor), 1.04 (s, 3 H, minor),
1.06 (s, 3 H, major), 1.09 (s, 3 H, major), 1.10 (s, 3 H, minor),
1.11 (s, 9 H, major), 2.77 (d, J ) 14.4 Hz, 1 H, minor), 2.95 (s,
2 H, 1 H major + 1 H minor), 3.27-3.41 (2 × d, AB system, J
) 15.3 Hz, 2 H, major), 3.37 (d, J ) 14.4 Hz, 1 H, minor), 3.74
(s, 2 H, minor), 3.76 and 3.80 (2 × d, AB system, J ) 8.3 Hz,
2 H, major), 7.18-7.34 (m, 10 H, 5 H major + 5 H minor); 13
C
3-Eth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-1-p en ten -3-ol
1
NMR (125 MHz) δ 26.4 (minor), 27.5 (minor), 27.7 (major),
31.8 (minor), 27.9 (major), 34.3 (major), 42.8 (minor), 59.8
(major), 60.4 (minor), 67.3 (major + minor), 70.1 (major), 70.7
(minor), 78.9 (minor), 79.1 (major), 126.3 (major), 126.7
(minor), 127.9 (major), 128.0 (minor), 129.3 (major), 129.6
(minor), 135.5 (minor), 136.9 (major), 161.3 (minor), 164.1
(major); GC-MS (70 eV) (major) m/z 287 (M+, 1), 230 (100),
200 (20), 158 (25), 112 (6), 91 (18), 55 (9); GC-MS (70 eV)
(minor); m/z 287 (M+, 1), 230 (72), 200 (12), 158 (13), 119 (13),
91 (100), 55 (10); FT-IR (film, cm-1) 3063, 3031, 2970, 2925,
2852, 1658 (s, CdN), 1452, 1365, 1193, 977, 732, 700.
(6c): yellow oil; 78%; H NMR (300 MHz) δ 0.84 (t, J ) 7.41
Hz, 6 H), 1.29 (s, 6 H), 1.72 (q, J ) 7.41 Hz, 4 H), 3.91 (s, 2 H),
5.43 (s, 1 H), 6.02 (s, 1 H), 6.20 (br. s, 1 H, exchanges with
D2O); 13C NMR (75.4 MHz) δ 8.37, 8.49, 28.3, 28.5, 29.9, 32.1,
68.0, 71.5, 77.8, 121.7, 139.6, 162.1; GC-MS (70 eV) m/z 194
(M+ - 17, 2), 183 (12), 182 (100), 154 (44), 110 (47), 73 (40),
57 (16), 55 (19); FT-IR (film, cm-1) 3359, 2962, 2931, 1645 (s,
CdN), 1599, 1463, 1365, 1261, 1099, 977. Anal. Calcd for
C
12H21NO2: C, 68.21; H, 10.02; N, 6.63. Found: C, 68.58; H,
10.25; N 6.58.
1-Cycloh exyl-2-(4,4-dim eth yl-2-oxazolin -2-yl)-2-pr open -
1-ol (6d ): colorless oil; 71%; 1H NMR (300 MHz) δ 0.81-1.41
(m, 6 H), 1.24 (s, 3 H), 1.27 (s,3 H), 1.46-1.88 (m, 4 H), 2.07-
2.09 (m, 1 H), 3.85-3.91 (m, 3 H), 4.59 (br. s, 1 H, exchanges
with D2O), 5.40 (d, J ) 1.2 Hz, 1 H), 5.84 (d, J ) 1.2 Hz, 1 H);
13C NMR (125 MHz) δ 26.0, 26.1, 26.4, 28.0, 28.2, 29.2, 29.9,
43.0, 67.6, 77.7, 79.3, 121.9, 137.0, 161.0; GC-MS (70 eV) m/z
219 (M+ - 18, 16), 204 (6), 176 (5), 154 (100), 140 (15), 55 (20),
41 (10); FT-IR (film, cm-1) 3385, 2961,2920, 2857, 1654 (s, Cd
N), 1602, 1451, 1367, 1120, 1034. Anal. Calcd for C14H23NO2:
C, 70.85; H, 9.77; N, 5.90. Found: C, 71.15; H, 10.02; N 5.90.
