Efficient preparation of polyunsaturated and functionalized acetylenic ketones from alkynylmanganese bromides

Article abstract of DOI:10.1055/s-0030-1258329

α, β-Acetylenic ketones are efficiently prepared, under mild conditions, by reacting alkynylmanganese compounds with acyl chlorides. The procedure is especially useful for preparing polyfunctionalized and polyunsaturated α, β-acetylenic ketones.

Full text of DOI:10.1055/s-0030-1258329

PAPER
4213
Efficient Preparation of Polyunsaturated and Functionalized Acetylenic
Ketones from Alkynylmanganese Bromides
P
olyunsaturated an
é
d
F
unction
r
alized A
a
cetylenic
K
r
etones d Cahiez,* Olivier Gager, Alban Moyeux, Blandine Laboue-Bertrand
SOSCOM, Unité CNRS - Université de Paris13 FRE3043, 74 Rue Marcel Cachin, 93017 Bobigny, France
Fax +33(1)48387363; E-mail: gerard.cahiez@univ-paris13.fr
Received 14 September 2010; revised 27 September 2010
Equation 1). We have previously shown that this draw-
back can be avoided by using 1-hexynylmanganese bro-
mide (1b) instead of 1a.9
Abstract: a,b-Acetylenic ketones are efficiently prepared, under
mild conditions, by reacting alkynylmanganese compounds with
acyl chlorides. The procedure is especially useful for preparing
polyfunctionalized and polyunsaturated a,b-acetylenic ketones.
Key words: organomanganese, acylation, acetylenic ketones, acyl
chlorides
MeCH=CHCOCl
Bu
MnX
Bu
2
Et2O, r.t., 2 h
O
1
1a: X = I: 0%
1b: X = Br: 87%
Acetylenic ketones are very useful synthetic intermedi-
ates and they are also present as subunits in several natural
or bioactive products.1 The main routes used to prepare
these compounds are the oxidation of allylic alcohols or
propargylic methylene groups,2 and the acylation of vari-
ous alkynylmetal derivatives.3 The latter route has been
extensively used, with the most efficient applications in-
volving the acylation of alkynylsilanes,4 owing to its large
scope. The direct acylation of terminal alkynes in the pres-
ence of a strong base (Et3N or i-Pr2EtN) and a metal salt5
(Cu, Zn, Pd) has also been recently developed, although it
should be noted that only non-enolizable ketones can be
obtained by the last procedure. Acylation of organoman-
ganese reagents is a very efficient and simple method that
can be used to prepare a vast array of simple and function-
alized ketones.6 The reaction was first developed by using
organomanganese iodides in diethyl ether, it takes place
under mild conditions and generally leads to high yields.7
Later, we reported that organomanganese chlorides, pre-
pared from manganese chloride in tetrahydrofuran (THF),
can also be used sucessfully.8 This is a clear improvement
for preparative chemistry since, in contrast to manganese
iodide, manganese chloride is a very common and inex-
pensive commercial material. In THF, aliphatic, vinylic,
allylic, and aromatic organomanganese chlorides readily
react with carboxylic acid chlorides, which are the most
common acylating agents. However, in this solvent, alky-
nylmanganese halides react sluggishly and lead to poor
yields. In fact, in this case, it is much more efficient to per-
form the acylation in diethyl ether and many simple acet-
ylenic ketones were thus prepared in good yields from
alkynylmanganese iodides.7 Unfortunately, we have ob-
served that the presence of iodides in the reaction mixture
is sometimes very detrimental, for instance in preparing
polyunsaturated acetylenic ketones. Thus, ketone 2 can-
not be obtained from 1-hexynylmanganese iodide (1a;
Equation 1 Acylation of hexynylmanganese iodide 1a and bromide
1b with crotyl chloride
Moreover, it is much more advantageous to use manga-
nese bromide, which is less expensive and more readily
available than manganese iodide. Until now, only one ex-
ample of acylation of alkynylmanganese bromides by car-
boxylic acid chlorides has been described.9 Herein, we
report that such a reaction is a very general way to effi-
ciently prepare various polyunsaturated and highly func-
tionalized acetylenic ketones.
