Formation of manganese-alkyne complexes mediated by trialkylmanganates and their application

Article abstract of DOI:10.1016/j.tet.2003.09.077

Treatment of dodec-6-yne with triallylmanganate in the presence of 1,3,5-trimethylbenzene provides (Z)-dodec-6-ene. An addition of D₂O before quenching the reaction affords the corresponding dideuterated alkene. The result suggests the existence of the manganese-alkyne complex as an intermediate. Treatment of methyl propargyl ethers as alkynes with tributylmanganate generates propargylmanganese species. The reaction of non-2-ynyl tetrahydropyran-2-yl ether with tributylmanganate provides tetradec-7-yn-1,5-diol and 6-hexylocta-6,7-dien-1,5-diol.

Full text of DOI:10.1016/j.tet.2003.09.077

Tetrahedron 59 (2003) 9661–9668
Formation of manganese–alkyne complexes mediated
by trialkylmanganates and their application
*
Toshihiro Nishikawa, Hiroshi Shinokubo and Koichiro Oshima
*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-Daigaku, Katsura, Nishikyo-ku,
Kyoto 615-8510, Japan
Received 4 August 2003; accepted 18 September 2003
Abstract—Treatment of dodec-6-yne with triallylmanganate in the presence of 1,3,5-trimethylbenzene provides (Z)-dodec-6-ene. An
addition of D O before quenching the reaction affords the corresponding dideuterated alkene. The result suggests the existence of the
2
manganese–alkyne complex as an intermediate. Treatment of methyl propargyl ethers as alkynes with tributylmanganate generates
propargylmanganese species. The reaction of non-2-ynyl tetrahydropyran-2-yl ether with tributylmanganate provides tetradec-7-yn-1,5-diol
and 6-hexylocta-6,7-dien-1,5-diol.
q 2003 Elsevier Ltd. All rights reserved.
1. Introduction
(Scheme 1). An addition of D O before quenching the
2
reaction afforded the corresponding dideuterated alkene
5
Recently transition metal–alkyne complexes have received
much attention. Among them, the Group IV and V metals
(.99% d-2). The result suggests the existence of the
6
manganese–alkyne complex 3 as an intermediate.
1
2
3
4
such as Ti, Zr, Nb, and Ta have been extensively studied
because of the unique properties and usefulness of their
alkyne complexes as synthetic intermediates. In contrast,
there are few reports on the utilization of manganese (Group
VII)–alkyne complexes for organic synthesis. Here we
describe a generation (but not isolated) of manganese–
alkyne complexes by treatment of alkynes with triallyl-
manganate in the presence of aromatic compounds such as
1
,3,5-trimethylbenzene. In addition, we wish to report that
the reaction of propargyl ethers with tributylmanganate
provides propargylmanganese species via manganese–
alkyne complexes.
Scheme 1.
Then, the reaction of dodec-6-yne (1) with triallylmanga-
nate was examined in the presence of various aromatic
compounds. Treatment of dodec-6-yne (1) with triallyl-
manganate (1.5 equiv.) in THF at 258C in the presence of
benzene, hexamethylbenzene, 1,3,5-trimethoxybenzene, or
2
. Results and discussion
1
,3,5-trimethylbenzene (2.0 equiv.) gave (Z)-dodec-6-ene
2
.1. Formation of manganese–alkyne complexes
mediated by triallylmanganate
(
2) in 52, 53, 60, or 80% yield, respectively, after aqueous
workup. Among aromatic compounds examined, 1,3,5-tri-
methylbenzene proved to be the best as an additive to
stabilize the manganese–alkyne complex 3. The amount of
the additive affected the yield of (Z)-dodec-6-ene (2). For
instance, the use of 4.0 or 15.0 equiv. of 1,3,5-trimethyl-
benzene provided (Z)-dodec-6-ene (2) in 80 or 26% yield,
respectively.
A solution of dodec-6-yne (1) in THF was added to a
solution of triallylmanganate (1.5 equiv.), which was
prepared in situ by mixing allylmagnesium chloride
and manganese chloride in a 3:1 ratio in THF at 08C.
After stirring at 258C for 23 h, aqueous workup of the
reaction mixture provided (Z)-dodec-6-ene (2) in 50% yield
Next, the reaction of the intermediary manganese–alkyne
complex 3 with various electrophiles was studied. In
contrast to Group IV and V metal–alkyne complexes which
react with carbonyl groups effectively, manganese–alkyne
Keywords: manganese–alkyne complex; diyne; tetrahydronaphthalene;
allylation; acetals.
*
Corresponding authors. Tel.: þ81-75-383-2437; fax: þ81-75-383-2438;
e-mail: oshima@fm1.kuic.kyoto-u.ac.jp; shino@fm1.kuic.kyoto-u.ac.jp
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2003.09.077

9662
T. Nishikawa et al. / Tetrahedron 59 (2003) 9661–9668
complex 3 did not react with aldehydes and ketones. Thus,
an addition of benzaldehyde (6.0 equiv.) to the reaction
mixture, generated from dodec-6-yne (1) and triallyl-
manganate, resulted in a recovery of dodec-6-yne (1)
would be stabilized by the coordination of 1,3,5-trimethyl-
benzene. An addition of deca-2,8-diyne (6) replaces the
1,3,5-trimethylbenzene as a coordinating ligand. The
reaction of deca-2,8-diyne (6) with manganese–alkyne
complex 8 would provide manganacycloheptatriene 9,
which would produce tetrahydronaphthalene derivative 5
(
67%) along with 1-phenylbut-3-en-1-ol, which was
generated by allylation of benzaldehyde. The desired
adduct, 1-phenyl-2-pentyloct-2-en-1-ol could not be
detected in the reaction mixture. An addition of 1,7-diyne
8
and Mn(0) species.
