Catalytic isomerization of 1-alkynyl-2,3-epoxy alcohols to substituted furans: Succinct routes to furanoid fatty acids and difurylmethanes

Article abstract of DOI:10.1021/jo980856a

A versatile procedure for the preparation of synthetically valuable 2,5- disubstituted and 2,3,5-trisubstituted furans via mercury(II)-mediated isomerization of 1-alkynyl-2,3-epoxy alcohols is described. Mercury(II)- catalyzed isomerization of alkynyl epoxides 3a-k derived from cyclic α- alkynyl allylic alcohols furnishes 2,3,5-substituted furans bearing an aldehyde or keto group on the C-2 side chain. The reaction is used in a succinct and efficient synthesis of the furanoid fatty acid F₅. In contrast, the mercury(II)-catalyzed reaction of a series of alkynyl epoxides 3m-p lacking ring fusion affords difurylmethanes 5, presumably by the dimerization of intermediate 2-(α hydroxyalkyl)furans 4.

Full text of DOI:10.1021/jo980856a

J . Org. Chem. 1998, 63, 9223-9231
9223
Ca ta lytic Isom er iza tion of 1-Alk yn yl-2,3-ep oxy Alcoh ols to
Su bstitu ted F u r a n s: Su ccin ct Rou tes to F u r a n oid F a tty Acid s a n d
Difu r ylm eth a n es
Charles M. Marson*,† and Steven Harper‡
Department of Chemistry, University of Sheffield, Sheffield S3 7HF, U.K.
Received May 6, 1998
A versatile procedure for the preparation of synthetically valuable 2,5-disubstituted and 2,3,5-
trisubstituted furans via mercury(II)-mediated isomerization of 1-alkynyl-2,3-epoxy alcohols is
described. Mercury(II)-catalyzed isomerization of alkynyl epoxides 3a -k derived from cyclic
R-alkynyl allylic alcohols furnishes 2,3,5-substituted furans bearing an aldehyde or keto group on
the C-2 side chain. The reaction is used in a succinct and efficient synthesis of the furanoid fatty
acid F5. In contrast, the mercury(II)-catalyzed reaction of a series of alkynyl epoxides 3m -p lacking
ring fusion affords difurylmethanes 5, presumably by the dimerization of intermediate 2-(R-
hydroxyalkyl)furans 4.
The furan ring1 is a ubiquitous structural element of
a variety of natural products, notably marine natural
products such as the pseudopteranolide kallolide B2
(Figure 1), calicogorin B,3 and the furanoid fatty acids.4
In addition, furans serve as diverse intermediates in
organic synthesis,5 and the variety of pharmaceuticals
and compounds of notable flavor and fragrance1 that
contain the furan ring underlies their importance. Con-
sequently, the construction of the furan ring enjoys
continued development of new methods. In view of the
difficulty that can be associated with the regioselective
introduction of carbon substituents to a furan ring, many
synthetic approaches rely on intramolecular cyclization
of an acyclic substrate, usually by formation of a C-O
bond. Several classes of acyclic acetylenic compounds,
including 2-alken-4-yn-1-ols,6-10 4-alken-1-yn-3-ols,10
F igu r e 1.
2-alkylidene-3-yn-1-ols,8 â,γ-alkynyl ketones,11,12 and 3,4-
epoxyalkynes,13-17 undergo cyclization to furans, and
such reactions have proved valuable in the synthesis of
natural products.18 However, although 4-alkynyl-1,2-
epoxides furnish furans under both acidic13 and basic14,16
conditions, and esters of 1-alkynyl-2,3-epoxy alcohols
undergo reductive elimination to 2-alken-4-yn-1-ols that
cyclize to the corresponding furan,19 the utility of the
related 1-alkynyl-2,3-epoxy alcohols in furan-forming
reactions has only recently been disclosed in two pre-
liminary accounts.20,21
† Current address: Department of Chemistry, Queen Mary and
Westfield College, University of London, London E1 4NS, U.K.
‡ Present address: IRBM, Via Pontina km 30,600, 00040 Pomezia,
Rome.
(1) Donnelly, D. M. X.; Meegan, M. J . In Comprehensive Heterocyclic
Chemistry; Katritzky, A. R., Rees, C. W., Eds.; Pergamon: Oxford,
1984; Vol. 4, pp 657-712.
(2) Look, S. A.; Burch, M. T.; Fenical, W.; Qi-tai, Z.; Clardy, J . J .
Org. Chem. 1985, 50, 5741.
(3) Ochi, M.; Yamada, K.; Kawakami, H.; Tatsukawa, A.; Kotsuki,
H.; Shibata, K. Tetrahedron Lett. 1992, 33, 7531.
(4) (a) Gunstone, F. D. Acc. Chem. Res. 1976, 9, 34. (b) Lie Ken J ie,
M. S. F.; Ahmad, F. J . Chem. Soc., Chem. Commun. 1981, 1110. (c)
Lie Ken J ie, M. S. F.; Sinha, S. J . Chem. Soc., Chem. Commun. 1980,
1002.
(5) (a) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (b) Piancatelli, G.;
Scettri, A.; D’Auria, M. Tetrahedron Lett. 1977, 2199. (c) Piancatelli,
G.; Scettri, A. Tetrahedron 1977, 33, 69. (d) Iesce, M. R.; Cermola, F.;
Piazza, A.; Scarpati, R.; Graziano, M. L. Synthesis 1995, 439.
(6) (a) Galesloot, W. G.; Brandsma, L.; Arens, J . F. Recl. Trav. Chim.
Pays-Bas 1969, 88, 671. (b) de J ong, A. J .; Brandsma, L.; Arens, J . F.
Recl. Trav. Chim. Pays-Bas 1974 93, 15. (c) Schreurs, P. H. M.;
Galesloot, W. G.; Brandsma, L. Recl. Trav. Chim. Pays-Bas 1975, 94,
70.
(7) (a) Landor, S. R.; Pepper, E. S. J . Chem. Soc. C 1966 2283. (b)
J acobs, T. L.; Dankner, D.; Dankner, A. R. J . Am. Chem. Soc. 1958,
80, 864. (c) Seiller, B.; Bruneau, C.; Dixneuf, P. H. J . Chem. Soc., Chem.
Commun. 1994, 493.
(11) Fukuda, Y.; Shiragami, H., Utimoto, K.; Nozaki, H. J . Org.
Chem. 1991, 56, 5816.
(12) Marshall, J . A.; Wang, X. J . Org. Chem. 1991, 56, 6264.
(13) Miller, D. J . Chem. Soc. C 1969, 12.
(14) Schreurs, P. H. M.; de J ong, A. J .; Brandsma, L. Recl. Trav.
Chim. Pays-Bas 1976, 95, 75.
(15) Eichinger, K.; Berbalk, H.; Machat, E.; Wimmer, J . J . Chem.
Res. 1983, 167.
(16) (a) Marshall, J . A.; DuBay, W. J . J . Org. Chem. 1991, 56, 1685.
(b) Marshall, J . A.; DuBay, W. J . J . Am. Chem. Soc. 1992, 114, 1450.
(17) McDonald, F. E.; Schultz, C. C. J . Am. Chem. Soc. 1994, 116,
9363.
(8) Marshall, J . A.; DuBay, W. J . J . Org. Chem. 1993, 58, 3435.
(9) Marshall, J . A.; Bennett, C. E. J . Org. Chem. 1994, 59, 6110.
(10) (a) Heilbron, I. H.; J ones, E. R. H.; Smith, P.; Weedon, B. C. L.
J . Chem. Soc. 1946, 54. (b) Haynes, L. J .; Heilbron, I. H.; J ones, E. R.
H.; Sondheimer, F. J . Chem. Soc. 1947, 1586.
(18) (a) Marshall, J . A.; Yu, B.-c. J . Org. Chem. 1994, 59, 324. (b)
Marshall, J . A.; DuBay, W. J . J . Org. Chem. 1994, 59, 703. (c) Bu¨chi,
G.; Wu¨est, H. J . Org. Chem. 1969, 34, 857.
(19) Aurrecoechea, J . M.; Solay-Ispizuo, M. Heterocycles 1994, 37,
223.
10.1021/jo980856a CCC: $15.00 © 1998 American Chemical Society
Published on Web 11/20/1998

9224 J . Org. Chem., Vol. 63, No. 25, 1998
Marson and Harper
Herein are described mild and efficient isomerizations
of secondary and tertiary 1-alkynyl-2,3-epoxy alcohols
mediated by catalytic aqueous mercury(II) in dilute
sulfuric acid (Scheme 1). Advantages of such isomeriza-
tions include (a) ease of assembly of the starting materi-
als, (b) catalytic processes that proceed at 25 °C, and (c)
generality, allowing access to a wide variety of substi-
tuted furans, including those bearing sensitive function-
ality and of the three different types of furan substitution
in groups 4a -k , 4l, and 5a -d . The isomerization of
1-alkynyl-2,3-epoxy alcohols derived from tertiary alicy-
clic allylic alcohols 2a -k and certain secondary acyclic
allylic alcohols such as 2l affords, respectively, 2,3,5-
trisubstituted and 2,5-disubstituted furans. A notable
feature of these reactions is the presence in the product
of additional oxygenated functionality on the C-2 sub-
stituent of the furan. In contrast to the above, 1-alkynyl-
2,3-epoxy alcohols derived from tertiary acyclic allylic
alcohols 2m -p undergo an isomerization-dimerization
sequence to afford the substituted difurylmethanes 5a -
d . Such furan-forming reactions have potential use in
the synthesis of biologically active natural products, as
demonstrated herein by a synthesis of the furanoid fatty
acid F5.
a catalytic amount of vanadyl acetylacetonate to give a
mixture of syn- and anti-epoxy alcohols 3.25 In accord
with the findings of our previous studies,22,26 epoxidation
of the tertiary cycloalkenyl alcohols 2a -k proceeded with
marked preference for the syn isomer. Even in the least
favorable cases, a syn diastereoselection in excess of 2:1
was observed. As expected,23 epoxidation of the acyclic
alcohols 2l-p proved somewhat less selective, the cor-
responding epoxides 3l-p typically being obtained in the
region of a 7:3 ratio in favor of the syn isomer.