Alkyl- and arylethynylmanganese bromides are easily and
quantitatively prepared in diethyl ether from alkyl- and
arylacetylenes 3 by metallation with n-butyllithium (Bu-
Li·LiBr prepared in diethyl ether) then transmetallation
with manganese bromide (Table 1). The presence of lithi-
um bromide in the reaction mixture is very important
since it allows the MnBr2 to be solubilized by forming the
ate-complex MnBr2·LiBr. Further acylation with acyl
chlorides leads to conjugated alkynones 4 in good yields.
It should be noted that functionalized (Table 1, entries 6
and 7) and conjugated ethylenic or dienic (entries 4 and 5)
carboxylic acid chlorides were successfully employed.
Alkynylmanganese bromides can also be prepared from
the corresponding Grignard reagents. However, in this
case it is then necessary to use the soluble ate-complex
MnBr2·LiBr to perform the transmetallation (Scheme 1).
It should be noted that the metallation of 1-alkyne with
Grignard reagents is less efficient than with organolithium
Et2O
MnBr2⋅LiBr
MnBr2
+ LiBr
r.t., 2 h
soluble
MgBr
R
30 min
R
MnBr
SYNTHESIS 2010, No. 24, pp 4213–4220
Advanced online publication: 15.11.2010
DOI: 10.1055/s-0030-1258329; Art ID: Z23210SS
x
x.
x
x
.
2
0
1
0
Scheme 1 Preparation of alkynylmanganese bromides via the solu-
ble ate-complex MnBr2·LiBr
© Georg Thieme Verlag Stuttgart · New York

4214
G. Cahiez et al.
PAPER
Table 2 Preparation of Functionalized Acetylenic Ketones 6
Table 1 Preparation of Akynyl Ketones from Alkynylmanganese
Bromides
1) BuLi or MeLi,
Et2O, –30 °C to r.t., 1 h
2) MnBr2, r.t., 45 min
1) BuLi or MeLi,
Et2O, –30 °C to r.t., 1 h
2) MnBr2, r.t., 45 min
R1
H
R1
MnBr
RFg
H
RFg
MnBr
5
3
R2
O
R
O
R2COCl
r.t., 2 h
RCOCl
r.t., 2 h
R1
6
RFg
4
Fg = MeO, BuS, PhS, Cl, and Br.
Entry Alkynyl ketone 4
Yield (%)a
95
Entry Alkynyl ketone 6
Yield (%)a
80
O
O
1
4a
MeO
1
2
6a
6b
O
2
4b
90
86
50
MeO
MeO
O
O
O
O
3
4c
3
4
5
6
7
6c
6d
6e
6f
49
73
41
66
73
Cl
Cl
MeO
MeO
4
5
4d
4e
97
79
O
O
COOMe
O
Bu
BuS
PhS
O
6
7
4f
83
80
COOMe
Et
6g
O
O
O
4g
8
6h
69
Me3Si
PhS
O
O
8
4h
76
O
9
10
11
6i
63
71
82
PhS
Cl
a All products were isolated by distillation.
Bu
6j
6k
compounds. Thus, the organolithium route is generally
preferred.
O
O
Various alkoxy-, alkylthio-, chloro- and bromoalkynyl-
manganese compounds 6 were successfully prepared
from the corresponding terminal alkynes 5. They are sta-
ble at room temperature and react chemoselectively with
various functionalized carboxylic acid chlorides to give,
in satisfactory yields, a vast array of polyfunctionalyzed
alkynyl ketones having functionality on both sides of the
keto group (Table 2).
Cl
12
6l
78
Cl
Cl
O
Ph
13
14
6m
6n
56
68
Acetylenic ketones, for example, 1-undecyn-8-one, can-
not be lithiated, however, it is possible to use the corre-
sponding ketal 7. After a one-pot sequence involving
lithiation–transmetallation–acylation, the expected acetyl-
enic ketone 8 was obtained in satisfactory yield
(Equation 2).