6
instead of carbonyl compounds, however, afforded a
2.2. Transformation of propargyl tetrahydropyranyl
ether into 1,5-diol by means of trialkylmanganate
tetrahydronaphthalene derivative in moderate yield. Treat-
ment of hex-3-yne (4) with triallylmanganate in the
presence of 1,3,5-trimethylbenzene followed by an addition
We next picked up propargyl ethers as alkynes. Treatment
9
of methyl propargyl ether 10 with tributylmanganate,
of deca-2,8-diyne (6) gave tetrahydronaphthalene derivative
7
5
in 20% yield along with hexaethylbenzene (20%). The
derived from 1.0 equiv. of manganese chloride and
3.0 equiv. of butylmagnesium bromide, followed by an
addition of benzaldehyde afforded a mixture of homo-
propargyl alcohol 11 in 22% yield and allenylated product
yield of tetrahydronaphthalene derivative 5 was improved
up to 44% by an addition of triallylmanganate to a mixture
of 4 and deca-2,8-diyne (6) in the presence of 1,3,5-tri-
methylbenzene (Scheme 2).
1
0
12 in 18% yield (Scheme 4).
Then, non-2-ynyl tetrahydropyran-2-yl ether (13a) was
chosen as a substrate instead of methyl propargyl ether 10.
Tributylmanganate (1.0 equiv.) and HMPA (3.0 equiv.)
were added to a solution of 13a in THF at 08C and the
resulting mixture was stirred for 23 h at 258C. Extractive
workup followed by silica-gel column purification provided
homopropargyl alcohol, tetradec-7-yn-1,5-diol (14a) (36%),
allenylated product, 6-hexylocta-6,7-dien-1,5-diol (15a)
(23%), and nonan-1,5-diol (16) (24%) (Scheme 5).
Scheme 2.
We assume the following reaction mechanism (Scheme 3).
An interaction of triallylmanganate with hex-3-yne (4)
would produce p-complex 7 which would afford manga-
nese–alkyne complex 8. Manganese–alkyne complex 8
The reactions of various propargyl tetrahydropyranyl ethers
were examined under the same conditions. The results are
shown in Table 1. Treatment of propargyl tetrahydropyranyl
ether 13b, generated from a primary propargyl alcohol, with
tributylmanganate afforded a mixture of homopropargyl
alcohol 14b and allenylated product 15b in addition to
butylated product 16. The product distribution heavily
depended on the nature of the starting materials. The acetals,
13c, 13d, and 13e, which were derived from secondary
propargyl alcohols, gave only homopropargyl alcohols 14
without contamination by 15.
We propose the following reaction mechanism. Oxidative
Scheme 3.
Scheme 4.
Scheme 5.

T. Nishikawa et al. / Tetrahedron 59 (2003) 9661–9668
Table 1. Reaction of propargyl tetrahydropyranyl ethers with tributylmanganate
9663
Entry
Substrate 13
Product/Yield (%)
1
R
2
R
14
15
16
1
2
1
2
3
4
5
13a: R ¼n-C
6
H
Si
Si
13
R ¼H
36
46
50
61
63
23
28
–
–
–
24
16
3
12
6
1
2
13b: R ¼Me
3
R ¼H
1
2
13c: R ¼Me
3
R ¼CH
3
3
2
1
2
13d: R ¼n-C
6
H
13
R ¼CH
1
2
13e: R ¼n-C
6
H
13
R ¼CH
vCH
Scheme 6.
Scheme 7.
addition of manganate (Mn(II)) to the triple bond of 13a
would give manganese–alkyne complex (Mn(IV)) A which
would be transformed into Mn(II) species B by reductive
followed by silica-gel column purification provided oct-7-
1
5
en-1,5-diol (20a) (55%) along with nonan-1,5-diol (16)
(3%). An addition of 3.0 equiv. of HMPA increased the
yield of 20a up to 84% (Scheme 8).
1
1
elimination under departure of n-Bu–n-Bu. Elimination
of magnesium oxide from B would provide manganese
species C and a magnesium salt of d-lactol D, which is
1
2
equilibrated with aldehyde E. Recombination of manga-
nese species and aldehyde E would afford tetradec-7-yn-
1
(
,5-diol (14a) and 6-hexylocta-6,7-dien-1,5-diol (15a)
Scheme 6).
Scheme 8.
Then, we also examined the reaction of allyl ethers with
tributylmanganate. Treatment of diallyl ether (17a) or allyl
octyl ether (17b) with tributylmanganate, followed by an
addition of benzaldehyde afforded 1-phenylbut-3-en-1-ol
Table 2 summarizes the reaction of various tetrahydro-
pyranyl and tetrahydrofuranyl ethers under the same
reaction conditions. Several comments are worth noting.
(1) Crotyl ether 19c provided the same product, 6-methyl-
oct-7-en-1,5-diol (20b), as 1-methylprop-2-enyl ether 19b.
None of an isomeric product, non-7-en-1,5-diol, could be
detected in the reaction mixture. Cinnamyl ether 19d and its
isomer 19e gave a trace of 8-phenyloct-7-en-1,5-diol in
,3% yield in addition to 20d. (2) The yield of 20b was
much higher in the case of reaction of 19b compared to the
1
3
(
18) in 50 or 49% yield, respectively (Scheme 7).
We next investigated the reaction of allyl tetrahydropyran-
1
4
2
-yl ether (19a). Tributylmanganate (1.0 equiv.) was
added to a solution of 19a in THF at 08C and the resulting
mixture was stirred for 12 h at 258C. Extractive workup

9664
T. Nishikawa et al. / Tetrahedron 59 (2003) 9661–9668
Table 2. Reaction of allyl ethers with tributylmanganate
manganate, prepared in situ by mixing allylmagnesium
chloride and manganese chloride in a 3:1 ratio in THF at
08C, provided a manganese–alkyne complex. The reaction
of the manganese–alkyne complex with 1,7-diyne induced
[
2þ2þ2] cyclization and provided a tetrahydronaphthalene
derivative. In the reaction of propargyl ethers with
tributylmanganate, propargylmanganese species were
obtained via manganese–alkyne complexes. Treatment of
a propargyl tetrahydropyranyl ether gave a mixture of a
homopropargyl alcohol and an allenylated alcohol.