4-Met h yl-2-(4,4-d im et h yl-2-oxa zolin -2-yl)-1-p en t en -3-
1-Cycloh exyl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-3-p h en -
yl-1,2-ep oxyp r op a n e (5e): inseparable mixture of two di-
astereoisomers, dr (1R*,2S*)/(1R*,2R*) ) 70/30; colorless oil;
55%; 1H NMR (300 MHz) δ 1.08-1.28 (m, 24 H, 12 H major +
12 H minor), 1.56-1.82 (m, 8 H, 4 H major + 4 H minor), 1.93-
2.02 (m, 2 H, 1 H major + 1 H minor), 2.66 (d, J ) 8.8 Hz, 1
H, minor), 2.84 (d, J ) 14.6 Hz, 1 H, minor), 2.94 (d, J ) 9.1
Hz, 1 H, major), 2.99 (d, J ) 14.9 Hz, 1 H, major), 3.36 (d, J
) 14.9 Hz, 1 H, major), 3.42 (d, J ) 14.6 Hz, 1 H, minor), 3.80
(s, 2 H, minor), 3.78 and 3.85 (2 × d, AB system, J ) 8.2 Hz,
2 H, major), 7.14-7.33 (m, 10 H, 5 H major + 5 H minor); 13
C
1
NMR (75.4 MHz) δ 25.1 (minor), 25.3 (major), 25.5 (minor),
26.0 (major), 27.9 (minor), 28.0 (major), 28.3 (minor), 28.6
(major), 30.2 (minor), 30.4 (major), 34.5 (major), 37.2 (major),
37.3 (minor), 40.1 (minor), 58.2 (major), 60.1 (minor), 66.7
(minor), 66.8 (major), 67.4 (major + minor), 79.0 (minor), 79.2
(major), 126.3 (major), 126.6 (minor), 128.0 (major), 128.1
(minor), 129.5 (major), 129.6 (minor), 135.7 (minor), 136.5
(major), 162.2 (minor), 163.8 (major); GC-MS (70 eV) (major)
m/z 313 (M+, 1), 296 (3), 230 (100), 200 (12), 158 (19), 91 (83),
55 (11); GC-MS (70 eV) (minor) m/z 313 (M+, 1), 296 (3), 230
(100), 201 (10), 200 (16), 158 (21), 91 (61), 55 (9); FT-IR (film,
cm-1) 3063, 3031, 2970, 2925, 2852, 1658 (s, CdN), 1452, 1365,
1193, 977, 732, 700.
ol (6e): colorless oil; 71%; H NMR (300 MHz) δ 0.80 (d, J )
6.7 Hz, 3 H), 0.99 (d, J ) 6.7 Hz, 3 H), 1.26 (s, 3 H), 1.29 (s, 3
H), 1.85-1.98 (m, 1 H), 3.84-3.95 (m, 3 H), 4.63 (br. s,
2
4
exchanges with D2O, 1 H), 5.46 (dd, J ) 1.4 Hz, J ) 0.9 Hz,
1 H), 5.87 (d, J ) 1.4 Hz, 1 H); 13C NMR (75.4 MHz) δ 18.9,
19.9, 28.3, 28.5, 33.7, 67.9, 68.1, 77.9, 80.3, 122.3, 137.5, 161.3;