O
O
Cl
Cl
Synthesis 2010, No. 24, 4213–4220 © Thieme Stuttgart · New York

PAPER
Polyunsaturated and Functionalized Acetylenic Ketones
4215
Table 2 Preparation of Functionalized Acetylenic Ketones 6
(continued)
Table 3 Preparation of Acetylenic Ketones from Propargylaldehyde
Diethyacetal 9
1) BuLi or MeLi,
1) BuLi, Et2O
Et2O, –30 °C to r.t., 1 h
2) MnBr2, r.t., 45 min
–70 °C to –30 °C, 1 h
2) MnBr2
RFg
H
RFg
MnBr
–30 °C to r.t., 1 h
(EtO)2CH
H
(EtO)2CH
MnBr
5
9
R
O
RCOCl
r.t., 2 h
6
RFg
R
O
RCOCl
r.t., 2 h
(EtO)2CH
Fg = MeO, BuS, PhS, Cl, and Br.
10
Entry Alkynyl ketone 6
Yield (%)a
61
Entry Alkynyl ketones 10
Yield (%)a
80
Br
EtO
Bu
15
6o
1
2
10a
10b
Cl
Cl
Cl
O
O
EtO
EtO
EtO
EtO
EtO
O
O
O
16
17
6p
6q
45
73
COOMe
75
87
COOMe
O
3
4
10c
10d
Bu
18
19
20
6r
6s
6t
79
77
53
Br
O
78
EtO
Br
Br
O
O
EtO
EtO
O
O
O
O
O
5
6
7
8
10e
10f
10g
10h
53
71
71
65
Cl
Cl
EtO
EtO
a All products were isolated by distillation.
Cl
EtO
EtO
1) BuLi, Et2O
–70 °C to –30 °C, 1 h
2) MnBr2
7
COOMe
8
O
O
O
O
–30 °C to r.t., 1 h
EtO
EtO
C
C
Pr
(CH2)5
C
CH
Pr
(CH2)5
61 %
C CCOPr
3) PrCOCl, r.t., 1.5 h
COOMe
O
EtO
Equation 2 Preparation of akynyl ketones 8 from the ketal of 1-un-
decyn-8-one 7
H
O
9
10i
82
EtO
EtO
Similarly, the propargylaldehyde diethylacetal 9 was effi-
ciently converted into a range of polyfunctionnalized
acetylenic ketones 10 (Table 3).
O
a All products were isolated by distillation.
Acetylenic alcohols 11 can be protected before metalla-
tion, for instance as a methyl ether (Table 2, entries 1–5).
However, it is also possible to convert them directly into
the corresponding alkynylmanganese bromide alcoholate
12 (Table 4). The acylation of 12 readily takes place but
the alcoholate group also reacts to give the acetylenic keto
esters 13.
1) BuLi (2 equiv), Et2O,
–30 °C to r.t., 30 min
2) MnBr2 (2 equiv), r.t., 1 h
HO
BrMnO
MnBr
14
H
PrCOCl (2 equiv)
r.t., 4 h
15
In the same way, 1-ethynylcyclohexanol (14) can be effi-
ciently converted into the acetylenic keto ester 15
(Scheme 2).
PrCOO
Pr
75%
O
In conclusion, the acylation of alkynylmanganese bro-
mides is a very efficient procedure that can be used to pre-
pare various highly polyunsaturated or polyfunctionalized
conjugated acetylenic ketones. The reaction can be easily
Scheme 2 Preparation of a keto ester from 1-ethynylcyclohexan-1-
ol
Synthesis 2010, No. 24, 4213–4220 © Thieme Stuttgart · New York

4216
G. Cahiez et al.
PAPER
Table 4 Preparation of Acetylenic Keto Esters 13
All reactions were performed under a nitrogen atmosphere. Prod-
ucts were purified by distillation, purity >95% (GC analysis). All
products gave satisfactory analyses, 1H and 13C NMR (Jeol MH100,
Jeol FX90Q and Jeol GSX400 spectrometers), IR (Perkin-Elmer 457
spectrometer) and GC (capillary column OV1, 25 m × 0.53 mm, 0.5
mm film thickness).