The tertiary cyclic alkynyl epoxides 3a -k (Table 1)
underwent efficient isomerization to the corresponding
furans 4a -k upon treatment with a dilute solution of
aqueous mercury(II), obtained by dissolving yellow mer-
cury(II) oxide in 2.5% v/v sulfuric acid; the catalytic
amount of mercury(II) used was in the range 1.5-4 mol
%. In general, syn/anti mixtures of the substrate epoxy
alcohols were used. The reaction products were not found
to be affected by the stereochemical configuration of the
substrate. Thus, isomerization of both syn-3c and anti-
3c gave, in each case, a comparable yield of the same
furanoid product 4c (Table 1). Each of the furans 4a -k
contains a carbonyl group at a position determined by
the size of the alicyclic ring in the corresponding epoxy
alcohol 3. The examples illustrated show the reaction
to be general for 5- to 12-membered alicyclic epoxy
alcohols. For entries 3 and 4, the stereoelectronic nature
of the alkynyl moiety, which has been found to influence
the cyclization of certain alkynes to furans,27 did not have
a significant effect on the reaction. The isomerization
of epoxy alcohol 3b without loss of the acid-sensitive
tetrahydropyranyl group is noteworthy and exemplifies
the scope of the reaction and the mild conditions involved.
Furanoid products were also obtained from the isomer-
ization of acyclic alkynyl epoxy alcohols 3l-p (Table 2).
In the case of the secondary epoxy alcohol 3l, the sole
isolated product was the 2-(R-hydroxyalkyl)furan 4l,
while the tertiary epoxy alcohols 3m -p furnished the
symmetrical difurylmethanes 5a -d .
Sch em e 1a
The formation of the furans 4 and 5 can be rationalized
by invoking an intermediate of the form 6. Isomerization
of the acyclic alkynyl epoxy alcohols 3l-p presumably
results in formation of the intermediates 6l-p (R3 ) H),
which can undergo direct dehydration, presumably via
the corresponding oxonium ion, to afford the 2-(R-hy-
droxyalkyl)furans 4l-p . In accordance with the acid-
catalyzed self-condensation of two molecules of a 2-(R-
hydroxyalkyl)furan bearing substituents at both the C-3
and C-5 positions,28 epoxy alcohols 3m -p furnish the
corresponding bisfurans 5a -d , while 4l, which lacks an
activating substituent in the C-3 position, did not un-
dergo further reaction. For the alicyclic examples, direct
dehydration of the intermediates 6a -k is blocked, and
the alternative fragmentation with aromatization occurs,
giving the furans 4a -k . The formation of 5a -d arises
by presumed protonation of the furan ring of 4l-p ,
a
Key: (i) R5-t, n-BuLi; (ii) t-BuOOH, VO(acac)2; (iii) HgO in
2.5% v/v H2SO4.
1-Alkynyl-2-alken-1-ols 2a -p (Tables 1 and 2) were
prepared in good yield by reaction of a cycloalkenyl
ketone 1, either readily available via methodology previ-
ously described22 or prepared by reacting a commercially
available R,â-unsaturated carbonyl compound with the
alkynyllithium generated by addition of excess n-butyl-
lithium to a terminal alkyne at 20 °C. In none of the
cases investigated was 1,4-addition realized to an incon-
venient extent. The alcohols 2 were epoxidized22-24 at
20 °C using tert-butyl hydroperoxide in the presence of
(23) Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda,
M.; Sharpless, K. B. J . Am. Chem. Soc. 1981, 103, 6237.
(24) Sharpless, K. B.; Verhoeven, T. R. Aldrichim. Acta 1979, 12,
63.
(25) For a full explanation and definition of the terms syn and anti
as used herein see: Marson, C. M.; Benzies, D. W. M.; Hobson, A. D.
Tetrahedron 1991, 47, 5491.
(26) Marson, C. M.; Walker, A. J .; Pickering, J .; Hobson, A. D.;
Wrigglesworth, R.; Edge, S. J . J . Org. Chem. 1993, 58, 5944.
(27) Holand, S.; Mercier, F.; Le Goff, N.; Epsztein, R. Bull. Soc.
Chim. Fr. 1972, 4357.
(20) For
a preliminary account of some of these mercury(II)-
catalyzed isomerizations, see: Marson, C. M.; Harper, S.; Wriggles-
worth, R. J . Chem. Soc., Chem. Commun. 1994, 1879.
(21) For a preliminary account of the synthesis of furanoid fatty acid
F 5 see: Marson; C. M.; Harper, S. Tetrahedron Lett. 1998, 39, 333.
(22) Marson, C. M.; Walker, A. J .; Pickering, J .; Harper, S.;
Wrigglesworth, R.; Edge, S. J . Tetrahedron 1993, 49, 10317.
(28) Marshall, J . A.; Wang, X. J . Org. Chem. 1991, 56, 960.

Catalytic Isomerization of 1-Alkynyl-2,3-epoxy Alcohols
J . Org. Chem., Vol. 63, No. 25, 1998 9225
Ta ble 1. P r ep a r a tion of Ter tia r y Alicyclic Alk yn yl Ep oxy Alcoh ols a n d Th eir Mer cu r y(II)-Ca ta lyzed Isom er iza tion to
2,3,5-Tr isu bstitu ted F u r a n s
a
b
All configurations depicted refer to racemic modifications. The cycloalkenyl ketone22 in THF was added to the alkynyllithium
(generated by addition of excess n-BuLi to the alkyne at 20 °C) and stirred for 30 min. c The allylic alcohol in benzene was treated with
VO (acac)2 (20 mg) and t-BuOOH (2 equiv) at 20 °C and monitored to completion by TLC. Isolated yield. e The epoxide in acetone was
d
treated with a 0.1 M solution of HgII (from HgO dissolved in 2.5% v/v sulfuric acid) and monitored to completion by TLC. f Reference 28.
g
Reference 24.
followed by cleavage of the 2-substituent (as the carbonyl
compound); the resulting furan then attacks the carboca-
tion derived from 4l-p by protonation on the hydroxy
group. Alternatively, acid-catalyzed fragmentation of
6a -p could be the route by which the 2-substituent is
cleaved.
fish lipids31 and other natural sources,32,33 can selectively
esterify cholesterol, and have been linked with reproduc-
tion in fish.31a,c Addition of 1-heptynyllithium to 1-acetyl-
1-cyclododecene afforded 2k , which on epoxidation gave
3k as an 4:1 mixture of diastereoisomers. This mixture
of 3k was treated with 0.32 mol % of mecury(II) in
The utility of these reactions with regard to the
synthesis of biologically active natural products was
demonstrated by synthesis of the furanoid fatty acid F5.
The furanoid fatty acids (F acids)29 were originally
isolated from Exocarpus seed oil;30 they are abundant in
(30) Morris, M. J .; Marshall, M. D.; Kelly, W. Tetrahedron Lett. 1966,
36, 4249.
(31) (a) Glass, R. L.; Krick, T. P.; Eckhardt, A. E. Lipids 1974, 9,
1004. (b) Glass, R. L.; Krick, T. P.; Sand, D. M.; Rahn, C. H.; Schlenk,
H. Lipids 1975, 10, 695. (c) Glass, R. L.; Krick, T. P.; Olson, D. L.;
Thorson, R. L. Lipids 1977, 12, 828. (d) Gunstone, F. D.; Wijesundra,
R. C.; Love, R. M.; Ross, D. J . Chem. Soc., Chem. Commun. 1976, 630.
(32) Ciminiello, P.; Fattorusso, E.; Magno, S.; Mangoni, A.; Ialenti,
A.; Dirosa, M. Experientia 1991, 47, 739.
(29) (a) Lie Ken J ie, M. S. F.; Sinha, S. J . Chem. Soc., Chem.
Commun. 1980, 1002. (b) Lie Ken J ie, M. S. F.; Ahmad, F. J . Chem.
Soc., Chem. Commun. 1981, 1110.
(33) Hasma, H.; Subramanian, A. Lipids 1978, 13, 905.

9226 J . Org. Chem., Vol. 63, No. 25, 1998
Marson and Harper
Ta ble 2. P r ep a r a tion of Acyclic Alk yn yl Ep oxy Alcoh ols a n d Th eir Mer cu r y(II) Ca ta lyzed Con ver sion in to
Su bstitu ted F u r a n s
a
The R,â-unsaturated carbonyl compound in THF was added to the alkynyllithium (generated by addition of n-BuLi to the alkyne at
b
20 °C) and stirred for 30 min. The allylic alcohol in benzene was treated with VO (acac)2 (20 mg) and t-BuOOH (2 equiv) at 20 °C and
monitored to completion by TLC. c Isolated yield. The epoxide in acetone was treated with a 0.1 M solution of HgII (from HgO dissolved
d
in 2.5% v/v sulfuric acid) and monitored to completion by TLC.
petroleum ether/ethyl acetate) to give 2a as a pale yellow oil
(3.92 g, 61%): IR (neat) 3390, 2240 cm-1; 1H NMR δ 5.20 (1H,
m) 2.58-2.20 (5H, m), 2.01 (2H, t, J ) 6.0 Hz), 1.73 (2H, m),
1.36 (3H, s), 1.30 (2H, m), 0.55 (3H, t, J ) 6 Hz); 13C NMR δ
148.2 (s), 124.9 (d), 83.6 (s), 83.5 (s), 67.3 (s), 32.3 (t), 31.1 (t),
29.2 (q), 23.7 (t), 22.1 (t), 20.3 (t), 13.4 (q); LRMS (EI) m/z 177
aqueous 1.5 mM sulfuric acid, giving 4k (88%) which with
4 equiv of PDC34 in DMF at room temperature resulted
in a smooth oxidation of the aldehyde group, the furanoid
fatty acid F5 being isolated in 65% yield. This synthesis
and other reactions herein described illustrate the suit-
ability of the mercury(II)-catalyzed isomerizations for the
synthesis of a variety of furanoid natural products under
extremely mild conditions.
(M-1, 21), 163 (100), 149 (72); HRMS calcd for C12H18
178.1358, found 178.1364.
O
2-(1-Cyclopen ten yl)-5-(tetr ah ydr opyr an -2-yloxy)-3-pen -
tyn -1-ol (2b). Following general procedure A above, 1-acetyl-
1-cyclopentene (3.60 g, 32.7 mmol) when treated with a
solution of [3-(tetrahydropyran-2-yloxy)-1-propynyl]lithium
[prepared from 3-(tetrahydropyran-2-yloxy)-1-propyne (5.52 g,
39.0 mmol) and n-butyllithium (17.0 mL, 42.5 mmol, 2.5 M)
at -10 °C] gave a residue that was purified by column
chromatography on silica (9:1 petroleum ether/ethyl acetate)
to give 2b as a pale yellow oil (5.83 g, 71%): IR (neat) 3425,
Exp er im en ta l Section
1H and 13C NMR spectra were obtained at 250 and 68.8 MHz
and were recorded in CDCl3. Mass spectra were obtained in
the chemical-ionization (CI) or electron-impact (EI) mode, as
specified. Thin-layer chromatography was performed on pre-
coated 0.2 mm aluminum-backed silica plates, and products
were visualized under ultraviolet light or developed using
cerium(IV) sulfate spray. Column chromatography was per-
formed on 70-230 mesh silica gel under gravity. Petroleum
ether (40-60 fraction) and ethyl acetate were distilled prior
to use. THF was freshly distilled from sodium benzophenone
ketyl prior to use. Evaporation refers to the removal of solvent
under reduced pressure.