GC-MS (70 eV) m/z 197 (M+, 1), 180 (10), 179 (12), 154 (100),
140 (7), 125 87), 83 (18), 73 (23), 55 (17), 41 (10); FT-IR (film
cm-1) 3398, 2969, 2930, 2873, 1653 (s, CdN), 1602, 1464, 1366,
1041, 972. Anal. Calcd for C11H19NO2: C, 66.97; H, 9.71; N,
7.10. Found: C, 66.96, H, 9.80, N, 7.14.
3-(4,4-Dim et h yl-2-oxa zolin -2-yl)-2-p h en yl-3-b u t en -2-
ol (6f): colorless oil; 42%; 1H NMR (300 MHz) δ 0.84 (s, 3 H),
1.19 (s, 3 H), 1.62 (s, 3 H), 3.77 (s, 2 H), 5.66 (br. s, 1 H,
exchanges with D2O), 5.98 (s, 1 H), 6.54 (s, 1 H), 7.10-7.30
(m, 3 H), 7.37-7.40 (m, 2 H); 13C NMR (75.4 MHz) δ 28.0, 28.1,
29.1, 67.9, 75.9, 78.1, 121.0, 125.2, 126.7, 127.9, 141.7, 147.5,
161.7; GC-MS (70 eV) m/z 245 (M+, 100), 244 (23), 230 (91),
202 (43), 168 (53), 158 (53), 154 (27), 130 (33), 125 (61), 105
(36), 77 (31), 55 (25), 43 (44); FT-IR (film, cm-1) 3346, 3060,
2980, 2940, 1687 (s, CdN), 1658, 1603, 1365, 1131, 977, 934,
766, 703. Anal. Calcd for C15H19NO2: C, 73.44; H, 7.81; N, 5.71.
Found: C, 73.68; H, 8.02; N 5.70.
2-Met h yl-3-(4,4-d im et h yl-2-oxa zolin -2-yl)-3-b u t en -2-
ol (6h ): colorless oil; 13%; 1H NMR (500 MHz) δ 1.31 (s, 6 H),
1.45 (s, 6 H), 3.94 (s, 2 H), 5.60 (d, J ) 0.7 Hz, 1 H), 5.85 (d,
J ) 0.7 Hz, 1 H), 6.03 (br s, 1 H, exchanges with D2O); 13C
NMR (75.4 MHz) δ 27.7, 28.7, 67.3, 71.0, 77.3, 118.7, 142.4,
161.0; GC-MS (70 eV) m/z 168 (M+ - 15, 100), 140 (34), 125
(14), 110 (10), 96 (23), 73 (39), 55 (17), 43 (14). 3385, 2960,
2925,2848, 1646 (s, CdN), 1601, 1459, 1257, 1094. Anal. Calcd
for C10H17NO2: C, 65.54; H, 9.35; N, 7.64. Found: C, 65.83;
H, 9.63; N 7.44.
Typ ica l P r oced u r e. A solution of 2a (1 mmol) and TMEDA
(1.5 mmol) in 5 mL of Et2O at -98 °C (with a methanol-liquid
nitrogen bath) and under N2 was reacted with s-BuLi (1.5
mmol), and the resulting orange mixture was stirred for 30
min at -98 °C. Alternatively, a solution of LDA (1.5 mmol from
1.5 mmol of i-Pr2NEt and 1.5 mmol of n-BuLi) in 5 mL of Et2O
was treated under N2 with a solution of 2a (1 mmol in 2 mL
of Et2O) for 30 min at -98 °C. Then, the reaction mixture was
warmed to room temperature, quenched with saturated aque-
ous NH4Cl, poured into 20 mL of saturated brine, extracted
with Et2O (3 × 10 mL), dried (Na2SO4), and evaporated under
reduced pressure. The crude mixture was flash chromato-
graphed (silica gel; petroleum ether:AcOEt ) 7-8:3-2) to give
the allylic alcohols with the following data:
2-(4,4-Dim eth yl-2-oxazolin -2-yl)-1,1-diph en yl-2-pr open -
1