Entry
Substrate 19
Product/Yield (%)
20 16 or 21
R
n
4
. Experimental
1
1
2
3
4
5
6
7
8
19a: CH
19b: CH
19c: CH
19d: PhCHvCHCH
19e: CH vCHCH(Ph)
vCHCH
vCHCH(CH
2
vCHCH
vCHCH(CH
CHvCHCH
2
2
2
2
2
2
1
1
1
20a: R ¼H
84 16
72 16
14 16
35 16
46 16
70 21 13
57 21 14
44 21
3
4
2
3
3
1
2
3
)
20b: R ¼CH
3
3
1
13
1
NMR spectra ( H and C) were recorded on a Varian
GEMINI 300 spectrometer in CDCl ; tetramethylsilane
3
2
20b: R ¼CH
1
20d: R ¼Ph
3
2
1
2
20d: R ¼Ph
(TMS) was used as an internal standard. IR spectra were
determined on a SHIMADZU FTIR-8200PC spectrometer
Mass spectra were determined on a JEOL Mstation 700
spectrometer. Silica gel (Wakogel 200 mesh) was used for
column chromatography. The analyses were carried out at
the Elemental Analysis Center of Kyoto University. Unless
otherwise noted, materials obtained from commercial
suppliers were used without further purification. Tetra-
hydrofuran (THF) was freshly distilled from sodium
benzophenone ketyl before use. Anhydrous manganese(II)
chloride purchased from Aldrich was heated at 1608C for
1
19f: CH
19g: CH
2
2
20f: R ¼H
1
2
3
)
20g: R ¼CH
3
1
19h: PhCHvCHCH
2
20h: R ¼Ph
8
reaction of 19c as the starting material. An attack of
manganate on an alkenic moiety might be impeded by the
methyl substituent in the case of 19c. (3) Whereas the
reaction of tetrahydropyranyl ethers with tributylmanganate
afforded a butylated byproduct 16 in only ,4% yield, the
reaction of tetrahydrofuranyl ethers gave slightly more a
butylated byproduct 21 in 8–14% yield.
2
h prior to use.
This transformation can be achieved by the use of a catalytic
amount of manganese chloride. For instance, an addition of
4
.1. General procedure for the reaction of dodec-6-yne
(1) with triallylmanganate
19a to a solution of butylmagnesium bromide (3.0 equiv.)
in THF containing HMPA (3.0 equiv.) and manganese
Dodec-6-yne (1, 166 mg, 1.0 mmol) was added to a THF
solution of triallylmanganate, generated from MnCl2
chloride catalyst (10 mol%) gave 20a in 80% yield after
1
2 h at 258C. 1-Methylprop-2-enyl tetrahydropyran-2-yl
ether (19b) also provided the corresponding 1,5-diol 20b in
6% yield. A byproduct, nonan-1,5-diol (16), was obtained
(
188 mg, 1.5 mmol), allylmagnesium chloride (1.51 M
THF solution, 3.0 mL, 4.5 mmol) and 1,3,5-trimethylben-
zene (0.28 mL, 2.0 mmol) at 08C under argon atmosphere.
The resulting mixture was stirred at 258C for 23 h. The reac-
tion was quenched with H O. Extractive workup followed
2
by purification gave (Z)-dodec-6-ene (2) in 80% yield.
6
in 3–8% yield along with the desired allylated products. In
the case of the reaction of the propargyl acetals a catalytic
reaction also proceeded smoothly. For instance, an addition
of 13c or 13f to a THF solution of butylmagnesium bromide
(
3.0 equiv.) in the presence of manganese chloride (10 mol%)
4
.1.1. [21212] Cyclization of deca-2,8-diyne (6) with the
provided homopropargyl alcohol 14c or 14f in good yield,
respectively, along with 16 (3%) or 21 (13%) (Scheme 9).
manganese–alkyne complex. In a flask equipped with a
balloon filled with argon, allylmagnesium chloride (1.51 M
THF solution, 3.0 mL, 4.5 mmol) and 1,3,5-trimethyl-
benzene (0.28 mL, 2.0 mmol) were added to a suspension
3. Conclusion
of MnCl (188 mg, 1.5 mmol, sonicated for 30 min) in THF
2
at 08C. After being stirred for 30 min, a solution of hex-3-
yne (4, 0.34 mL, 3.0 mmol) and deca-2,8-diyne (6, 0.13 g,
We found that treatment of dodec-6-yne with triallyl-
Scheme 9.

T. Nishikawa et al. / Tetrahedron 59 (2003) 9661–9668
9665
0
(neat) 2932, 2860, 1958, 1732, 1445, 1371, 1234, 1020,
1
.0 mmol) in THF (2 mL) was added and the resulting
4.2.4. 4,8-Diacetoxy-3-hexylocta-1,2-diene (15a ). IR
mixture was stirred at 258C for 16.5 h. The mixture was
poured into 1 M HCl and extracted with hexane (20 mL£3).
GC analysis indicated that tetrahdronaphthalene derivative
954 cm2 ; H NMR (CDCl ) d 0.88 (t, J¼6.9 Hz, 3H),
1
1
3
1.20–1.50 (m, 10H), 1.60–1.73 (m, 4H), 1.90–2.00 (m,
2H), 2.04 (s, 3H), 2.06 (s, 3H), 4.05 (t, J¼6.6 Hz, 2H),
5
was obtained in 44% yield.