1705 cm-1 1H NMR δ 5.79 (1H, m), 4.82 (1H, t, J ) 3 Hz),
;
4.28 (2H, qAB), 3.82 (1H, m), 2.53 (1H, m), 2.48-2.21 (4H, m),
1.92-1.42 (9H, m), 1.57 (3H, s); 13C NMR δ 147.3 (s), 125.2
(d), 96.3 (d), 89.0 (s), 78.8 (s), 66.8 (s), 61.6 (t), 54.0 (t), 32.0
(t), 30.9 (t), 30.0 (t), 28.7 (t), 25.1 (t), 23.5 (t), 18.7 (q); LRMS
(EI) m/z 232 (M - 18, 35), 148 (32), 130, (27), 105 (48), 85,
(100); HRMS calcd for C15H20O2 (M - H2O) 232.1463, found
232.1469.
Diastereoisomeric ratios of 2,3-epoxy alcohols were deter-
mined from 1H NMR spectra of the products prior to chroma-
tography. Compounds 2c and 3c were prepared according to
literature procedures.26
2-(1-Cycloh exen yl)-3-n on yn -2-ol (2d ). Following general
procedure A above, 1-(1-oxoethyl)-1-cyclohexene (2.00 g, 16.1
mmol) when treated with a solution of 1-heptynyllithium
[prepared from 1-heptyne (1.86 g, 19.3 mmol) and n-butyl-
lithium (8.41 mL, 21.0 mmol, 2.5 M)] gave a residue that was
purified by column chromatography on silica (9:1 petroleum
ether/ethyl acetate) to give 2d as a pale yellow oil (3.30 g,
93%): IR (neat) 3390, 2240 cm-1; 1H NMR δ 6.02 (1H, m), 2.18
(2H, t, J ) 7 Hz), 2.17-2.02 (4H, m), 1.90 (1H, bs), 1.58-1.41
(6H, m), 1.51 (3H, s), 1.40-1.22 (4H, m), 0.88 (3H, t, J ) 7
Hz); 13C NMR δ 140.7 (d), 118.1 (s), 83.5 (s), 82.9 (s), 70.6 (s),
31.0 (t), 29.1 (q), 28.4 (t), 25.0 (t), 23.9 (t), 22.9 (t), 22.2 (t),
22.1 (t), 18.6 (t), 13.9 (q); LRMS (EI) m/z 219 (M-1, 52), 205
(86), 163 (78), 149 (24), 91 (39), 43 (100); HRMS calcd for
P r ep a r a tion of r-Alk yn yl Allylic Alcoh ols 2: Gen er a l
P r oced u r e A. 2-(1-Cyclop en ten yl)-3-h ep tyn -2-ol (2a ). A
stirred solution of 1-pentyne (2.97 g, 43.6 mmol) in THF (100
mL) was treated dropwise at 20 °C with a solution of n-
butyllithium (18.9 mL, 47.2 mmol, 2.5 M in hexanes). The
mixture was stirred for 30 min and then treated with a
solution of 1-acetyl-1-cyclopentene (4.00 g, 36.3 mmol) in THF
(100 mL). After a further 3 h, the mixture was poured into
saturated aqueous ammonium chloride (100 mL). The aque-
ous layer was separated and extracted with ether (3 × 50 mL).
The combined organic extracts were washed with water (50
mL) and brine (50 mL), dried (MgSO4), and evaporated. The
residue was purified by column chromatography on silica (9:1
C
14H21O (M - CH3) 205.1592, found 205.1591.
2-(1-Cycloh exen yl)-1,4-d ip h en yl-3-bu tyn -2-ol (2f). Fol-
(34) Corey, E. J .; Schmidt, G. Tetrahedron Lett. 1979, 399.
lowing general procedure A above, 1-(1-oxo-2-phenylethyl)-1-

Catalytic Isomerization of 1-Alkynyl-2,3-epoxy Alcohols
J . Org. Chem., Vol. 63, No. 25, 1998 9227
cyclohexene (3.00 g, 20.3 mmol) when treated with a solution
of (1-phenylethynyl)lithium [prepared from phenylacetylene
(1.84 g, 18.0 mmol) and n-butyllithium (7.80 mL, 19.50 mmol,
2.5 M)] gave a residue that was purified by column chroma-
tography on silica (9:1 petroleum ether/ethyl acetate) to give
2f as a yellow oil (2.91 g, 64%): IR (neat) 3400, 2240 cm-1; 1H
NMR δ 7.32 (10H, m), 6.06 (1H, m), 3.10 (2H, qAB), 2.48 (2H,
m), 2.20 (1H, s), 2.06 (2H, m), 1.75-1.55 (4H, m); 13C NMR δ
138.7 (s), 136.3 (s), 131.5 (d), 130.9 (d), 128.2 (d), 128.2 (d),
127.8 (d), 126.8 (d), 123.4 (d), 122.8 (s), 91.1 (s), 86.7 (s), 74.2
(s), 47.3 (t), 25.1 (t), 24.5 (t), 22.9 (t), 22.2 (t); HRMS calcd for
[prepared from 1-heptyne (0.45 g, 4.67 mmol) and n-butyl-
lithium (2.0 mL, 5.00 mmol, 2.5 M)] gave a residue that was
purified by column chromatography on silica (9:1 petroleum
ether/ethyl acetate) to give 2k as a pale yellow oil (0.79 g,
68%): IR (neat) 3450, 2240 cm-1; δH (CDCl3) 5.88 (1H, t, J )
8 Hz), 2.37-1.98 (4H, m), 2.23 (2H, t, J ) 7 Hz), 1.91 (1H, s),
1.73-1.20 (22H, m), 1.56 (3H, s), 0.91 (3H, s); 13C NMR δ 142.8
(s), 126.1 (d), 84.2 (s), 71.1 (s), 71.1 (s), 30.9 (t), 30.9 (t), 28.1
(t), 26.7 (t), 25.9 (t), 25.7 (t), 25.5 (t), 25.2 (t), 24.9 (t), 24.6 (t),
24.4 (t), 23.2 (t), 22.3 (t), 22.0 (t), 18.5 (q), 13.7 (q); LRMS (EI)
m/z 304 (M, 16), 289 (25), 247 (32), 208 (100), 183 (47), 137
(55); HRMS calcd for C21H36O 304.2766, found 304.2758.
2-Un d ecen -5-yn -2-ol (2l). Following general procedure A
(above), 2-butenal (3.5 g, 0.05 mol) when treated with a
solution of 1-heptynyllithium [prepared from 1-heptyne (5.75
g, 0.06 mol) and n-butyllithium (26.0 mL, 65.0 mmol, 2.5 M)]
gave a residue that was purified by column chromatography
on silica (9:1 petroleum ether/ethyl acetate) to give 2l as a pale
C
22H22O 302.1671, found 302.1676.
2-(2-Met h yl-1-cycloh exen yl)-4-p h en yl-3-b u t yn -2-ol (2
g). Following general procedure A above, 1-(1-oxoethyl)-2-
methyl-1-cyclohexene (0.50 g, 3.60 mmol) when treated with
a solution of (1-phenylethynyl)lithium [prepared from phenyl-
acetylene (0.55 g, 5.40 mmol) and n-butyllithium (2.30 mL,
5.75 mmol, 2.5 M)] gave a residue that was purified by column
chromatography on silica (9:1 petroleum ether/ethyl acetate)
to give 2g as a pale yellow oil (0.37 g, 43%): IR (neat) 3540,
1
yellow oil (6.37 g, 77%): IR (neat) 3350, 2220 cm-1; H NMR
δ 5.87 (1H, ddq, J ) 15, 6, 1.5 Hz), 5.60 (1H, ddq, J ) 15, 6,
1 Hz), 4.77 (1H, d, J ) 6 Hz), 2.22 (2H, dt, J ) 7, 1.5 Hz), 1.87
(1H, bs), 1.57 (3H, dd, J ) 6, 1.5 Hz), 1.52 (2H, m), 1.27 (4H,
m), 0.89 (3H, t, J ) 6.5 Hz); 13C NMR δ 130.9 (d), 128.1 (d),
86.7 (s), 79.6 (s), 63.0 (d), 31.0 (t), 28.3 (t), 22.1 (t), 18.7 (t),
17.4 (q), 13.9 (q); HRMS calcd for C11H18O 166.1358, found
166.1364.
1
2220 cm-1; H NMR δ 7.48 (2H, m), 7.38 (3H, m), 2.29-1.92
(4H, m), 1.96 (3H, s), 1.68 (3H, s), 1.56 (5H, m); 13C NMR δ
132.9 (s), 131.5 (d), 130.4 (s), 128.2 (d), 128.1 (d), 123.1 (s),
93.9 (s), 83.5 (s), 70.5 (s), 33.7 (t), 29.6 (q), 26.7 (t), 23.4 (t),
22.7 (t), 21.3 (q); HRMS calcd for C17H20O 240.1514, found
240.1508.