1-ol (6a ): colorless oil; 76%; H NMR (300 MHz) δ 1.08 (s, 6
H), 3.90 (s, 2 H), 5.03 (d, J ) 0.9 Hz, 1 H), 6.13 (d, J ) 0.9 Hz,
1 H), 7.06 (br s, 1 H, exchanges with D2O), 7.22-7.33 (m, 6
H), 7.37-7.45 (m, 4 H); 13C NMR (125 MHz) δ 27.6, 67.6, 78.0,
81.2, 124.8, 127.0, 127.4, 127.6, 141.4, 144.9, 162.0; GC-MS
(70 eV) m/z 307 (M+, 49), 306 (100), 230 (12), 202 (16), 158
(12), 125 (22), 105 (44), 77 (26), 55 (6); FT-IR (film, cm-1) 3313,
3060, 2969, 2929, 1655 (s, CdN), 1602, 1450, 1366, 1177, 1114,
2-(4,4-Dim et h yl-2-oxa zolin -2-yl)-3-p h en yl-3-b u t en -2-
ol (7a ): colorless oil; 89%; 1H NMR (300 MHz) δ 1.10 (s, 3 H),
1.20 (s, 3 H), 1.65 (s, 3 H), 3.28 (br. s, 1 H, exchanges with
J . Org. Chem, Vol. 67, No. 24, 2002 8357

Perna et al.
D2O), 3.90 and 3.98 (2 × d, AB system, J ) 8.1 Hz, 2 H), 5.23
(d, J ) 0.7 hz, 1 H), 5.51 (d, J ) 0.7 Hz, 1 H), 7.23-7.36 (m,
5 H); 13C NMR (75.4 MHz) δ 25.5, 28.2, 28.3, 67.2, 73.2, 80.9,
115.6, 127.6, 127.9, 128.8, 140.2, 151.8, 168.9; GC-MS (70 eV)
m/z 245 (M+, 1), 229 (26), 228 (100), 200 (11), 157 (9), 91 (7),
77 (10), 43 (9); FT-IR (film, cm-1) 3461, 3044, 2968, 2928, 1660
(s, CdN), 1490, 1460, 1366, 1283, 1097, 777, 702.
3287, 3052, 2961, 2927, 1632 (s, CdN), 1608, 1462, 1368, 1292,
1017, 969, 755, 701. Anal. Calcd for C18H25NO2: C, 75.22; H,
8.77; N, 4.87. Found: C, 74.95; H, 8.98; N 4.90.
2-Met h yl-2-(4,4-d im et h yl-2-oxa zolin -2-yl)-4-p h en yl-3-
bu ten -2-ol (8c) (Z): colorless oil; 80%; 1H NMR (300 MHz) δ
1.31 (s, 6 H), 1.49 (s, 6 H), 3.83 (s, 2 H), 4.51 (br. s, 1 H,
exchanges with D2O), 6.94 (s, 1 H), 7.24-7.30 (m, 5 H); 13C
NMR (125 MHz) δ 28.2, 28.9, 67.8, 72.3, 78.8, 128.1, 128.2,
128.6, 131.5, 136.3, 136.5, 162.5; GC-MS (70 eV) m/z 259 (M+,
20), 258 (100), 244 (4), 186 (20), 172 (22), 130 (13), 43 (6); FT-
IR (film, cm-1) 3382, 3059, 3026, 2971, 2929, 1667 (s, CdN),
1627, 1462, 1365, 1180, 1021, 960, 753, 698. Anal. Calcd for
2-(4,4-Dim et h yl-2-oxa zolin -2-yl)-3-p r op yl-3-b u t en -2-
1
ol (7b): colorless oil; 76%; H NMR (300 MHz) δ 0.91 (t, J )
7.3 Hz, 3 H), 1.27 (s, 6 H), 1.42-1.52 (m, 2 H), 1.54 (s, 3 H),
1.99-2.08 (m, 2 H), 3.30 (br. s, 1 H, exchanges with D2O), 3.99
and 4.02 (2 × d, AB system, J ) 8.1 Hz, 2 H), 4.95 (d, J ) 0.7
Hz, 1 H), 5.22 (d, J ) 0.7 Hz, 1 H); 13C NMR (125 MHz) δ
14.2, 21.7, 25.1, 28.3, 28.4, 33.0, 67.3, 73.5, 80.8, 110.2, 151.0,
169.2; GC-MS (70 eV) m/z 211 (M+, 1), 194 (100), 166 (9), 143
(8), 69 (8), 55 (8), 43 (14); FT-IR (film, cm-1) 3483, 2962, 2928,
2873, 1660 (s, CdN), 1464, 1366, 1284, 1137, 1099, 974, 905.