1
3
4
.80–4.84 (m, 2H), 5.21 (t, J¼6.6 Hz, 1H); C NMR
4.1.2. 6,7-Diethyl-5,8-dimethyl-1,2,3,4-tetrahydronaph-
thalene (5). Mp 338C IR (neat) 3419, 2874, 1732, 1434,
(CDCl ) d 14.09, 20.96, 21.16, 21.99, 22.62, 27.42, 28.13,
3
28.28, 28.95, 31.67, 32.41, 64.18, 73.73, 77.86, 103.37,
170.23, 170.83, 205.74. Found: C, 69.65; H, 9.62%. Calcd
for C H O : C, 69.64; H, 9.74%.
020, 839 cm2 ; H NMR (CDCl ) d 1.15 (t, J¼7.6 Hz,
1 1
1
6
2
2
8
3
H), 1.75–1.82 (m, 4H), 2.18 (s, 6H), 2.61–2.63 (m, 4H),
.70 (q, J¼7.6 Hz, 4H); C NMR (CDCl ) d 14.92, 15.07,
1
8 30 4
1
3
3
2.86, 23.27, 28.37, 131.79, 133.48, 137.12. Found: C,
8.96; H, 11.31%. Calcd for C H : C, 88.82; H, 11.18%.
4.2.5. 8-Trimethylsilyloct-7-yn-1,5-diol (14b). IR (neat)
3267, 2869, 2176, 1423, 1430, 1011, 842 cm2 ; H NMR
1 1
1
6 24
(CDCl ) d 0.15 (s, 9H), 1.40–1.70 (m, 7H), 2.10 (bs, 1H),
3
4
.2. General procedure for the reaction of non-2-ynyl
2.35 (dd, J¼16.8, 6.9 Hz, 1H), 2.46 (dd, J¼16.8, 4.8 Hz,
1
3
tetrahydropyran-2-yl ether (13a) with
tributylmanganate
1H), 3.60–3.70 (m, 2H), 3.70–3.80 (m, 1H); C NMR
(CDCl ) d 0.11, 21.69, 28.84, 32.19, 35.59, 62.11, 69.67,
3
87.05, 103.43. This compound was converted to its diacetate
14b to obtain an analytically pure sample.
0
Manganese(II) chloride (125 mg, 1.0 mmol) was sonicated
in THF (10 mL) under argon atmosphere for 20 min.
Butylmagnesium bromide (1.03 M THF solution, 2.9 mL,
0
(neat) 2957, 2179, 1732, 1435, 1371, 1242, 1030, 845,
4.2.6. 4,8-Diacetoxy-l-trimethylsilyloct-l-yne (14b ). IR
3.0 mmol) and HMPA (0.52 mL, 3.0 mmol) were added to
the suspension of MnCl in THF at 08C. The mixture turned
into a clear brown solution and then was stirred for 20 min at
762 cm2 ; H NMR (CDCl ) d 0.14 (s, 9H), 1.30–1.50 (m,
1 1
2
3
2H), 1.58–1.78 (m, 4H), 2.04 (s, 3H), 2.06 (s, 3H), 2.45 (dd,
J¼17.1, 6.3 Hz, 1H), 2.51 (dd, J¼17.1, 6.0 Hz, 1H), 4.05 (t,
0
8C. A solution of 13a (0.22 g, 1.0 mmol) in THF (2 mL)
was added at 08C and the mixture was stirred at 258C for
3 h. The mixture was poured into water. Extractive workup
followed by purification gave tetradec-7-yn-1,5-diol (14a,
1
3
J¼6.9 Hz, 2H), 4.88–4.97 (m,1H); C NMR (CDCl ) d
3
2
20.07, 20.85, 20.97, 21.59, 25.30, 28.26, 32.64, 63.98,
71.39, 86.85, 101.84, 170.05, 170.65. Found: C, 60.48; H,
9.05%. Calcd for C H O Si: C, 60.37; H, 8.78%.
82 mg) in 36% yield, 6-hexylocta-6,7-dien-1,5-diol (15a,
52 mg) in 23% yield, and nonan-1,5-diol (16, 38 mg) in
24% yield.
1
5 26 4
4.2.7. 6-Trimethylsilylocta-6,7-dien-1,5-diol (15b). IR
1
(
1
neat) 3302, 2866, 1927, 1408, 1248, 1014, 812 cm2
;
H NMR (CDCl ) d 0.15 (s, 9H), 1.40–1.80 (m, 8H), 3.65
1
5
15
Compounds 20a and 20b are found in the literature.
3
(
t, J¼6.3 Hz, 2H), 4.14–4.20 (m, 1H), 4.49–4.59 (m, 2H);
C NMR (CDCl ) d 20.79, 21.86, 32.32, 37.36, 62.39,
3
1
3
4
1
0
6
2
3
2
6
.2.1. Tetradec-7-yn-1,5-diol (14a). IR (neat) 3306, 2858,
2
1 1
956, 1456, 1317, 1030, 916,842 cm ; H NMR (CDCl ) d
3
70.38, 71.63, 100.47, 206.97. This compound was converted
0
.89 (t, J¼6.9 Hz, 3H), 1.20–1.80 (m, 16H), 2.16 (ddt, J¼
.9, 4.8, 2.4 Hz, 2H), 2.27 (ddt, J¼16.5, 6.9, 2.4 Hz, 1H),
.40 (ddt, J¼16.5, 4.8, 2.4 Hz, IH), 3.66 (t, J¼6.6 Hz, 2H),
to its diacetate 15b to obtain an analytically pure sample.