1) BuLi (2 equiv), Et2O,
–30 °C to r.t., 30 min
2) MnBr2 (2 equiv), r.t., 1 h
HO
( )n
BrMnO
( )n
H
MnBr
11
12
RCOCl (2 equiv)
r.t., 4 h
RCOO
R
O
MnBr2
( )n
Anhydrous MnBr2 can be obtained from commercial sources. How-
ever, in a very convenient procedure, the material can be prepared
according to the following procedure:
13
Entry Alkynyl ketone 13
Yield (%)a
77
To a suspension of manganese powder (20–50 mesh; 2 mol, 110 g)
in anhydrous EtOAc (ethanol free; 1.5 L) was added dropwise un-
der vigorous stirring, bromine (2.02 mol, 323.2 g). The reaction was
exothermic and the temperature of the reaction mixture was kept be-
low 35 °C with an ice bath. Stirring was then continued for 3 h at
30 °C. The precipitate was separated by filtration and washed sev-
eral times with EtOAc until a colorless filtrate was obtained, then
with Et2O (200 mL). The solid was then dried under vacuo (0.01
torr) under progressive heating until 200 °C. It is then finely
crushed and dried again under vacuo (200 °C, 6 h). The yield was
generally better than 90% (>390 g). The product is hygroscopic and
must be stored in the absence of moisture.
PrCOO
Pr
1
2
3
13a
13b
13c
O
i-PrCOO
i-Pr
76
70
O
t-BuCOO
t-Bu
O
Me2C=CHCOO
4
13d
78
Preparation of RC≡CMnBr from RC≡CH; General Procedure
To a solution of RC≡CH (50 mmol) in Et2O (40 mL), was added
BuLi (1.2 M in Et2O, 52 mmol), keeping the temperature between
–50 to –20 °C (see Table 5). Stirring was continued at this temper-
ature for 10 min, then the reaction mixture was allowed to warm to
r.t. and stirred for 30 min to 1.5 h (see Table 5). After addition of
MnBr2 (55 mmol) at –30 °C, stirring was continued for 1–4 h (see
Table 5) at r.t. The alkynylmanganese bromide RC≡CMnBr was
generally obtained as a beige or brownish suspension.
O
Et
5
6
13e
13f
52
71
EtCOO
PrCOO
O
Pr
O
a All products were isolated by distillation.
Acylation of RC≡CMnBr; General Procedure
performed on a large scale because the simple and func-
tionalized alkynylmanganeses are stable at room temper-
ature and smoothly react with carboxylic acid chlorides
without troublesome exothermic effects.
To a suspension of RC≡CMnBr (50 mmol) in Et2O (80 mL) was
added R¢COCl (50 mmol) dropwise between –20 and –30 °C. The
reaction mixture was then allowed to warm to r.t. and stirred for 1–
4 h (the progress of the reaction was monitored by GC analysis, see
Table 5) then quenched by addition of a 1 N HCl (100 mL) at –10 °C.
After extraction with petroleum ether (2 × 50 mL) the combined or-
ganic layers were dried with MgSO4 and the solvents were removed
under vacuo. The alkynyl ketones were isolated by distillation
(Table 6).
Et2O was distilled from sodium/benzophenone under a nitrogen at-
mosphere before use. Manganese powder (Mn 99%, 20–50 mesh)
was purchased from STREM.
Table 5 Reaction Conditions (General Procedure)
RC≡CH to
RC≡CCOR¢
Metallation by BuLi
Temp (°C)
Transmetallation Li/Mn
Acylation
Temp (°C)
Time (min)
Temp (°C)
Time (h)
Time (h)
2
3 to 4
–30 then r.t.
–70 then r.t.
–70 then r.t.
–80 then –30
–30 then r.t.
–60 then –30
–60 then –30
–50 then r.t.
–50 then r.t.
60
45
45
90
60
60
60
30
30
0 then r.t.
1
–20 then r.t.
–30 then r.t.
–30 then r.t.
–30 then r.t.
–30 then r.t.
–30 then r.t.