Anal. Calcd for C12H21NO2: C, 68.21; H, 10.02; N, 6.63.
Found: C, 68.49; H, 10.29; N 6.58.
C
16H21NO2: C, 74.10; H, 8.16; N, 5.40. Found: C, 74.36; H,
8.20; N 5.38. (E): colorless oil; 30%; 1H NMR (300 MHz) δ
1.24 (s, 6 H), 1.27 (s, 6 H), 3.95 (s, 2 H), 6.69 (br. s, 1 H,
exchanges with D2O), 7.12-7.25 (m, 5 H), 7.54 (s, 1 H); 13C
NMR (125 MHz) δ 27.9, 28.2, 67.7, 72.2,?77.6, 127.1, 127.4,
127.9, 136.2, 136.3, 137.8 162.8; GC-MS (70 eV) m/z 259 (M+,
21), 258 (77), 244 (90), 201 (23), 186 (25), 172 (100), 130 (37),
43 (14); FT-IR (film, cm-1) 3358, 3059, 2970, 2929, 1666 (s,
CdN), 1613, 1366, 1170, 735, 700 Anal. Calcd for C16H21NO2:
C, 74.10; H, 8.16; N, 5.40. Found: C, 74.32; H, 8.30; N 5.40.
3-Met h yl-2-(4,4-d im et h yl-2-oxa zolin -2-yl)-3-b u t en -2-
ol (7c): colorless oil; 81%; 1H NMR (500 MHz) δ 1.26 (s, 6 H),
1.52 (s, 3 H), 1.75-1.76 (m, 3 H), 3.35 (br. s, 1 H, exchanges
with D2O), 3.99 and 4.01 (2 × d, AB system, J ) 8.3 Hz, 2H),
4.91-4.93 (m, 1 H), 5.10-5.11 (m, 1 H); 13C NMR (75.4 MHz)
δ 18.5, 24.4, 28.1, 67.0, 73.0, 80.6, 111.5, 146.7, 168.7; GC-
MS (70 eV) m/z 166 (M+ - 17, 100), 138 (20), 112 (9), 84 (10),
69 (19), 55 (11), 43 (19), 41 (15); FT-IR (film, cm-1) 3387, 2971,
2927, 1657 (s, CdN), 1462, 1367, 1287, 1139, 1108, 973. Anal.
Calcd for C10H17NO2: C, 65.54; H, 9.35; N, 7.64. Found: C,
65.85; H, 9.68; N 7.60.
4,4-Dim eth yl-2-(4,4-d im eth yl-2-oxa zolin -2-yl)-1-p h en yl-
1-p en ten -3-ol (8d ) (Z): white solid; mp 100-102 °C (Et2O);
81%; 1H NMR (300 MHz) δ 0.96 (s, 9 H), 1.27 (s, 3 H), 1.35 (s,
3 H), 3.77 and 3.82 (2 × d, AB system, J ) 8.2 Hz, 2 H), 4.08
(s, 1 H), 4.80 (br. s, exchanges with D2O, 1 H), 6.80 (s, 1 H),
7.24-7.33 (m, 5 H); 13C NMR (75.4 MHz) δ 26.5, 27.8, 28.5,
36.9, 67.7, 78.7, 84.1, 128.1, 128.2, 128.5, 129.1, 136.2, 137.4,
162.5; GC-MS (70 eV) m/z 287 (M+, 16), 286 (66), 231 (28),
230 (100), 158 (80), 140 (25), 130 (12), 103 (18), 77 (9); FT-IR
(film cm-1) 3307, 3061, 2964, 2930, 2871, 1661 (s, CdN), 1612,
1463, 1365, 1194, 969, 751, 699. Anal. Calcd for C18H25NO2:
C, 75.22; H, 8.77; N, 4.87. Found: C, 75.44; H, 9.03;N, 4.93.