7-(1-Cycloh ep ten yl)-5-tr id ecyn -7-ol (2h ). Following gen-
eral procedure A above, 1-(1-oxoheptyl)-1-cycloheptene (1.50
g, 7.20 mmol) when treated with a solution of 1-hexynyllithium
[prepared from 1-hexyne (0.71 g, 8.65 mmol) and n-butyl-
lithium (4.0 mL, 10.0 mmol, 2.5 M)] gave a residue that was
purified by column chromatography on silica (9:1 petroleum
ether/ethyl acetate) to give 2h as a pale yellow oil (1.38 g,
66%): 1H NMR δ 6.19 (1H, t, J ) 6.5 Hz), 2.28-2.12 (4H, m),
2.22 (2H, t, J ) 7 Hz), 1.81-1.21 (21H, m), 0.86 (3H, t, J ) 7
Hz), 0.73 (3H, t, J ) 6.5 Hz); 13C NMR δ 146.2 (s), 126.8 (d),
85.8 (s), 82.5 (s), 75.0 (s), 40.4 (t), 32.9 (t), 31.8 (t), 30.9 (t),
29.3 (t), 28.5 (t), 28.1 (t), 27.2 (t), 26.8 (t), 24.6 (t), 22.6 (t),
22.0 (t), 18.4 (t), 14.1 (q), 13.6 (q); LRMS (EI) m/z 290 (M, 21),
3-Meth yl-5-p h en yl-1-p en ten -4-yn -3-ol (2m ). Following
general procedure A above, 3-buten-2-one (1.00 g, 14.3 mmol)
when treated with a solution of (1-phenylethynyl)lithium
[prepared from phenylacetylene (1.74 g, 17.0 mmol) and
n-butyllithium (7.42 mL, 18.6 mmol, 2.5 M)] gave a residue
that was purified by column chromatography on silica (19:1
petroleum ether/ethyl acetate) to give 2m as a pale yellow oil
(1.86 g, 76%): IR (liquid film) 3370, 2190 cm-1 1H NMR δ
;
7.45 (2H, m), 7.32 (3H, m), 6.06 (1H, dd, J ) 17, 10 Hz), 5.58
(1H, dd, J ) 17, 1 Hz), 5.17 (1H, dd, J ) 10, 1 Hz), 2.23 (1H,
bs), 1.51 (3H, s); 13C NMR δ 142.1 (d), 131.7 (d), 128.7 (d), 128.4
(d), 122.6 (s), 113.7 (t), 91.0 (s), 84.8 (s), 68.7 (s), 30.1 (q); HRMS
calcd for C12H12O 172.0888, found 172.0880.
209 (71), 181 (91), 112 (100); HRMS calcd for
290.2610, found 290.2608.
C
20H34
O
4-Meth yl-2-n on en -5-yn -4-ol (2n ). Following general pro-
cedure A above, 3-penten-2-one (1.0 g, 11.9 mmol) when
treated with a solution of 1-pentynyllithium [prepared from
1-pentyne (0.97 g, 14.3 mmol) and n-butyllithium (6.20 mL,
15.5 mmol, 2.5 M)] gave a residue that was purified by column
chromatography on silica (19:1 petroleum ether/ethyl acetate)
to give 2n as a yellow oil (1.43 g, 79%): IR (neat) 3370, 2230
3-(1-Cycloocten yl)-1-p h en yl-1-octyn -3-ol (2i). Following
general procedure A above, 1-(1-oxohexyl)-1-cyclooctene (2.51
g, 12.0 mmol) when treated with a solution of (1-phenylethy-
nyl)lithium [prepared from phenylacetylene (2.65 g, 26.0 mmol)
and n-butyllithium (11.3 mL, 28.3 mmol, 2.5 M)] gave a residue
that was purified by column chromatography on silica (19:1
petroleum ether/ethyl acetate) to give 2i as a pale yellow oil
(5.80 g, 87%): IR (neat) 3465 cm-1; 1H NMR δ 7.50-7.20 (5H,
m), 6.07 (1H, t, J ) 7.5 Hz), 2.50 (2H, t, J ) 7 Hz), 2.21 (2H,
m), 2.01 (1H, bs), 1.86-1.40 (4H, m), 1.38-1.15 (12H, m), 0.89
(3H, t, J ) 7 Hz); 13C NMR δ 142.4 (s), 131.8 (d), 128.5 (d),
128.4 (d), 125.6 (d), 123.3 (s), 92.4 (s), 85.3 (s), 75.3 (s), 41.3
(t), 32.1 (t), 31.0 (t), 29.1 (t), 26.7 (t), 26.5 (t), 26.2 (t), 26.1 (t),
24.5 (t), 22.8 (t), 14.3 (q); LRMS (EI) m/z 310 (M, 6), 292 (19),
84 (100); HRMS calcd for C22H30O 310.2297, found 310.2289.
6-(1-Cyclododecen yl)-4-dodecyn -5-ol (2j). Following gen-
eral procedure A above, 1-(1-oxoheptyl)-1-cyclododecene (1.50
g, 5.39 mmol) when treated with a solution of 1-pentynyl-
lithium [prepared from 1-pentyne (0.45 g, 6.61 mmol) and
n-butyllithium (2.80 mL, 7.00 mmol, 2.5 M)] gave a residue
that was purified by column chromatography on silica (9:1
petroleum ether/ethyl acetate) to give 2j as a pale yellow oil
(0.93 g, 50%): 1H NMR δ 5.88 (1H, t, J ) 8 Hz), 2.20 (2H, t,
J ) 7 Hz), 2.00 (4H, m), 1.83 (1H, bs), 1.77-1.16 (28H, m),
0.98 (3H, t, J ) 7 Hz), 0.86 (3H, t, J ) 7 Hz); 13C NMR δ 141.7
(s), 127.7 (d), 85.7 (s), 83.4 (s), 75.1 (s), 42.2 (t), 31.8 (t), 29.3
(t), 28.4 (t), 26.9 (t), 26.2 (t), 26.0 (t), 25.8 (t), 24.8 (t), 24.7 (t),
24.6 (t), 24.5 (t), 23.4 (t), 22.6 (t), 22.4 (t), 22.1 (t), 20.7 (t),
14.0 (q), 13.5 (q); LRMS (EI) m/z 346 (M, 7), 328 (28), 285 (28),
261 (100), 181 (36); HRMS calcd for C24H42O 346.3236, found
346.3231.
1
cm-1; H NMR δ 5.92 (1H, dq, J ) 16, 7 Hz), 5.56 (1H, dq, J
) 16, 1 Hz), 2.11 (2H, t, J ) 7 Hz), 1.69 (3H, dd, J ) 7, 1 Hz),
1.42-1.56 (3H, m), 1.51 (3H, s), 0.95 (3H, t, J ) 7 Hz); 13C
NMR δ 135.8 (d), 124.7 (d), 84.8 (s), 83.0 (s), 72.0 (s), 30.6 (q),
22.1 (t), 20.6 (t), 17.2 (q), 13.4 (q); LRMS (EI) m/z 137 (M-15,
100), 123 (90); HRMS calcd for C10H16O 152.1201, found
152.1209.
1-P h en yl-3-eth yl-4-h exen -1-yn -3-ol (2o). Following gen-
eral procedure A above, 4-hexen-3-one (2.02 g, 20.4 mmol)
when treated with a solution of (1-phenylethynyl)lithium
[prepared from phenylacetylene (2.50 g, 24.5 mmol) and
n-butyllithium (14.7 mL, 36.8 mmol, 2.5 M)] gave a residue
that was purified by column chromatography on silica (9:1
petroleum ether/ethyl acetate) to give 2o as a pale yellow oil
1
(2.74 g, 67%): IR (neat) 3365 cm-1; H NMR δ 7.45 (2H, m),
7.33 (3H, m), 6.05 (1H, dd, J ) 15, 6.5 Hz), 5.57 (1H, dd, J )
15, 1.5 Hz), 2.53 (1H, bs), 1.82-1.72 (2H, m), 1.73 (3H. dd, J
) 6.5, 1.5 Hz), 1.25 (3H, t, J ) 7.5 Hz); 13C NMR δ 134.2 (d),
131.6 (d), 128.2 (d), 128.2 (d), 126.4 (d), 122.8 (s), 90.5 (s), 85.6
(s), 72.2 (s), 35.7 (t), 17.3 (q), 8.8 (q); LRMS (EI) m/z 200 (M,
10), 185 (11), 171 (100); HRMS calcd for C14H16O 200.1201,
found 200.1197.
4-Eth yl-2-u n d ecen -5-yn -4-ol (2p ). Following general pro-
cedure A above, 4-hexen-3-one (1.01 g, 10.2 mmol) when
treated with a solution of 1-heptynyllithium [prepared from
1-heptyne (1.18 g, 12.27 mmol) and n-butyllithium (4.90 mL,
12.25 mmol, 2.5 M)] gave a residue that was purified by
column chromatography on silica (9:1 petroleum ether/ethyl
acetate) to give 2p as a light yellow oil (1.33 g, 67%): IR (neat)
2-(1-Cyclod od ecen yl)-3-n on yn -2-ol (2k ). Following gen-
eral procedure A above, 1-acetyl-1-cyclododecene21,22 (0.80 g,
3.84 mmol) when treated with a solution of 1-heptynyllithium

9228 J . Org. Chem., Vol. 63, No. 25, 1998
3385, 2235 cm-1 1H NMR δ 5.98 (1H, dq, J ) 15, 6.5 Hz),
5.51 (1H, dq, J ) 15, 1.5 Hz), 2.24 (2H, t, J ) 7 Hz), 2.12 (1H,
bs), 1.73 (3H, dd, J ) 6.5, 1.5 Hz), 1.80-1.30 (8H, m), 0.97
(3H, t, J ) 7.5 Hz), 0.91 (3H, t, J ) 7 Hz); 13C NMR δ 134.7
(d), 126.0 (d), 86.3 (s), 81.4 (s), 72.0 (s), 35.8 (t), 31.0 (t), 28.5
(t), 22.1 (t), 18.6 (t), 17.3 (q), 13.9 (q), 8.9 (q); LRMS (EI) m/z
176 (M-18, 13), 165 (100); HRMS calcd for C13H20 (M - H2O)
176.1565, found 176.1561.
Marson and Harper
;
colorless oil (0.73 g, 58%): IR (neat) 3445, 2235 cm-1; 1H NMR
δ 3.33 (1H, dd, J ) 6, 1 Hz), 2.45 (1H, bs), 2.30 (1H, dd, J )
14, 6 Hz), 2.16 (2H, t, J ) 7 Hz), 2.12 (1H, m), 1.83-1.13 (22H,
m), 0.87 (3H, t, J ) 6 Hz), 0.84 (3H, t, J ) 7 Hz); 13C NMR δ
85.0 (s), 81.4 (s), 72.2 (s), 66.7 (s), 57.6 (d), 38.1 (t), 31.7 (t),
31.0 (t), 30.7 (t), 29.4 (t), 28.8 (t), 27.8 (t), 24.2 (t), 23.6 (t),
23.4 (t), 22.5 (t), 21.8 (t), 18.3 (t), 14.0 (q), 13.5 (q); LRMS (EI)
m/z 306 (M, 12), 112 (100); HRMS calcd for C20H34O2 306.2559,
found 306.2554.