–30 then r.t.
–30 then r.t.
–30 then r.t.
5 to 6a–e
5 to 6f–i
5 to 6j–q
5 to 6r–t
7 to 8
–10 then r.t.
–10 then r.t.
–30 then r.t.
–30 then r.t.
–50 then r.t.
–50 then r.t.
–10 then r.t.
–10 then r.t.
4
1–3
1–3
1–4
1–4
2–3
2–3
4
2
2
2
1–3a
1–3
2
9 to 10
11 to 12
14 to 15
2
4
a Until a solution was obtained.
Synthesis 2010, No. 24, 4213–4220 © Thieme Stuttgart · New York

PAPER
Polyunsaturated and Functionalized Acetylenic Ketones
13C NMR (ppm)d
4217
Table 6 Physical and Spectral Data of Acetylenic Ketones
IR (cm–1)
C=O
T
Product Bp (°C/torr)
nD
C≡C
C=C
1630
C-O-C
2
55/0.1
1.4830a
1.4480a
1.4819a
1.5430a
1650
1670
1675
1640
2200
178.30, 148.90, 134.0, 94.25, 79.10, 30.00,
22.10, 18.65, 18.30, 13.55
4a
4b
4c
42/0.01
58/0.01
60/0.01
2210
2200
2200
187.80, 93.60, 81.20, 45.40, 26.40, 22.30,
21.55, 20.95, 13.90, 13.50
190.70, 94.20, 88.45, 52.30, 29.00, 28.50
(2C), 26.10, 25.60 (2C), 21.60, 13.55
1450, 1580
177.95, 136.95, 133.85, 129.45 (2C),
128.50 (2C), 96.65, 79.75, 29.88, 22.10,
18.85, 13.55
4d
4e
62/0.05
60/0.01
1.4940a
1.5380a
1650
1625
2210
2210
1615
1580
176.40, 156.90, 126.25, 92.15, 83.46,
30.05, 27.70, 22.10, 20.90, 18.70, 13.60
178.30, 148.15, 141.70, 130.20, 130.05,
93.95, 79.40, 30.00, 22.05, 18.90, 18.65,
13.53
4f
88–89/0.05 1.4640a
1670, 1735
1675
2210
2200
2240
2220
2220
2220
2200
2205
186.60, 173.15, 94.10, 80.90, 51.40, 44.50,
32.80, 29.95, 22.10, 19.30, 18.60, 13.55
4g
4h
6a
6b
6c
6d
6e
53/0.01
70/0.05
65/11
1.5762a
1.4473c
1.4975c
1.5440
1.4798
1.4727
1.4598
1490, 1175
1615
184.15, 133.00 (2C), 130.75, 128.65 (2C),
119.90, 90.05, 88.30, 32.60
1680
187.45, 102.30, 97.10, 45.30, 31.70, 29.00
(2C), 24.05, 22.65, 14.05, –0.75 (3C)
1655
1110, 1150
1110, 1255
1110
175.50, 158.65, 125.65, 87.70, 85.85,
59.60, 57.85, 27.75, 21.10
100/0.3
70/0.1
1630
177.60, 149.10, 142.65, 130.10, 129.45,
87.70, 83.85, 59.60, 57.90, 18.90
1680
185.65, 88.15, 85.15, 59.50, 58.00, 43.95,
42.35, 26.60
70/0.01
110/0.01
1675
1100
186.80, 87.70, 85.30, 59.50, 57.90, 45.10,
44.70, 32.35, 26.20, 23.15
1655, 1730
1105
186.95, 173.90, 87.50, 85.40, 59.50, 57.85,
51.35, 45.25, 33.90, 28.80, 28.60, 24.75,
23.75
6f
95/0.01
90/0.01
1.4960b
1.5740b
1.4568
1675
1675
1670
2220
2220
2210
1740 (C-S-C) 187.45, 88.60, 81.90, 45.30, 31.70, 31.10,
26.15, 22.15, 21.95, 19.35, 13.80, 13.70
6g
6h
1480
187.65, 134.05, 130.85 (2C), 129.10 (2C),
127.50, 88.15, 82.15, 38.70, 22.85, 7.80
115/0.01
1435, 1480
191.55, 135.80, 129.50 (2C), 128.90 (2C),
126.20, 93.25, 80.35, 42.90, 32.60, 27.25,
17.90 (2C), 17.80
6i
150/0.01
1.5749
1640
2210
1435, 1475
178.10, 148.95, 135.80, 133.85, 129.45
(2C), 128.90 (2C), 126.15, 92.70, 79.60,
32.60, 27.25, 18.25, 17.80
6j
6k
6l
63/0.01
85/0.05
80/0.01
1.4719a
1.5074
1.5605
1670
1680
1620
2210
2210
2210
187.75, 91.50, 81.52, 45.30, 43.30, 30.65,
26.25, 22.20, 16.40, 13.80
1420
1585
178.10, 149.25, 133.85, 92.00, 79.65,
43.45, 30.65, 18.30, 16.40
178.20, 148.55, 142.15, 130.05, 129.75,
91.75, 79.90, 43.40, 30.55, 18.90, 16.45
Synthesis 2010, No. 24, 4213–4220 © Thieme Stuttgart · New York