2-(4,4-Dim eth yl-2-oxa zolin -2-yl)-1,1,3-tr ip h en yl-2-p r o-
p en -1-ol (8a ) (Z): white solid; mp 140-141 °C (Et2O); 80%;
1H NMR (300 MHz) δ 0.95 (s, 6 H), 3.62 (s, 2 H), 6.35 (s, 1 H),
6.89 (br. s, 1 H, exchanges with D2O), 7.20-7.57 (m, 15 H);
13C NMR (75.4 MHz) δ 27.5, 67.4, 78.6, 82.5, 127.4, 128.0,
128.1, 128.2, 128.5, 128.8, 134.8, 136.1, 137.5, 144.6, 163.5;
GC-MS (70 eV) m/z 383 (M+, 94), 382 (100), 366 (13), 364 (12),
306 (10), 278 (36), 234 (13), 201 (52), 200 (28), 186 (19), 156
(14), 105 (99), 77 (55); FT-IR (film, cm-1) 3325, 3059, 2967,
2926, 1659 (s, CdN), 1609, 1449, 1387, 1201, 1022, 753, 700.
Anal. Calcd for C26H25NO2: C, 81.43; H, 6.57; N, 3.65. Found:
C, 81.15; H, 6.81; N 3.70. (E): white solid; mp 140-142 °C;
32%; 1H NMR (300 MHz) δ 1.00 (s, 3 H), 1.07 (s, 3 H) 3.63 and
3.67 (2 × d, AB system, J ) 8.2 Hz, 2 H), 6.48 (s,1 H), 6.82
(br. s, 1 H, exchanges with D2O), 7.11-7.41 (m, 10 H), 7.48-
7.51 (m, 3 H), 7.60-7.63 (m, 2 H); 13C NMR (75.4 MHz) δ 27.5,
27.6, 67.4, 78.5, 83.5, 124.2, 126.7, 127.7, 127.9, 128.2 128.6,
128.8, 129.2, 132.1, 135.8, 136.4, 141.8, 142.9, 143.4, 163.2;
GC-MS (70 eV) m/z 366 (M+ - 17, 1), 262 (28), 260 (32), 201
(16), 200 (48), 186 (70), 183 (27), 181 (16), 152 (12), 130 (22),
1
(E): white solid; mp 100-102 °C; 9%; H NMR (500 MHz) δ
0.72 (s, 9 H), 1.27 (s, 3 H), 1.35 (s, 3 H), 3.91 and 3.97 (2 × d,
AB system, J ) 8.0 Hz, 2 H), 4.05 (s, 1 H), 4.90 (br s, exchanges
with D2O, 1 H), 7.22-7.32 (m, 5 H), 7.46 (s, 1 H); 13C NMR
(125 MHz) δ 26.7, 27.9, 28.0, 38.0, 68.0, 76.1, 77.6, 127.7, 128.7,
129.0, 136.2, 138.0, 162.8; GC-MS (70 eV) m/z 287 (M+, 1),
231 (23), 230 (100), 159 (14), 158 (61), 140 (18), 103 (14), 77
(7); FT-IR (film cm-1) 3344, 3028, 2964, 2930, 2871, 1642 (s,
CdN), 1612, 1463, 1365, 1190, 1053, 756, 700. Anal. Calcd for
C
18H25NO2: C, 75.22; H, 8.77; N, 4.87. Found: C, 75.50; H,
8.90; N, 4.90.