P r ep a r a tion of 2,3-Ep oxy Alcoh ols. Gen er a l P r oce-
d u r e B. 2-(1,2-Ep oxycyclop en tyl)-3-h ep tyn -2-ol (3a ). A
solution of 2a (3.00 g, 16.9 mmol) and vanadyl acetylacetonate
(20 mg) in benzene (100 mL) was treated dropwise at room
temperature with a 70% aqueous solution of tert-butyl hydro-
peroxide (4.34 g, 33.7 mmol). The mixture was stirred at 20
°C and judged to be complete (TLC) after 4 h. The mixture
was washed with saturated sodium sulfite solution (50 mL),
dried (MgSO4), and evaporated. The residue was purified by
column chromatography on silica (9:1 petroleum ether/ethyl
acetate) to give syn-3a as a colorless oil (1.56 g, 48%) [IR (neat)
3-(1,2-Ep oxycyclooctyl)-1-p h en yl-1-octyn -3-ol (3i). Fol-
lowing general procedure B above, 2h (1.50 g, 4.84 mmol)
afforded a residue that was purified by column chromatogra-
phy on silica (24:1 petroleum ether/ethyl acetate) to give syn-
3i as a colorless oil (0.65 g, 41%) [IR (neat) 3450, 2225 cm-1
;
1H NMR δ 7.45 (2H, m), 7.28 (3H, m), 3.22 (1H, m), 2.90 (1H,
bs), 2.17 (1H, m), 2.25 (1H, m), 1.96-1.25 (18H, m), 0.95 (3H,
t, J ) 6 Hz); 13C NMR δ 131.7 (d), 128.3 (d), 128.2 (d), 122.8
(s), 90.2 (s), 85.5 (s), 73.1 (s), 65.5 (s), 58.8 (d), 39.3 (t), 32.2
(t), 28.8 (t), 27.2 (t), 26.4 (t), 26.0 (t), 24.6 (t), 24.6 (t), 24.1 (t),
22.7 (t), 14.1 (q); LRMS (EI) m/z 326 (M, 41), 201 (100); HRMS
calcd for C22H30O2 326.2246, found 326.2241] anti-3i as a pale
1
3470, 2245 cm-1; H NMR δ 3.48 (1H, s), 2.77 (1H, bs), 2.13
(2H, t, J ) 7 Hz), 2.04-1.91 (2H, m), 1.65-1.50 (6H, m), 1.49
(3H, s), 0.92 (3H, t, J ) 7 Hz); 13C NMR δ 84.3 (s), 82.0 (s),
73.1 (s), 65.9 (s), 61.3 (d), 27.3 (t), 26.2 (t), 26.1 (t), 21.9 (t),
20.5 (t), 19.4 (q), 13.3 (q); LRMS (EI) m/z 194 (M, 34), 111 (100);
HRMS calcd for C12H18O2 194.1307, found 194.1299] and a
mixture of syn- and anti-3a as a colorless oil (0.57 g, 17%).
2-(1,2-Ep oxycyclop en tyl)-5-(tetr a h yd r op yr a n -2-yloxy)-
3-p en tyn -2-ol (3b). Following general procedure B above, 2b
(1.80 g, 14.4 mmol) afforded a residue that was purified by
column chromatography on silica (9:1 petroleum ether/ethyl
acetate) to give 3b as a light yellow oil (1.13 g, 59%): IR (neat)
1
yellow oil (0.32 g, 20%) by H NMR (CDCl3), and a mixture of
syn- and anti-3i as a pale yellow oil (0.17 g, 11%).
6-(1,2-Ep oxycyclod od ecyl)-4-d od ecyn -5-ol (3j). Follow-
ing general procedure B above, 2j (0.35 g, 1.01 mmol) afforded
a residue that was purified by column chromatography on
silica (9:1 petroleum ether/ethyl acetate) to give 3j as a
colorless oil (0.28 g 77%): IR (neat) 3450, 2240 cm-1; 1H NMR
δ 3.09 (m, 1 H), 2.74 (1H, bs), 2.18 (2H, t, J ) 6 Hz), 1.75-
1.25 (32H, m), 0.94 (3H, t, J ) 7 Hz), 0.82 (3H, t, J ) 6 Hz);
13C NMR δ 85.2 (s), 81.2 (s), 71.1 (s), 67.6 (s), 59.7 (d), 39.2 (t),
31.7 (t), 29.5 (t), 27.0 (t), 26.8 (t), 26.4 (t), 26.4 (t), 25.4 (t),
25.1 (t), 23.9 (t), 23.9 (t), 23.2 (t), 22.8 (t), 22.5 (t), 22.0 (t),
21.9 (t), 20.6 (t), 14.0 (q), 13.4 (q); LRMS (EI) m/z 362 (M, 15),
182 (100); HRMS calcd for C24H42O2 362.3175, found 362.3175.
2-(1,2-Ep oxycyclod od ecyl)-3-n on yn -2-ol (3k ). Following
general procedure B above, 2k (0.40 g, 1.31 mmol) afforded a
residue that was purified by column chromatography on silica
(9:1 petroleum ether/ethyl acetate) to give 3k as a colorless
3430, 2225 cm-1 1H NMR δ 4.80 (1H, t, J ) 3.5, Hz), 4.34
;
(1H, d, J ) 15 Hz), 4.24 (1H, d, J ) 15 Hz), 3.82 (1H, m), 3.51
(2H, m), 2.11-1.42 (13H, m), 1.54 (3H, s); LRMS (EI) m/z 265
(M - 1, 1), 164 (4), 85 (100); HRMS calcd for C10H12O2 (M -
C5H10O2) 164.0837, found 164.0841.
2-(1,2-Ep oxycycloh exyl)-3-n on yn -2-ol (3d ). Following
general procedure B above, 2d (1.50 g, 6.81 mmol) afforded a
residue that was purified by column chromatography on silica
(9:1 petroleum ether/ethyl acetate) to give 3d as a colorless
1
oil (0.29 g, 69%): IR (neat) 3480, 2240 cm-1; H NMR δ 3.05
1
oil (1.01 g, 63%): IR (neat) 3440, 2940, 2860, 2125 cm-1; H
(1H, m), 2.82 (1H, bs), 2.15 (2H, t, J ) 7 Hz), 1.72-1.15 (26H,
m), 1.45 (3H, s), 0.83 (3H, t, J ) 7 Hz); 13C NMR δ 84.8 (s),
81.8 (s), 68.1 (s), 67.7 (s), 59.8 (d), 31.0 (t), 28.3 (t), 27.2 (q),
27.1 (t), 26.9 (t), 26.7 (t), 26.5 (t), 25.7 (t), 25.1 (t), 24.0 (t),
23.5 (t), 22.9 (t), 22.2 (t), 21.9 (t), 18.6 (t), 14.0 (q); LRMS (EI)
m/z 320 (M, 28), 165 (100); HRMS calcd for C21H36O2 320.2715,
found 320.2709.
NMR δ 3.32 (1H, m), 2.60 (1H, m), 2.16 (2H, t, J ) 7 Hz), 1.95
(2H, m), 1.55-1.15 (12H, m), 1.42 (3H, s), 0.86 (3H, t, J ) 7
Hz); 13C NMR δ 84.4 (s), 81.5 (s), 67.8 (s), 64.3 (s), 55.2 (d),
31.0 (t), 28.2 (t), 25.6 (q), 25.0 (t), 24.5 (t), 22.4 (t), 20.7 (t),
20.5 (t), 18.5 (t), 13.9 (q); LRMS (EI) m/z 236 (M, 12), 218 (13),
98 (100); HRMS calcd for C13H19O2 (M - C2H5) 207.1385, found
207.1378.
2-(1,2-Ep oxycycloh exyl)-1,4-d ip h en yl-3-bu tyn -2-ol (3f).
Following general procedure B above, 2f (1.50 g, 4.96 mmol)
afforded a residue that was purified by column chromatogra-
phy on silica (9:1 petroleum ether/ethyl acetate) to give 3f as
a colorless oil (0.83 g, 52%): 1H NMR δ 7.50-7.22 (10H, m),
3.20 (2H, qAB, J ) 14 Hz), 3.02 (1H, m), 2.88 (1H, bs), 2.14
(2H, m), 1.89 (1H, m), 1.70-1.20 (5H, m); 13C NMR δ 135.7
(s), 131.7 (d), 130.9 (d), 128.4 (d), 128.2 (d), 127.9 (d), 126.9
(d), 122.6 (s), 89.8 (s), 85.5 (s), 71.5 (s), 62.9 (s), 55.9 (d), 44.3
(t), 25.2 (t), 24.3 (t), 20.4 (t), 19.0 (t); LRMS (EI) m/z 318 (M,
4), 227 (18), 129 (100); HRMS calcd for C15H15O2 (M - CH2-
Ph) 227.1072, found 227.1067.
2-(1,2-Ep oxy-2-m eth ylcycloh exyl)-4-p h en yl-3-bu tyn -2-
ol (3g). Following general procedure B above, 2g (0.3 g, 1.17
mmol) afforded a residue that was purified by column chro-
matography on silica (9:1 petroleum ether/ethyl acetate) to give
3g as a colorless oil (0.21 g, 66%): 1H NMR δ 7.40 (2H, m),
7.25 (3H, m), 3.01 (1H, bs), 2.03 (2H, m), 1.75-1.08 (6H, m),
1.55 (3H, s), 1.52 (3H, s); 13C NMR δ 131.6 (d), 128.1 (d), 128.1
(d), 122.8 (s), 91.7 (s), 83.6 (s), 69.6 (s), 68.6 (s), 63.8 (s), 33.9
(t), 27.6 (t), 24.9 (q), 21.9 (t), 20.3 (q), 19.6 (t); LRMS (EI) m/z
256 (M, 1), 145 (83), 112 (100); HRMS calcd for C17H20O2
256.1463, found 256.1457.
2,3-Ep oxy-5-u n d ecyn -4-ol (3l). Following general proce-
dure B above, 2l (2.00 g, 12.0 mmol) afforded a residue that
was purified by column chromatography on silica (9:1 petro-
leum ether/ethyl acetate) to give 3l as a colorless oil (1.31 g,
69%): IR (neat) 3410, 2240 cm-1 1H NMR δ 4.57 and 4.29
;
(1H, m), 3.18 and 3.06 (1H, m), 2.97 and 2.75 (1H, m), 2.29
(1H, m), 2.21 (2H, dt, J ) 6.5, 1.5 Hz), 1.52 (2H, m), 1.41-
1.20 (7H, m), 0.91 (3H, t, J ) 7 Hz); 13C NMR δ 87.3 (s), 86.9
(s), 77.3 (s), 76.7 (s), 62.4 (d), 61.8 (d), 61.1 (d), 61.0 (d), 52.6
(d), 52.2 (d), 31.0 (t), 28.1 (t), 22.1 (t), 18.6 (t), 16.9 (q), 14.1
(q), 13.9 (q); LRMS (EI) m/z 181 (M-1, 38), 81 (100); HRMS
calcd for C11H17O2 (M - H) 181.1229, found 181.1232.