4.2.8. 4,8-Diacetoxy-3-trimethylsilylocta-1,2-diene
(15b ). IR (neat) 2955, 1931, 1738, 1369, 1240, 1020, 842,
1
3
0
.63–3.74 (m, 1H); C NMR (CDCl ) d 14.03, 18.74,
3
758 cm2 ; H NMR (CDCl ) d 0.13 (s, 9H), 1.30–1.50 (m,
1 1
1.76, 22.53, 27.74, 28.54, 28.94, 31.30, 32.28, 35.58,
2.16, 70.05, 76.12, 82.88. This compound was converted to
3
2H), 1.55–1.75 (m, 4H), 2.04 (s, 3H), 2.05 (s, 3H), 4.04 (t,
13
0
its diacetate 14a to obtain an analytically pure sample.
J¼6.6 Hz, 2H), 4.50–4.51 (m, 2H), 5.29–5.35 (m, 1H);
C
NMR (CDCl ) d 20.84, 20.99, 21.26, 22.02, 28.28, 34.61,
3
0
860, 1740, 1435, 1371, 1240, 1030 cm
4
2
.2.2. 1,5-Diacetoxytetradec-7-yne (14a ). IR (neat) 2932,
2
64.21, 71.11, 72.87, 96.43, 169.98, 170.86, 208.83. Found: C,
60.31; H, 8.61%. Calcd for C H O Si: C, 60.37; H, 8.78%.
1
1
;
H NMR
1
5 26 4
(
1
CDCl ) d 0.89 (t, J¼6.9 Hz, 3H), 1.20–1.60 (m, 10H),
3
.65–1.80 (m, 4H), 2.04 (s, 3H), 2.06 (s, 3H), 2.10–2.16
4.2.9. 6-Methyl-8-trimethylsilyloct-7-yn-1,5-diol (14c,
60/40 diastereomeric mixture). IR (neat) 3346, 2878,
(
m, 2H), 2.40–2.43 (m, 2H), 4.05 (t, J¼6.6 Hz, 2H),
1
3
21
1
4
2
3
.85–4.93 (m, 1H); C NMR (CDCl ) d 14.05, 18.69,
3
2166, 1250, 1057, 989, 918, 843, 759 cm ; H NMR
(CDCl ) d 0.15 (s, 9H), 1.16 (d, J¼6.9 Hz, 1.20H), 1.20 (d,
0.93, 21.13, 21.18, 22.56, 24.26, 28.38, 28.47, 28.84,
1.32, 32.62, 64.14, 74.07, 74.96, 82.49, 170.26, 170.79.
3
J¼6.9 Hz, 1.80H), 1.38–1.50 (m, 6H), 1.76 (s, 2H), 2.50–
Found: C, 69.60; H, 9.87%. Calcd for C H O C, 69.64;
8 30 4
H, 9.74%.
2.65 (m, 1H), 3.38–3.43 (m, 0.60H), 3.52–3.57 (m, 0.40H),
3.66 (t, J¼6.3 Hz, 1.20H), 3.67 (t, J¼6.6 Hz, 0.80H);
1
1
3
C
NMR (CDCl ) d 0.26, 15.80, 17.46, 22.01, 22.10, 32.55,
3
4
2
.2.3. 6-Hexylocta-6,7-dien-1,5-diol (15a). IR (neat) 3306,
32.58, 33.18, 34.00, 34.31, 34.61, 62.74, 73.98, 74.08,
86.68, 87.61, 107.38, 108.58. Found: C, 62.87; H, 10.69%.
Calcd for C H O Si: C, 63.10; H, 10.59%.
858, 1956, 1456, 1030, 916, 843 cm2 ; H NMR (CDCl )
1
1
3
d 0.87 (t, J¼6.6 Hz, 3H), 1.20–1.70 (m, 16H), 1.90–2.10
1
2 24 2
(
m, 2H), 3.65 (t, J¼6.3 Hz, 2H), 4.00–4.05 (m, 1H), 4.83–
1
3
4
2
7
.87 (m, 2H); C NMR (CDCl ) d 14.09, 21.79, 22.63,
3
4.2.10. 6-Methyltetradec-7-yn-1,5-diol (14d, 23/77 dia-
stereomeric mixture). IR (neat) 3354, 2932, 2860, 1458,
7.61, 27.82, 29.09, 31.71, 32.33, 35.07, 62.31, 71.69,
8.21, 107.35, 204.13. This compound was converted to its
1436, 1377, 1056, 1004, 920 cm2 ; H NMR (CDCl ) d
1 1
3
0
diacetate 15a to obtain an analytically pure sample.
0.88 (t, J¼6.6 Hz, 3H), 1.12 (d, J¼6.9 Hz, 0.69H), 1.17 (d,

9666
T. Nishikawa et al. / Tetrahedron 59 (2003) 9661–9668
J¼6.6 Hz, 2.31H), 1.20–1.70 (m, 14H), 1.90–2.10 (m, 2H),
5.1 Hz, 0.33H), 4.06 (t, J¼6.3 Hz, 2H), 4.79–4.88 (m,
1
3
2
0
.12–2.19 (m, 2H), 2.40–2.54 (m, 1H), 3.34–3.40 (m,
.77H), 3.48–3.52 (m, 0.23H), 3.65 (t, J¼6.0 Hz, 2H);
0.67H), 4.88–4.95 (m, 0.33H); C NMR (CDCl ) d 0.09,
3
1
3
C
0.12, 16.32, 17.31, 21.25, 21.83, 24.57, 25.90, 28.02, 28.15,
31.09, 31.75, 62.29, 64.05, 74.07, 75.68, 86.66, 87.00,
107.23, 107.81, 170.81, 171.70. Found: C, 60.41; H, 8.56%.
Ca1cd for C H O Si: C, 60.34; H, 8.78%.
NMR (CDCl ) d 13.91, 16.30, 17.76, 18.64, 21.96, 22.02,
3
2
3
2.45, 28.44, 28.95, 31.23, 32.50, 33.03, 33.16, 33.24,
4.55, 62.52, 74.41, 80.45, 81.66, 82.68, 83.56. This
1
5 26 4
0
compound was converted to its diacetate 14d to obtain an
analytically pure sample.