1-Cycloh exyl-3-(4,4-d im eth yl-2-oxa zolin -2-yl)-3-p h en -
yl-2-p r op en -1-ol (8e) (Z): colorless oil; 80%; 1H NMR (300
MHz) δ 0.85-1.22 (m, 5 H), 1.28 (s, 3 H), 1.33 (s, 3 H), 1.42-
1.56 (m, 1 H), 1.59-1.82 (m, 4 H), 2.06-2.18 (m, 1 H), 3.82
and 3.87 (2 × d, AB system, J ) 8.2 Hz, 2 H), 3.97 (d, J ) 8.0
Hz, 1 H), 4.25 (br. s, exchanges with D2O, 1 H), 6.78 (s, 1 H),
7.22-7.32 (m, 5 H); 13C NMR (75.3 MHz) δ 26.1, 26.2, 26.4,
28.0, 28.1, 29.1, 29.8, 43.1, 67.2, 78.4, 81.0, 128.0, 128.6, 130.5,
135.6, 135.8, 161.9; GC-MS (70 eV) m/z 313 (M+, 21), 312 (88),
115 (23), 105 (100), 77 (48), 76 (16), 51 (16); FT-IR (film, cm-1
)
3280, 3059, 2965, 2926, 2855, 1656 (s, CdN), 1608, 1449, 1260,
1201, 1030, 754, 700. Anal. Calcd for C26H25NO2: C, 81.43; H,
6.57; N, 3.65. Found: C, 81.76; H, 6.23; N 3.79.
230 (100), 158 (57), 140 (14), 103 (11), 55 (10); FT-IR (film cm-1
)
3-Eth yl-2-(4,4-dim eth yl-2-oxazolin -2-yl)-1-ph en yl-1-pen t-
en -3-ol (8b) (Z): white solid; mp 120-121 °C (Et2O); 85%;
1H NMR (300 MHz) δ 0.96 (t, J ) 7.4 Hz, 6 H), 1.27 (s, 6 H),
1.64-1.87 (m, 4 H), 3.57 (br s, 1 H, exchanges with D2O), 3.82
(s, 2 H), 6.85 (s, 1 H), 7.20-7.32 (m, 5 H); 13C NMR (75.4 MHz)
δ 8.2, 28.1, 31.9, 67.8, 77.3, 78.6, 127.9, 128.2, 128.6, 133.3,
134.5, 136.6, 162.2; GC-MS (70 eV) m/z 287 (M+, 29), 286
(100), 258 (46), 187 (11), 186 (67), 130 (30), 115 (7), 57 (8);
FT-IR (film, cm-1) 3415, 3024, 2969, 2927, 1664, 1622 (s,
CdN), 1461, 1365, 968, 752, 697. Anal. Calcd for C18H25NO2:
C, 75.22; H, 8.77; N, 4.87. Found: C, 75.09; H, 9.09; N 4.87.
(E): white solid; mp 121-123 °C; 21%; 1H NMR (300 MHz) δ
0.86 (t, J ) 7.3 Hz, 6 H), 1.34 (s, 6 H), 1.43-1.61 (m, 4 H),
3.95 (s, 2 H), 6.62 (br., 1 H, exchanges with D2O), 7.16-7.34
(m, 5 H), 7.61 (s, 1 H); 13C NMR (75.4 MHz) δ 8.5, 28.4, 34.3,
68.2, 77.7, 78.2, 127.3, 127.4, 128.1, 133.9, 136.7, 138.0, 163.7;
GC-MS (70 eV) m/z 287 (M+, 6), 286 (26), 258 (97), 230 (17),
3254, 3022, 1667 (s, CdN), 1614, 1449, 1366, 1193, 752, 697.