1,2-Ep oxy-3-m eth yl-5-p h en yl-4-p en tyn -3-ol (3m ). Fol-
lowing general procedure B above, 2m (4.00 g, 23.3 mmol)
afforded a residue that was purified by column chromatogra-
phy on silica (9:1 petroleum ether/ethyl acetate) to give 3m
as a colorless oil (2.87 g, 66%): IR (neat) 3425, 2240 cm-1; 1H
NMR δ 7.45 (2H, m), 7.27 (3H, m), 3.29 and 3.21 (1H, dd, J )
3, 4 Hz), 3.01 and 2.92 (1H, dd, J ) 5, 3 Hz), 2.86 and 2.78
(1H, dd, J ) 5, 4 Hz), 2.51 (1H, bs), 1.67 and 1.60 (3H, s); 13
C
NMR δ 131.8 (d), 128.6 (d), 128.6 (d), 128.3 (d), 123.3 (s), 123.2
(s), 90.2 (s), 88.4 (s), 84.9 (s), 84.0 (s), 67.2 (s), 65.8 (s), 57.8
(d), 57.7 (d), 45.2 (t), 44.2 (t), 27.3 (q), 25.7 (q); LRMS (EI) m/z
188 (M, 12), 145 (100); HRMS calcd for C12H12O2 188.0837,
found 188.0833.
7-(1,2-Ep oxycycloh ep tyl)-5-tr id ecyn -7-ol (3h ). Follow-
ing general procedure B above, 2h (1.20 g, 4.13 mmol) afforded
a residue that was purified by column chromatography on
silica (9:1 petroleum ether/ethyl acetate) to give 3h as a
2,3-Ep oxy-4-m eth yl-5-n on yn -4-ol (3n ). Following gen-
eral procedure B above, 2n (2.01 g, 13.2 mmol) afforded a
residue that was purified by column chromatography on silica

Catalytic Isomerization of 1-Alkynyl-2,3-epoxy Alcohols
J . Org. Chem., Vol. 63, No. 25, 1998 9229
(9:1 petroleum ether/ethyl acetate) to give 3n as a colorless
oil (1.48 g, 67%): 1H NMR δ 3.16 and 3.09 (1H, dq, J ) 5, 2
Hz), 2.83 and 2.79 (1H, d, J ) 2 Hz), 2.54 (1H, bs), 2.12 (2H,
t, J ) 7 Hz), 1.48 and 1.44 (3H, s), 1.32 and 1.30 (3H, d, J )
5 Hz), 1.20-1.00 (2H, m), 0.92 (3H, t, J ) 7 Hz); 13C NMR δ
85.0 (s), 84.3 (s), 81.6 (s), 80.2 (s), 66.3 (s), 65.5 (s), 64.9 (d),
64.8 (d), 52.7 (d), 52.2 (d), 27.3 (q), 26.0 (q), 21.8 (t), 20.4 (t),
16.8 (q), 13.3 (q); LRMS (EI) m/z 167 (M - 1, 85), 125 (87), 58
(100); HRMS calcd for C10H16O2 168.1147, found 168.1150.
1-P h en yl-4,5-ep oxy-3-eth yl-1-h exyn -3-ol (3o). Following
general procedure B above, 2n (1.20 g, 6.00 mmol) afforded a
residue that was purified by column chromatography on silica
(9:1 petroleum ether/ethyl acetate) to give syn-3o as a colorless
M in HgII) obtained by dissolving yellow mercury(II) oxide in
2.5% v/v H2SO4 (0.5 mL) for 35 min and worked up as for 4a ,
afforded a residue that was purified by column chromatogra-
phy on silica (9:1 petroleum ether/ethyl acetate) to give 4b as
a pale yellow oil (109 mg, 55%): IR (neat) 1730 cm-1; 1H NMR
δ 9.67 (1H, t, J ) 1.5 Hz), 6.08 (1H, s), 4.67 (1H, t, J ) 3.5
Hz), 4.50 (2H, qAB, J ) 18 Hz), 3.87 (1H, m), 3.51 (1H, m),
2.58 (2H, t, J ) 6 Hz), 2.40 (2H, dt, J ) 7, 1.5 Hz), 1.89 (3H,
s), 1.80-1.40 (8H, m); 13C NMR δ 202.0 (d), 150.1 (s), 149.1
(s), 115.3 (s), 112.6 (d), 97.0 (d), 61.9 (t), 60.6 (t), 42.9 (t), 30.3
(t), 25.3 (t), 24.9 (t), 21.0 (t), 19.1 (t), 9.6 (q); LRMS (EI) m/z
266 (M, 17), 121 (100); HRMS calcd for C15H22O4 266.1518,
found 266.1523.
5-[(3-Meth yl-5-p h en yl)-2-fu r yl]p en ta n a l (4c). Meth od
A. Following general procedure C above, syn-3c (300 mg, 1.24
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.5
mL) for 15 min and worked up as for 4a , afforded a residue
that was purified by column chromatography on silica (98:2
petroleum ether/ethyl acetate) to give 4c as a pale yellow oil
(242 mg, 81%): IR (neat) 1730 cm-1; 1H NMR δ 9.31 (1H, t, J
) 1 Hz), 7.18 (2H, m), 6.91 (2H, m), 6.77 (1H, tt, J ) 7, 1 Hz),
6.03 (1H, s), 2.23 (2H, m), 2.03 (2H, m), 1.57 (3H, s), 1.35 (4H,
m); 13C NMR δ 202.4 (d), 151.1 (s), 150.6 (s), 131.2 (s), 128.6
(d), 126.7 (d), 123.2 (d), 116.3 (s), 108.4 (d), 43.6 (t), 28.1 (t),
25.8 (t), 21.6 (t), 10.0 (q); LRMS (EI) m/z 242 (M, 12), 105 (100);
HRMS calcd for C16H18O2 242.1307, found 242.1300.
Meth od B. Following typical procedure C (above), anti-3c
(105 mg, 0.43 mmol), when treated with a 0.1 M solution of
yellow HgO in 2.5% (v/v) H2SO4 (0.5 mL) for 3 h and worked
up as for 4a , afforded a residue that was purified by column
chromatography on silica (19:1 petroleum ether/ethyl acetate)
to give 4c as a pale yellow oil (80 mg 76%).
5-[(3-Meth yl-5-p en tyl)-2-fu r yl]p en ta n a l (4d ). Following
general procedure C (above), syn-/anti-3d (300 mg, 1.55 mmol),
when treated with a solution (0.1 M in HgII) obtained by
dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.25
mL) for 10 min and worked up as for 4a , afforded a residue
that was purified by column chromatography on silica (19:1
petroleum ether/ethyl acetate) to give 4d as a pale yellow oil
(254 mg, 85%): IR (neat) 1730 cm-1; 1H NMR δ 9.73 (1H, t, J
) 2 Hz), 5.65 (1H, m), 2.50-2.30 (6H, m), 1.85 (3H, s), 1.55
(6H, m), 1.25 (4H, m), 0.84 (3H, t, J ) 7 Hz); 13C NMR δ 202.6
(d), 154.2 (s), 148.4 (s), 114.3 (s), 107.7 (d), 43.6 (t), 31.4 (t),
28.2 (t), 28.0 (t), 27.8 (t), 25.5 (t), 22.4 (t), 21.6 (t), 14.0 (q), 9.8
(q); LRMS (EI) m/z 236 (M, 23), 165 (100); HRMS calcd for
1
oil (0.18 g, 14%) [IR (neat) 3420, 2240 cm-1; H NMR δ 7.42
(2H, m), 7.28 (3H, m), 3.19 (1H, dq, J ) 5, 2 Hz), 2.96 (1H, d,
J ) 2 Hz), 2.63 (1H, m), 1.83 (2H, dq, J ) 7, 2.5 Hz), 1.33 (3H,
d, J ) 5 Hz), 1.12 (3H, t, J ) 7 Hz); 13C NMR δ 131.7 (d),
128.4 (d), 128.1 (d), 122.4 (s), 89.4 (s), 84.7 (s), 69.1 (s), 64.1
(d), 51.5 (d), 32.0 (t), 16.8 (q), 8.1 (q); LRMS (EI) m/z 216 (M,
6), 159 (100)], anti-3o as a pale yellow oil (0.14 g, 11%) [IR
(neat) 3405, 2218 cm-1; 1H NMR δ 7.44 (2H, m), 7.28 (3H, m),
3.28 (1H, dq, J ) 5.5, 2 Hz), 2.90 (1H, d, J ) 2 Hz), 2.68 (1H,
m), 1.85 (2H, m), 1.35 (3H, d, J ) 5.5 Hz), 1.10 (3H, t, J ) 7.5
Hz); 13C NMR δ 131.8 (d), 128.5 (d), 128.4 (d), 122.2 (s), 87.5
(s), 85.7 (s), 70.7 (s), 63.8 (d), 52.9 (d), 33.2 (t), 16.9 (q), 8.4 (q);
LRMS (EI) m/z 216 (30), 187 (32), 159 (100), 129 (60), 115 (11),
57 (34); HRMS calcd for C14H16O2 216.1150, found 216.1157],
and a mixture of syn- and anti-3o as a pale yellow oil (0.53 g,
41%).
2,3-Ep oxy-4-eth ylu n d ec-5-yn -4-ol (3p ). Following gen-
eral procedure B above, 2o (1.50 g, 7.73 mmol) afforded a
residue that was purified by column chromatography on silica
(9:1 petroleum ether/ethyl acetate) to give syn-3p as a colorless
1
oil (0.58 g, 36%) [IR (neat) 3450, 2240 cm-1; H NMR δ 3.12
(1H, dq, J ) 5, 2 Hz), 2.82 (1H, d, J ) 2 Hz), 2.50 (1H, bs),
2.06 (2H, t, J ) 7 Hz), 1.69 (2H, dq, J ) 7 Hz), 1.59-1.15.