4.2.16. 6-Methyloct-7-en-1,5-diol (20b, 55/45 diastereo-
meric mixture). IR (neat) 3333, 3078, 2870, 1639, 1418,
0
21 1
4
(
.2.11. 1,5-Diacetoxy-6-methyltetradec-7-yne (14d ). IR
1339, 1263, 999, 966 cm ; H NMR (CDCl ) d 1.02 (d,
3
neat) 2934, 2360, 1740, 1369, 1240, 1022, 970 cm21; 1H
J¼6.9 Hz, 1.65H), 1.03 (d, J¼6.9 Hz, 1.35H), 1.35–2.00
(m, 8H), 2.18–2.30 (m, 0.45H), 2.22–2.35 (m, 0.55H),
3.38–3.42 (m, 0.45H), 3.48–3.50 (m, 0.55H), 3.65 (t, J¼
NMR (CDCl ) d 0.88 (t, J¼6.6 Hz, 3H), 1.10 (d, J¼7.2 Hz,
3
3
2
4
H), 1.20–1.80 (m, 14H), 2.03 (s, 3H), 2.07 (s, 3H), 2.10–
.15 (m, 2H), 2.63–2.69 (m, 1H), 4.04 (t, J¼6.6 Hz, 2H),
1
3
6.0 Hz, 2H), 5.04–5.14 (m, 2H), 5.68–5.84 (m, 1H);
C
1
3
.81–4.87 (m, 1H); C NMR (CDCl ) d 13.91, 16.78,
3
NMR (CDCl ) d 14.26, 16.34, 21.94, 22.32, 32.57, 32.61,
13
1
3
1
7.60, 18.65, 20.80, 20.93, 22.11, 22.49, 28.39, 28.92,
0.19, 30.96, 31.28, 64.18, 75.53, 80.24, 82.35, 170.61,
70.92. Found: C, 70.24; H, 10.11%. Calcd for C H O :
33.58, 33.71, 43.59, 44.25, 62.67, 74.53, 74.59, 115.20,
116.27, 140.18, 140.82. Found: C, 68.20; H, 11.69%. Calcd
for C H O : C, 68.31; H, 11.47%.
19
32
4
9 18 2
C, 70.33; H, 9.94%.
4.2.17. 6-Phenyloct-7-en-1,5-diol (20d, 74/26 diastereo-
meric mixture). IR (neat) 3352, 2937, 2866, 1638, 1601,
1493, 1452, 1001, 918, 759, 702 cm ; H NMR (CDCl ) d
3
4
3
.2.12. 6-Vinyltetradec-7-yn-1,5-diol (14e). IR (neat)
1
350, 2931, 2860, 1640, 1402, 1329, 920 cm2 ; H NMR
1
21 1
(
2
3
CDCl ) d 0.89 (t, J¼6.9 Hz, 3H), 1.20–1.70 (m, 16H),
1.25–1.80 (m, 8H), 3.24 (dd, J¼9.0, 9.0 Hz, 0.74H), 3.31
(dd, J¼8.7, 8.7 Hz, 0.26H), 3.59 (t, J¼6.0 Hz, 1.48H), 3.64
(t, J¼6.0 Hz, 0.52H), 3.77–3.83 (m, 0.74H), 3.83–3.92 (m,
0.26H), 5.10–5.16 (m, 0.52H), 5.19–5.25 (m, 1.48H), 6.04
(ddd, J¼17.4, 9.9, 8.7 Hz, 0.74H), 6.12 (ddd, J¼16.8, 10.5,
3
.22 (dt, J¼6.9, 2.4 Hz, 2H), 3.15 (m, 1H), 3.55 (m, 1H),
.70 (m, 2H), 5.21 (dt, J¼10.2, 1.5 Hz, IH), 5.39 (dt,
J¼17.1, 1.5 Hz, 1H), 5.81 (ddd, J¼17.1, 10.2, 6.3 Hz,
1
3
1
2
7
H); C NMR (CDCl ) d 14.12, 18.85, 22.08, 22.61,
3
1
3
8.61, 28.99, 31.35, 32.56, 34.30, 43.46, 62.70, 73.23,
6.44, 86.52, 117.26, 135.29. This compound was con-
9.0 Hz, 0.26H), 7.10–7.35 (m, 5H); C NMR (CDCl ) d
3
21.89, 32.45, 32.56, 33.92, 34.01, 57.40, 57.50, 62.65,
73.81, 74.11, 116.73, 117.86, 126.58, 126.80, 127.84,
128.35, 128.60, 128.68, 138.18, 138.52, 140.73, 141.40.
Found: C, 76.28; H, 9.04%. Calcd for C H O : C, 76.33;
0
verted to its diacetate 14e to obtain an analytically pure
sample.
1
4 20 2
0
4
(
.2.13. 4,8-Diacetoxy-3-(oct-l-ynyl)oct-1-ene (14e ). IR
H, 9.15%.