Anal. Calcd for C20H27NO2: C, 76.64; H, 8.68; N, 4.47. Found:
C, 77.00; H, 8.98; N, 4.49. (E): colorless oil; 9%; 1H NMR (300
MHz) δ 0.85-1.22 (m, 5 H), 1.23 (s, 3 H), 1.25 (s, 3 H), 1.42-
1.85 (m, 5 H), 2.04-2.16 (m, 1 H), 3.93 and 4.01 (2 × d, AB
system, J ) 8.2 Hz, 2 H), 4.43 (d, J ) 8.0 Hz, 1 H), 4.75 (br.
s, exchanges with D2O, 1 H), 7.22-7.32 (m, 5 H), 7.41 (s, 1 H);
13C NMR (75.4 MHz) δ 26.0, 26.2, 26.3, 28.0, 28.3, 29.6, 29.7,
43.8, 67.8, 73.6, 77.5, 127.9, 128.4, 129.0, 130.5, 130.7, 135.5,
136.7, 162.0; GC-MS (70 eV) m/z 313 (M+, 2), 312 (8), 252
(17), 230 (100), 158 (38), 140 (10), 103 (8), 55 (10); FT-IR (film
cm-1) 3368, 3022, 2964, 2927, 2852, 1648 (s, CdN), 1610, 1450,
1365, 762, 701. Anal. Calcd for C20H27NO2: C, 76.64; H, 8.68;
N, 4.47. Found: C, 76.70; H, 8.87; N, 4.49.
3-Met h yl-2-(4,4-d im et h yl-2-oxa zolin -2-yl)-1-p h en yl-3-
bu ten -2-ol (9): colorless oil; 48%; 1H NMR (300 MHz) δ 0.92
(s, 3 H), 1.18 (s, 3 H), 1.86 (s, 3 H), 3.06 (d, J ) 13.2 Hz, 1 H),
187 (16), 186 (100), 130 (42), 115 (9), 57 (11); FT-IR (film, cm-1
)
8358 J . Org. Chem., Vol. 67, No. 24, 2002

Synthesis of Allylic Alcohols
3.25 (d, J ) 13.2 Hz, 1 H), 3.40 (br. s, 1 H, exchanges with
D2O), 3.96 and 4.01 (2 × d, AB system, J ) 8.0 Hz, 2 H), 5.02
(s, 1 H), 5.22 (s, 1 H), 7.12-7.24 (m, 5 H); 13C NMR (75.4 MHz)
δ 19.0, 28.1, 31.0, 42.5, 66.6, 75.4, 80.8, 112.5, 126.5, 127.7,
130.6, 135.7, 145.7, 167.2; GC-MS (70 eV) m/z 259 (M+, 1),
242 (3), 168 (100), 91 (24), 73 (20), 69 (37), 41 (15); FT-IR (film,
cm-1) 3473, 3088, 3063, 3031, 2970, 2924, 1669 (s, CdN), 1455,
1290, 1100, 735, 700. Anal. Calcd for C16H21NO2: C, 74.10; H,
8.16; N, 5.40. Found: C, 74.44; H, 8.38; N 5.25.
ported by the Ministero dell’Universita` e della Ricerca
Scientifica e Tecnologica (MURST, Rome), by the Uni-
versity of Bari and CNR (Rome) and by C.I.N.M.P.I.S.
(Consorzio Interuniversitario Nazionale Metodologie e
Processi Innovativi di Sintesi).
Su p p or tin g In for m a tion Ava ila ble: 13C NMR spectra for
compounds 2c,i,j, 4b,c, (1R*,2S*)-4d , (1R*,2R*)-4d , (1R*,2R*)-
4e, 5c-e, and 7a . This material is available free of charge
via the Internet at http://pubs.acs.org.
Ack n ow led gm en t. This work was carried out under
the framework of the National Project “Stereoselezione
in Sintesi Organica. Metodologie ed Applicazioni” sup-
J O026234D
J . Org. Chem, Vol. 67, No. 24, 2002 8359