(6H, m), 1.31 (3H, d, J ) 5 Hz), 1.03 (3H, t, J ) 7 Hz), 0.86
(3H, t, J ) 7 Hz); 13C NMR δ 85.5 (s), 80.5 (s), 68.8 (s), 64.3
(d), 51.5 (d), 32.2 (t), 31.0 (t), 28.3 (t), 22.1 (t), 18.5 (t), 16.8
(q), 13.9 (q), 8.1 (q); LRMS (EI) m/z 181 (M-29, 11), 153 (100);
HRMS calcd for C11H17O2 (M-C2H5) 181.1229, found 181.1225],
anti-3p as a colorless oil (0.37 g, 23%) [1H NMR δ 3.13 (1H,
dq, J ) 5, 1 Hz), 2.74 (1H, d, J ) 1 Hz), 2.53 (1H, bs), 2.13
(2H, t, J ) 6 Hz), 1.80-1.60 (2H, m), 1.54-1.20 (6H, m), 1.28
(3H, d, J ) 5 Hz), 1.00 (3H, t, J ) 7 Hz), 0.83 (3H, t, J ) 7
Hz); 13C NMR δ 86.4 (t), 78.6 (t), 70.1 (t), 63.9 (t), 52.5 (t), 33.2
(t), 30.8 (t), 28.1 (t), 22.0 (t), 18.4 (t), 16.8 (t), 13.8 (t), 8.3 (t)],
and a mixture of syn- and anti-3p as a colorless oil (0.19 g,
12%).
C
15H24O2 236.1776, found 236.1771.
6-[(3-(1-P h en yl-3-b u t en yl)-5-p h en yl)-2-fu r yl]h exa n a l
(4e). Following general procedure C (above), syn-3e (200 mg,
0.56 mmol), when treated with a solution (0.1 M in HgII)
obtained by dissolving yellow mercury(II) oxide in 2.5% v/v
H2SO4 (0.1 mL) for 10 min and worked up as for 4a , afforded
a residue that was purified by column chromatography on
silica (98:2 petroleum ether/ethyl acetate) to give 4e as a pale
yellow oil (155 mg, 78%): IR (neat) 1730, 1640 cm-1; 1H NMR
δ 9.58 (1H, t, J ) 1.5 Hz), 7.53 (2H, m), 7.30-7.10 (8H, m),
6.06 (1H, s), 5.65 (1H, m), 4.97 (1H, dm, J ) 17 Hz), 4.90 (1H,
dm, J ) 10 Hz), 3.76 (1H, t, J ) 8 Hz), 2.70-2.50 (4H, m),
2.28 (2H, m), 1.48 (12H, m); 13C NMR δ 202.3 (d), 151.5 (s),
150.7 (s), 144.6 (s), 136.7 (d), 131.1 (s), 128.6 (d), 128.4 (d),
127.5 (d), 126.8 (d), 126.2 (d), 124.1 (s), 123.3 (d), 116.4 (t),
105.5 (d), 43.5 (t), 41.8 (d), 40.6 (t), 27.9 (t), 25.9 (t), 21.6 (t);
LRMS (EI) m/z 358 (M, 20), 91 (100); HRMS calcd for C25H34O2
358.1933, found 358.1925.
Mer cu r y(II)-Ca ta lyzed Isom er iza tion of 2,3-Ep oxy Al-
coh ols. Gen er a l P r oced u r e C. 4-[(3-Meth yl-5-p r op yl)-
2-fu r yl]bu ta n a l (4a ). A solution of 3a (300 mg, 1.54 mmol)
in acetone (30 mL) was treated at 20 °C with a solution (0.1
M in HgII) obtained by dissolving yellow mercury(II) oxide in
2.5% v/v H2SO4 (0.25 mL). The mixture was stirred for 10
min and neutralized by the addition of solid sodium hydrogen
carbonate. The resulting mixture was filtered and evaporated
to give a residue that was taken up in water (5 mL) and ether
(10 mL). The layers were separated, and the aqueous layer
was extracted with ether (2 × 10 mL). The combined organic
extracts were washed with saturated aqueous sodium hydro-
gen carbonate (5 mL) and brine (5 mL), dried (MgSO4), and
evaporated. Purification of the residue by column chroma-
tography on silica (19:1 petroleum ether/ethyl acetate) gave
1
4a as an oil (254 mg, 85%): IR (neat) 1730 cm-1; H NMR δ
5-[(5-P h en yl-3-ben zyl)-2-fu r yl]p en ta n a l (4f). Following
general procedure C (above), syn-/anti-3f (0.40 g, 1.26 mmol),
when treated with a solution (0.2 M in HgII) obtained by
dissolving yellow mercury(II) oxide in 5% v/v H2SO4 (0.4 mL)
for 1 h and worked up as for 4a , afforded a residue that was
purified by column chromatography on silica (9:1 petroleum
ether/ethyl acetate) to give 4f as a pale yellow oil (0.19 g,
48%): IR (neat) 1730 cm-1; 1H NMR δ 9.75 (1H, t, J ) 2 Hz),
7.60 (4H, m), 7.45-7.15 (6H, m), 6.45 (1H, s), 3.75 (2H, s), 2.70
9.65 (1H, t, J ) 1 Hz), 5.71 (1H, s), 2.56 (2H, t, J ) 6 Hz), 2.47
(2H, t, J ) 6 Hz), 2.40 (2H, dt, J ) 7, 1 Hz), 1.92 (3H, s), 1.70-
1.50 (4H, m), 0.92 (3H, t, J ) 7 Hz); 13C NMR δ 202.2 (d),
153.8 (s), 147.6 (s), 114.9 (s), 107.8 (d), 42.9 (t), 29.9 (t), 24.9
(t), 21.4 (t), 21.2 (t), 13.7 (q), 9.7 (q); LRMS (EI) m/z 194 (M,
19), 137 (100); HRMS calcd for C12H18O2 194.1307, found
194.1300.
4-[[3-Meth yl-5-(tetr a h yd r op yr a n -2-yloxy)m eth yl]-2-fu -
r yl]bu ta n a l (4b). Following general procedure C above, syn-/
anti-3b (200 mg, 0.55 mmol), when treated with a solution (0.1
(2H, t, J ) 7 Hz), 2.45 (2H, dt, J ) 7, 2 Hz), 1.75 (4H, m); 13
NMR δ 202.2 (d), 151.5 (s), 150.9 (s), 140.6 (s), 131.0 (s), 128.5
C

9230 J . Org. Chem., Vol. 63, No. 25, 1998
Marson and Harper
(d), 128.5 (d), 128.4 (d), 128.3 (d), 126.0 (d), 123.2 (d), 123.2
(d), 107.5 (d), 43.5 (t), 31.0 (t), 28.0 (t), 25.8 (t), 21.5 (t); HRMS
calcd for C22H22O2 318.1620, found 318.1612.
(s), 107.6 (d), 43.9 (t), 31.4 (t), 29.5 (t), 29.3 (t), 29.3 (t), 29.1
(t), 29.1 (t), 29.0 (t), 28.7 (t), 28.0 (t), 27.8 (t), 25.9 (t), 22.4 (t),
22.1 (t), 14.6 (q), 9.8 (q); LRMS (EI) m/z 320 (M, 5), 139 (100);
HRMS calcd for C21H36O2 320.2715, found 320.2723.
6-[(3-Meth yl-5-p h en yl)-2-fu r yl]-2-h exa n on e (4g). Fol-
lowing general procedure C (above), syn-/anti-3g (73 mg, 0.28
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.1
mL) for 1 h and worked up as for 4a , afforded a residue that
was purified by column chromatography on silica (19:1 petro-
leum ether/ethyl acetate) to give 4g as a pale yellow oil (62
mg, 86%): 1H NMR δ 7.53 (2H, dd, J ) 8, 1 Hz), 7.32-7.20
(3H, m), 6.38 (1H, s), 2.57 (2H, t, J ) 7 Hz), 2.38 (2H, t, J )
7 Hz), 2.07 (3H, s), 1.91 (3H, s), 1.71-1.50 (4H, m); 13C NMR
δ 208.9 (s), 151.0 (s), 150.8 (s), 131.3 (s), 128.6 (d), 126.6 (d),
123.2 (d), 116.2 (s) 108.4 (d), 43.4 (t), 29.8 (q), 28.0 (t), 25.8 (t),
23.3 (t), 9.9 (q); HRMS calcd for C17H20O2 256.1463, found
256.1470.
6-[(5-Bu tyl-3-h exyl)-2-fu r yl]h exan al (4h ). Following gen-
eral procedure C (above), syn-3h (200 mg, 0.65 mmol), when
treated with a solution (0.1 M in HgII) obtained by dissolving
yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.25 mL) for 2 h
and worked up as for 4a , afforded a residue that was purified
by column chromatography on silica (98:2 petroleum ether/
ethyl acetate) to give 4h as a clear oil (163 mg, 82%): 1H NMR
δ 9.74 (1H, t, J ) 2 Hz), 5.75 (1H, s), 2.50 (4H, m), 2.41 (2H,
dt, J ) 7, 2 Hz), 2.22 (2H, t, J ) 7.5 Hz), 1.64-1.15 (18H, m),
0.91 (3H, t, J ) 7 Hz), 0.87 (3H, t, J ) 7 Hz); 13C NMR δ 202.7
(d), 153.7 (s), 148.5 (s), 119.5 (s), 106.3 (d), 43.8 (t), 31.7 (t),
30.6 (t), 30.2 (t), 29.1 (t), 28.7 (t), 28.6 (t), 27.8 (t), 25.7 (t),
24.8 (t), 22.6 (t), 22.3 (t), 21.9 (t), 14.1 (q), 13.8 (q); LRMS (EI)
m/z 306 (M, 8), 259 (100); HRMS calcd for C20H34O2 306.2559,
found 306.2566.
7-[(3-P en tyl-5-p h en yl)-2-fu r yl]h ep ta n a l (4i). Following
general procedure C (above), syn-3i (200 mg, 0.61 mmol), when
treated with a solution (0.1 M in HgII) obtained by dissolving
yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.25 mL) for 40
min and worked up as for 4a , afforded a residue that was
purified by column chromatography on silica (98:2 petroleum
ether/ethyl acetate) to give 4i as a pale yellow oil (165 mg,
83%): 1H NMR δ 9.73 (1H, t, J ) 1.5 Hz), 7.58 (2H, dd, J ) 6,
1 Hz), 7.38-7.12 (3H, m), 6.49 (1H, s), 2.58 (2H, t, J ) 6 Hz),
2.40 (2H, dt, J ) 6, 1.5 Hz), 2.32 (2H, t, J ) 6 Hz), 1.55-1.48
(6H, m), 1.45-1.25 (8H, m), 0.88 (3H, t, J ) 6 Hz); 13C NMR
δ 202.8 (d), 151.0 (s), 150.9 (s), 131.3 (s), 128.5 (d), 126.5 (d),
123.2 (d), 121.4 (s) 107.1 (d), 43.8 (t), 31.5 (t), 30.2 (t), 28.9 (t),
28.9 (t), 28.5 (t), 26.0 (t), 24.7 (t), 22.5 (t), 22.0 (t), 14.1 (q);
LRMS (EI) m/z 326 (M, 81), 227 (100); HRMS calcd for
1-(5-P en tyl-2-fu r yl)eth a n -1-ol (4l). Following typical pro-
cedure C (above), syn-/anti-3l (300 mg, 1.64 mmol), when
treated with a solution (0.1 M in HgII) obtained by dissolving
yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.5 mL) for 2 h
and worked up as for 4a , afforded a residue that was purified
by column chromatography on silica (98:2 petroleum ether/
ethyl acetate) to give 4l as a colorless oil (220 mg, 73%): IR
(neat) 3460 cm-1; 1H NMR δ 6.06 (1H, dd, J ) 3, 0.5 Hz), 5.92
(1H, dt, J ) 3, 0.5 Hz), 4.72 (1H, m), 4.14 (1H, d, J ) 5 Hz),
2.56 (2H, dt, J ) 7.5, 0.5 Hz), 1.56 (2H, m), 1.41 (3H, d, J ) 7
Hz), 1.30 (4H, m), 0.90 (3H, t, J ) 7 Hz); 13C NMR δ 158.1 (s),
155.8 (s), 105.8 (d), 105.7 (d), 63.6 (d), 32.1 (t), 28.5 (t), 28.4
(t), 23.0 (t), 22.2 (q), 14.3 (q); LRMS (EI) m/z 182 (M, 25), 167
(100); HRMS calcd for C11H18O2 182.1307, found 182.1313.