neat) 2932, 2860, 1744, 1371, 1238, 1026, 924 cm21; 1H
NMR (CDCl ) d 0.88 (t, J¼6.9 Hz, 3H), 1.20–1.80 (m,
4.2.18. Hept-6-en-1,5-diol (20f). IR (neat) 3308, 2872,
3
1641, 1435, 1346, 1009, 914 cm2 ; H NMR (CDCl ) d
1 1
1
4H), 2.03 (s, 3H), 2.05 (s, 3H), 2.20 (dt, J¼7.2, 2.4 Hz,
3
2
H), 3.30–3.36 (m, 1H), 4.04 (t, J¼6.6 Hz, 2H), 4.96 (dt,
1.46–1.54 (m, 1H), 1.60–1.80 (m, 3H), 2.15–2.32 (m, 2H),
2.60–3.20 (m, 2H), 3.60–3.80 (m, 3H), 5.10–5.15 (m, 2H),
J¼8.7, 4.8 Hz, 1H), 5.15–5.21 (m, 1H), 5.34–5.42 (m, 1H),
1
3
13
5
2
3
1
.60–5.81 (m, 1H); C NMR (CDCl ) d 14.14, 18.85,
3
5.76–5.91 (m, 1H); C NMR (CDCl ) d 28.98, 33.66,
3
1.06, 21.16, 22.23, 22.65, 28.41, 28.56, 28.96, 30.93,
1.39, 40.16, 64.26, 74.49, 76.16, 85.70, 117.41, 133.85,
70.45, 170.95. Found: C, 71.47; H, 9.66%. Calcd for
41.95, 62.61, 70.72, 117.64, 134.82. Found: C, 76.28; H,
9.04%. Calcd for C H O : C, 76.33; H, 9.15% This
1
4 20 2
0
compound was converted to its diacetate 20f to obtain an
analytically pure sample.
C H O : C, 71.39; H, 9.59%.
20 32 4
0
4
6
2
.2.14. 5-Methyl-7-trimethylsilylhept-6-yn-1,4-diol (14f,
7/33 diastereomeric mixture). IR (neat) 3333, 2878,
166, 1452, 1249, 1053, 842, 759 cm ; H NMR (CDCl )
3
4.2.19. 4,7-Diacetoxyhept-1-ene (20f ). IR (neat) 3080,
2958, 1738, 1643, 1439, 1371, 1238, 1024, 997 cm2 ; H
1 1
2
1 1
NMR (CDCl ) d 1.60–1.80 (m, 4H), 2.02 (s, 3H), 2.03 (s,
3
d 0.14 (s, 6H), 0.15 (s, 3H), 1.16 (d, J¼6.9 Hz, 0.99H), 1.17
3H), 2.27–2.33 (m, 2H), 4.04 (t, J¼6.3 Hz, 2H), 4.88–4.96
1
3
(
d, J¼6.9 Hz, 2.01H), 1.50–1.80 (m, 4H), 2.10–2.40 (bs,
(m, 1H), 5.03–5.10 (m, 2H), 5.65–5.80 (m, 1H); C NMR
(CDCl ) d 20.83, 21.05, 24.62, 30.03, 38.57, 64.05, 72.73,
2
5
0
1
6
H), 2.56 (dq, J¼6.9, 5.4 Hz, 0.33H), 2.59 (dq, J¼6.9,
3
.4 Hz, 0.67H), 3.41–3.48 (m, 0.33H), 3.54–3.60 (m,
.67H), 3.65–3.76 (m, 2H); C NMR (CDCl ) d 0.26,
117.77, 133.41, 170.55, 170.92. Found: C, 61.41; H, 8.46%.
Calcd for C H O : C, 61.66; H, 8.47%.
1
3
3
11 18 4
5.94, 17.37, 29.36, 29.44, 30.88, 31.73, 34.11, 34.51,
2.92, 62.99, 74.17, 74.25, 86.78, 107.34, 108.49. This
4.2.20. 5-Methylhept-6-en-1,4-diol (20g, 58/42 diastereo-
meric mixture). IR (neat) 3305, 2874, 1639, 1417, 999,
0
compound was converted to its diacetate 14f to obtain an
analytically pure sample.
1 1
914 cm2 ; H NMR (CDCl ) d 1.03 (d, J¼6.6 Hz, 1.26H),
3
1
.04 (d, J¼6.9 Hz, 1. 74H), 1.20–1.80 (m, 4H), 2.20–2.40
4.2.15. 4,7-Diacetoxy-3-methyl-l-trimethylsilylhept-1-
yne (14f , 67/33 diastereomeric mixture). IR (neat) 2990,
(m, 3H), 3.39–3.45 (m, 0.42H), 3.48–3.54 (m, 0.58H),
3.60–3.73 (m, 2H), 5.05–5.15 (m, 2H), 5.68–5.85 (m, 1H);
0
169, 1738, 1371, 1236, 1024, 844, 761 cm ; H NMR
2
1
1
13
2
C NMR (CDCl ) d 14.88, 16.12, 29.26, 29.47, 31.05,
3
(
CDCl ) d 0.14 (s, 9H), 1.14 (d, J¼7.2 Hz, 0.99H), 1.15 (d,
31.24, 43.86, 44.16, 62.64, 74.67, 74.82, 114.88, 115.82,
140.22, 140.83. Found: C, 66.37; H, 11.09%. Calcd for
C H O : C, 66.63; H, 11.18%.
3
J¼7.2 Hz, 2.01H), 1.60–1.90 (m, 4H), 2.04 (s, 3H), 2.07 (s,
3
H), 2.68 (dq, J¼7.2, 0.3 Hz, 0.67H), 2.74 (dq, J¼7.2,
8
16 2

T. Nishikawa et al. / Tetrahedron 59 (2003) 9661–9668
9667
Scheme 10.
4.2.21. 5-Phenylhept-6-en-1,4-diol (20h, 56/44 diastereo-
meric mixture). IR (neat) 3354, 2874, 1637, 1001, 918,
Yamada, M.; Odaka, H.; Utimoto, K.; Fujii, T.; Furukawa, I.
Chem. Lett. 1995, 315.
2
1 1
7
2
8
0
2
7
3
1
1
59 cm ; H NMR (CDCl ) d 1.30–1.90 (m, 4H), 1.95 (bs,
3
5. Treatment of dodec-6-yne (1) with tributylmanganate also
gave (Z)-dodec-6-ene (2) in quantitative yield after hydrolysis.