4218
G. Cahiez et al.
PAPER
Table 6 Physical and Spectral Data of Acetylenic Ketones (continued)
IR (cm–1)
C=O
13C NMR (ppm)d
T
Product Bp (°C/torr)
nD
C≡C
C=C
C-O-C
6m
135/0.05
1.5664
1640
2190
1575, 1595
177.75, 136.75, 134.00, 129.45 (2C),
128.55 (2C), 94.25, 80.20, 43.40, 30.50,
16.60
6n
6o
6p
6q
96/0.1
1.4900
1.5072a
1.4822
1.4749
1670
2200
2200
2200
2200
187.25, 91.85, 81.35, 45.20, 44.70, 43.35,
32.35, 30.55, 26.20, 23.25, 16.40
130/0.01
110.0.05
120/0.01
1670
187.10, 91.75, 81.30, 45.15, 43.40, 33.55,
32.40, 30.45, 27.40, 23.05, 16.35
1670, 1735
1670, 1735
186.60, 173.15, 92.05, 81.10, 51.50, 44.40,
43.35, 32.80, 30.55, 19.20, 16.35
187.50, 173.80, 91.55, 81.45, 51.30, 45.40,
43.35, 33.90, 30.60, 28.80, 28.60, 24.75,
23.85, 16.40
6r
6s
6t
8
70/0.01
68/0.05
84/0.01
105/0.05
1.4879a
1.5273
1.5065
1.4638
1670
1645
1670
1670
2200
2200
2205
2220
187.60, 91.25, 81.50, 45.25, 31.80, 30.65,
26.20, 22.15, 17.65, 13.80
1610
176.10, 157.55, 125.95, 89.70, 83.85,
31.95, 30.70, 27.70, 21.00, 17.70
186.00, 92.20, 81.25, 44.00, 42.35, 31.90,
30.50, 26.65, 17.65
1090, 1170
187.75, 111.90, 93.75, 81.05, 72.15, 71.40,
47.40, (40.05, 40.35)e, (37.55, 37.70)e,
29.15, 27.80, (23.10, 23.45)e, 18.85, 18.30,
17.65, (17.00, 17.35)e, 14.40, 13.55
10a
10b
10c
80/0.01
85/0.1
1.4445b
1.4680
1.4850
1685
1650
1660
2200
2220
2230
1120
186.80, 91.20, 84.95, 82.70, 61.45 (2C),
45.25, 25.95, 22.15, 15.10 (2C), 13.80
1440
1620
1250, 1050
1060, 1120
177.20, 150.35, 133.65, 91.30, 85.80,
81.05, 61.55 (2C), 18.45, 15.10 (2C)
79/0.01
212.20, 175.25, 125.60, 91.30, 85.00,
83.40, 61.45 (2C), 27.80, 21.25, 15.10
(2C)
10d
114/0.01
1.5155
1630
2220
1590
1060, 1120
177.35, 149.25, 142.70, 130.15, 129.55,
91.35, 85.65, 81.45, 61.55 (2C), 18.95,
15.10 (2C)
10e
10f
93/0.01
1.4625
1.4615
1680
1680
2220
2220
1050, 1130
1050
185.35, 91.15, 85.65, 82.40, 61.55 (2C),
42.45, 43.85, 26.50, 10.05 (2C)
100/0.01
186.45, 91.10, 85.25, 82.55, 61.45 (2C),
45.20, 44.60, 32.35, 26.20, 23.05, 15.05
(2C)
10g
10h
10i
104/0.01
115/0.01
100/0.01
88/0.01
1.4554a
1.4541a
1.4550a
1.4535a
1680, 1740