1,1-Bis[(3-m eth yl-5-p h en yl)-2-fu r yl]m eth a n e (5a ). Fol-
lowing general procedure C (above), syn-/anti-3m (150 mg, 0.80
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.3
mL) for 2.5 h and worked up as for 4a , afforded a residue that
was purified by column chromatography on silica (39:1 petro-
leum ether/ethyl acetate) to give 5a as a pale oil (110 mg,
84%): IR (neat) 1605, 1555 cm-1; 1H NMR δ 7.52 (4H, m), 7.25
(4H, m), 7.10 (2H, m), 6.36 (2H, s), 3.90 (2H, s), 1.94 (6H, s);
13C NMR δ 151.4 (s), 146.7 (s), 131.1 (s), 128.6 (d), 126.8 (d),
123.4 (d), 117.3 (s), 108.7 (d), 24.1 (t), 9.9 (q); LRMS (EI) m/z
328 (M, 100), 313 (39); HRMS calcd for C23H20O2 328.1463,
found 328.1456.
1,1-Bis-[(3-m eth yl-5-n -p r op yl)-2-fu r yl]eth a n e (5b). Fol-
lowing general procedure C (above), syn-/anti-3n (200 mg, 1.19
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.2
mL) for 15 min and worked up as for 4a , afforded a residue
that was purified by column chromatography on silica (39:1
petroleum ether/ethyl acetate) to give 5b as a pale yellow oil
(117 mg, 72%): IR (neat) 1630, 1570 cm-1 1H NMR δ 5.76
;
(2H, s), 4.17 (1H, q, J ) 7 Hz), 2.55 (4H, dt, J ) 8, 1 Hz), 1.82
(6H, s), 1.64 (4H, m), 1.59 (3H, d, J ) 7 Hz), 0.98 (6H, t, J )
7.5 Hz); 13C NMR δ 153.3 (s), 149.1 (s), 113.7 (s), 108.3 (d),
30.0 (d), 30.0 (t), 21.5 (t), 17.8 (q), 13.7 (q), 9.6 (q); LRMS (EI)
m/z 274 (M, 18), 259 (100); HRMS calcd for C18H26O2 274.1933,
found 274.1924.
1,1-Bis[(3-eth yl-5-p h en yl)-2-fu r yl]eth a n e (5c). Follow-
ing general procedure C (above), syn-/anti-3o (220 mg, 1.02
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.5
mL) for 2 h and worked up as for 4a , afforded a residue that
was purified by column chromatography on silica (petroleum
ether) to give 5c as a pale yellow oil (140 mg, 74%): IR (neat)
C
22H30O2 326.2246, found 326.2242.
11-[(3-Hexyl-5-p r op yl)-2-fu r yl]u n d eca n a l (4j). Follow-
ing general procedure C (above), syn-/anti-3j (300 mg, 1.54
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.5
mL) for 10 min and worked up as for 4a , afforded a residue
that was purified by column chromatography on silica (19:1
petroleum ether/ethyl acetate) to give 4j as a pale yellow oil
(180 mg, 60%): 1H NMR δ 9.75 (1H, t, J ) 1.5 hz), 5.73 (1H,
s), 2.53-2.45 (4H, m), 2.41 (2H, dt, J ) 5, 1.5 Hz), 2.23 (2H,
t, J ) 7 Hz), 1.70-1.15 (26H, m), 0.93 (3H, t, J ) 7 Hz), 0.86
(3H, t, J ) 7 Hz); 13C NMR δ 202.7 (d), 153.3 (s), 149.0 (s),
119.2 (s), 106.4 (d), 43.9 (t), 31.7 (t), 30.6 (t), 30.1 (t), 29.7 (t),
29.5 (t), 29.3 (t), 29.3 (t), 29.2 (t), 29.1 (t), 29.0 (t), 28.9 (t),
25.9 (t), 24.8 (t), 22.6 (t), 22.1 (t), 21.4 (t), 14.0 (q), 13.7 (q);
LRMS (EI) m/z 362 (M, 72), 207 (100); HRMS calcd for
1
2960, 2865, 1600 cm-1; H NMR δ 7.54 (4H, dd, J ) 7, 1 Hz),
7.29 (4H, m), 7.09 (2H, m), 6.41 (2H, m), 4.25 (1H, q, J ) 7
Hz), 2.24 (4H, q, J ) 7.5 Hz), 1.64 (3H, d, J ) 7 Hz), 1.01 (6H,
t, J ) 7.5 Hz); 13C NMR δ 151.3 (s), 150.1 (s), 131.3 (s), 128.6
(d), 126.8 (d), 123.4 (d), 122.9 (s), 107.1 (d), 30.5 (d), 18.4 (q),
17.9 (t), 15.1 (q); LRMS (EI) m/z 370 (M, 25), 199 (100); HRMS
calcd for C26H26O2 370.1933, found 370.1925.
1,1-Bis[(3-eth yl-5-n -p en tyl)-2-fu r yl]eth a n e (5d ). Fol-
lowing general procedure C (above), syn-/anti-3p (325 mg, 1.55
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.5
mL) for 2 h and worked up as for 4a , afforded a residue that
was purified by column chromatography on silica (98:2 petro-
leum ether/ethyl acetate) to give 5d as a pale yellow oil (231
mg, 83%): 1H NMR δ 5.72 (2H, s), 4.08 (1H, q, J ) 7 Hz), 2.46
(4H, t, J ) 7.5 Hz), 2.13 (4H, q, J ) 6 Hz), 1.51-1.44 (4H, m),
1.46 (3H, d, J ) 6 Hz), 1.33-1.17 (8H, m), 0.96 (6H, t, J ) 7.5
Hz), 0.82 (6H, t, J ) 6 Hz); 13C NMR δ 153.8 (s), 148.5 (s),
120.5 (s), 106.3 (d), 31.4 (t), 30.0 (d), 28.0 (t), 27.8 (t), 22.4 (t),
18.2 (q), 17.7 (t), 15.0 (q), 14.0 (q); LRMS (EI) m/z 358 (M, 18),
343 (100); HRMS calcd for C24H38O2 358.2872, found 358.2864.
11-[(3-Meth yl-5-p en tyl)-2-fu r yl]u n d eca n oic Acid (F 5).
A solution of 4k (21.2 mg, 0.066 mmol) in dichloromethane (1
C
24H42O2 362.3185, found 362.3179.
11-[(3-Meth yl-5-p en tyl)-2-fu r yl]u n d eca n a l (4k ). Fol-
lowing general procedure C (above), syn-/anti-3k (100 mg, 3.13
mmol), when treated with a solution (0.1 M in HgII) obtained
by dissolving yellow mercury(II) oxide in 2.5% v/v H2SO4 (0.1
mL) for 10 min and worked up as for 4a , afforded a residue
that was purified by column chromatography on silica (9:1
petroleum ether/ethyl acetate) to give 4k as a pale yellow oil
1
(88 mg, 88%): IR (neat) 1730 cm-1; H NMR δ 9.75 (1H, t, J
) 2 Hz), 5.72 (1H, s), 2.49 (4H, m), 2.40 (2H, dt, J ) 7, 2 Hz),
1.90 (3H, s), 1.79-1.48 (6H, m), 1.40-1.15 (16H, m), 0.88 (3H,
t, J ) 7 Hz); 13C NMR δ 202.8 (d), 153.5 (s), 149.3 (s), 113.8

Catalytic Isomerization of 1-Alkynyl-2,3-epoxy Alcohols
J . Org. Chem., Vol. 63, No. 25, 1998 9231
mL) was treated with pyridinium dichromate (124 mg, 0.331
mmol) at room temperature. The mixture was stirred for 6 h
and then diluted with water (10 mL). The mixture was
extracted with ether (4 × 5 mL) and with ether/n-pentane (50:
50) (3 × 5 mL). The combined extracts were washed with brine
(5 mL) and concentrated to afford an oil that was purified by
column chromatography on silica (183:15:2 petroleum ether/
ethyl acetate/acetic acid) to afford F 5 as a colorless oil (14.6
mg, 65%): 1H NMR δ 5.73 (1H, s), 2.50 (4H, m), 2.34 (2H, t, J
) 8 Hz), 1.89 (3H, s), 1.58 (6H, m), 1.29 (16H, m), 0.89 (3H,
m); 13C NMR δ 179.3 (s), 153.5 (s), 149.4 (s), 113.8 (s), 107.6,
(d), 33.9 (t), 31.4 (t), 29.7 (t), 29.5 (t), 29.4 (t), 29.3 (t), 29.2 (t),
29.1 (t), 28.7 (t), 28.0 (t), 27.8 (t), 25.9 (t), 24.7 (t), 22.4 (t),
14.0 (q), 9.9 (q); HRMS calcd for C21H26O3 336.2664, found
336.2657.
Ack n ow led gm en t. Financial support by Sandoz
(London and Basle), and the Engineering and Physical
Sciences Research Council (CASE studentship to S.H.)
is gratefully acknowledged.
Su p p or tin g In for m a tion Ava ila ble: Copies of the 1H
NMR spectra of selected compounds (39 pages). This material
is contained in libraries on microfiche, immediately follows this
article in the microfilm version of the journal, and can be
ordered from the ACS; see any current masthead page for
ordering information.
J O980856A