When D O was added before quenching the reaction, however,
H), 3.25 (dd, J¼8.6, 8.6 Hz, 0.56H), 3.32 (dd, J¼8.6,
.6 Hz, 0.44H), 3.54–3.65 (m, 1.12H), 3.60–3.72 (m,
.88H), 3.83 (dt, J¼6.0, 3.0 Hz, 0.56H), 3.90 (dt, J¼9.3,
.7 Hz, 0.44H), 5.10–5.25 (m, 2H), 5.97–6.18 (m, 1H),
2
corresponding dideuterated alkene was not obtained in this
case.
1
3
.18–7.38 (m, 5H); C NMR (CDCl ) d 29.19, 31.52,
3
6. A couple of alkyne complexes of cyclopentadienylcarbonyl-
manganese have been reported Coughlan, S. M.; Yang, G. K.
J. Organomet. Chem. 1993, 450, 151. (b) Alt, H. G.;
Engelhardt, H. E.; Zhvanko, O. S.; Ivanov, L. L.; Batsanov,
A. S.; Struchkov, Y. T. J. Organomet. Chem. 1986, 302, 235.
1.56, 57.31, 62.68, 73.95, 74.17, 116.66, 117.60, 126.50,
26.69, 127.84, 128.29, 128.53, 128.58, 138.24, 138.33,
40.82, 141.40. This compound was converted to its
0
diacetate 20h to obtain an analytically pure sample.
7
. [2þ2þ2] Cyclization of 1,7-diyne with tantalum–alkyne
complex has been reported Takai, K.; Yamada, M.; Utimoto,
K. Chem. Lett. 1995, 851.
0
stereomeric mixture). IR (neat) 3062, 1738, 1639, 1494,
4
.2.22. 4,7-Diacetoxy-3-phenylhept-1-ene (20h , 57/43 dia-
2
1 1
1
1
1
3
0
369, 1238, 1026, 923 cm ; H NMR (CDCl ) d 1.40–
3
8. The Mn(0) species might contribute to the formation of
hexaethylbenzene, the cyclotrimerization product of hex-3-
yne. In the reaction without an addition of 1,7-diyne, only a
trace amount of cyclotrimerization product was produced.
.80 (m, 4H), 1.85 (s, 1.29H), 1.97 (s, 1.71H), 2.02 (s,
.29H), 2.04 (s, 1.71H), 3.39 (dd, J¼8.4, 8.4 Hz, 0.57H),
.50 (dd, J¼8.4, 8.4 Hz, 0.43H), 3.96 (m, 1.14H), 4.03 (m,
.86H), 5.05–5.18 (m, 2H), 5.22–5.30 (m, 1H), 5.95–6.08
9
. Normant, J.-F.; Cahiez, G. Organomanganous Reagent in
Modern Synthetic Methods; Schefford, R., Ed.; Otto Salle/
GmbH: Frankfurt am Main, 1983; Vol. 3.
1
3
(
m, 1H) 7.18–7.36 (m, 5H); C NMR (CDCl ) d 20.88,
3
2
5
1
1
0.95, 21.00, 21.20, 24.57, 24.66, 28.65, 28.71, 54.56,
5.15, 63.88, 64.01, 75.15, 116.80, 117.27, 126.62, 126.80,
27.89, 128.25, 128.64, 137.23, 137.78, 140.15, 140.47,
70.30, 170.53, 170.78, 170.84. Found: C, 70.55; H, 7.78%.
1
0. Treatment of methyl propargyl ether 10 with triallylmanganate
gave a complex mixture.
1
1. Hexadecane could be detected in only 20% yield in the
Calcd for C H O : C, 70.32; H, 7.64%.
17 22 4
3
reaction of 19a with (n-Octyl) MnMgBr. Thus, stepwise
elimination of the butyl radicals, which would collapse to
butane and butene, could be an alternative route to B.
Acknowledgements
12. Recombination of manganese species and aldehyde E
proceeds intermoleculary. Thus, treatment of a mixture of
19a (0.5 mmol) and 19g (0.5 mmol) with tributylmanganate
Financial support by Grant-in-Aids for Scientific from the
Ministry of Education, Culture, Sports, Science, and
Technology, Japan, is acknowledged. T. N. thanks the
JSPS Research Fellowship for Young Scientists.
(
1.0 mmol) provided the intermolecular addition products 20b
and 20f in addition to the intramolecular addition products 20a
and 20g. The ratio of these compounds was 20a/20b/20f/
20g¼42:24:14:20 (Scheme 10).
3. Allylmanganese reagents from Mn(0) and allylic bromide:
1
Hiyama, T.; Obayashi, M.; Nakamura, A. Organometallics
References
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982, 1, 1249–1251. (b) Kim, S.-H.; Hanson, M. V.; Rieke,
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/Me SiCl: Takai, K.; Ueda, T.;
. (a) Takahashi, T.; Swanson, D. R.; Negishi, E. Chem. Lett.
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. (a) Kataoka, Y.; Takai, K.; Oshima, K.; Utimoto, K.
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bromide: Hojo, M.; Harada, H.; Ito, H.; Hosomi, A. J. Chem.
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allylic stannane: Tang, J.; Yorimitsu, H.; Kakiya, H.; Inoue,
MnLi/allyl
3
. (a) Takai, K.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1990,
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Utimoto, K. J. Org. Chem. 1992, 57, 1973. (c) Takai, K.;
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019–9022.
4. Triethylmanganate (Et
tributylmanganate. However, trimethylmanganate derived
from MnCl and MeMgI was not effective for the transforma-
tion. For instance, treatment of 19f with Me MnMgI gave a
methylated product (1,4-pentanediol) in only 13% in addition
to unidentified complex products. The use of n-Bu MnLi
9
3
1
3
MnMgBr) was also effective as
derived from n-BuLi instead of n-BuMgBr afforded 20f in
only 31% yield along with 21 (7%).
2
15. Einhorn, C.; Luche, J. L. J. Organomet. Chem. 1987, 322,
177–182.
3