1680, 1740
1680, 1725
1675, 1740
2220
2220
2220
2220
1050, 1140
1050, 1200
1050, 1150
1160
185.85, 173.05, 91.20, 85.40, 82.55, 61.55
(2C), 51.50, 44.45, 32.70, 19.00, 15.10
(2C)
186.60, 173.70, 91.15, 85.10, 82.60, 61.45
(2C), 51.25, 45.35, 33.90, 28.85, 28.60,
24.75, 23.65, 15.05 (2C)
186.45, 160.95, 91.15, 85.20, 82.55, 63.50,
61.50 (2C), 45.25, 28.35, 25.30, 23.35,
15.05 (2C)
13a
186.80, 172.40, 85.30, 84.85, 51.25, 47.15,
35.70, 18.40, 17.40, 13.60, 13.50
Synthesis 2010, No. 24, 4213–4220 © Thieme Stuttgart · New York

PAPER
Polyunsaturated and Functionalized Acetylenic Ketones
4219
Table 6 Physical and Spectral Data of Acetylenic Ketones (continued)
T
Product Bp (°C/torr)
nD
IR (cm–1)
C=O
13C NMR (ppm)d
C≡C
C=C
1610
C-O-C
1140
13b
13c
13d
77/0.01
85/0.01
140/0.2
1.4490
1.4700
1.5161
1675, 1740
1680, 1740
1650, 1720
2210
190.70, 175.80, 86.50, 83.95, 51.40, 42.95,
33.80, 18.85 (2C), 17.75 (2C)
2220
2210
1140
192.70, 177.10, 87.35, 82.95, 51.50, 44.65,
38.75, 27.05 (3C), 25.80 (3C)
175.25, 165.10, 159.00, 158.85, 125.55,
114.85, 86.90, 84.25, 50.70, 27.80, 27.40,
21.15, 20.30
13e
13f
70/0.01
80/0.01
1.4555a
1.4565
1680, 1740
1670, 1735
2220
2205
1180
1175
188.00, 173.90, 89.15, 81.45, 61.10, 38.80,
27.45, 19.55, 9.10, 8.00
186.75, 172.50, 85.35, 84.90, 51.30, 45.05,
33.60, 27.00, 26.00, 22.20, 22.30, 13.80
(2C)
15
135/0.1
1.4749
1675, 1740
2200
187.40, 171.45, 91.70, 85.20, 74.15, 47.60,
36.75, 36.50 (2C), 25.05, 22.40 (2C),
17.60, 17.55, 13.55 (2C)
a T = 20 °C.
b T = 22 °C.
c T = 25 °C.
d 25 MHz, CDCl3, TMS.
e Stereoisomers.
(2) (a) Cahiez, G. Manganese dioxide, In Encyclopedia of
Reagents for Organic Synthesis; Paquette, L., Ed.; Wiley:
Chichester, 1995, 199. See also: (b) Aijou, A. N.; Ferguson,
G. Tetrahedron Lett. 2006, 47, 3719. (c) Maeda, Y.;
Kakiuchi, N.; Matsumura, S.; Nishimura, T.; Kawamura, T.;
Uemura, S. J. Org. Chem. 2002, 67, 6718; and references
quoted therein.
Acknowledgment
We thank CNRS for financial support.
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Synthesis 2010, No. 24, 4213–4220 © Thieme Stuttgart · New York