Isomerization of Allylic Alcohols to Saturated Carbonyl Compounds
FULL PAPER
ture was allowed to react for about 10Ϫ15 min before a solution
of the allylic alcohol 19 (154µL, 1 mmol) in dry THF was added.
Compound 38b: 1H NMR: δ ϭ 0.90 (t, J ϭ 6.9 Hz, 3 H, CH3),
1.23Ϫ1.62 (m, 6 H, CH2), 2.28 (dt, J ϭ 5.0, 2.0 Hz, 2 H,
The reaction mixture was heated at reflux and the progress of the CCϪCH2), 3.41 (s, 3 H, OCH3), 4.67 (ddt, J ϭ 6.0, 2.0, 1.5 Hz, 1
reaction was monitored by thin layer chromatography. Upon com- H, CHϪOCH3), 6.25 (dd, J ϭ 16.0, 6.0 Hz, 1 H, PhϪCHϭCH),
pletion of isomerization, the reaction mixture was cooled to ambi-
ent temperature and THF removed under reduced pressure. The
crude reaction mixture was purified by column chromatography
(silica gel, pentane/ether, 9:1) to afford pure octan-3-one.
6.76 (d, J ϭ 16.0 Hz, 1 H, Ph-CH), 7.22Ϫ7.41 (m, 5 H, Ph).
Compounds (E)-38a ؉ (Z)-38a ؉ 38b: 13C NMR: δ ϭ 13.9, 13.95
(2), 18.7, 19.3, 19.4, 22.1, 22.15, 28.25, 28.3, 28.35, 31.0 (2), 31.05,
55.3, 56.3, 56.4, 71.4, 76.7, 76.75, 78.2, 80.5, 83.6, 88.4, 91.7, 96.3,
111.8, 126.2, 126.7, 126.8, 127.5, 127.7, 127.9, 128.4, 128.45 (2),
132.7, 136.2, 140.2, 141.0, 141.3, 141.5. Ϫ HRMS (m/z) calcd. for
C17H22O: 242.1671, found 242.1671.
General Procedure for the Isomerization of Allylic Alcohols to Cor-
responding Ketones with Catalyst 12: To a stirred suspension of
(PPh3)3RuCl2 (48 mg, 0.05 mmol, 5 mol %) in 5Ϫ10 mL of dry
THF, under an atmosphere of nitrogen, were added two equivalents
(63 µL, 0.1 mmol) of nBuLi (1.6 solution in hexane) at room
temperature. A wine red solution was quickly formed and this mix-
ture was allowed to react for about 10Ϫ15 min before a solution
of the allylic alcohol 19 (154 µL, 1 mmol) in dry THF was added.
The reaction mixture was heated at reflux and the progress of the
reaction was monitored by thin layer chromatography. Upon com-
pletion of isomerization, the reaction mixture was cooled to ambi-
ent temperature and THF removed under reduced pressure. The
crude reaction mixture was purified by column chromatography
(silica gel, pentane/ether, 9:1) to afford pure octan-3-one.
Acknowledgments
We thank P. Guenot (CRMPO, Rennes) for performing mass spec-
tral experiments. We thank CNRS and Ministry of Education and
Research for the award of a research associate position to R. U.
[1]
For representative examples using different metals see: [1a] J.-E.
Bäckvall, U. Andreasson, Tetrahedron Lett. 1993, 34,
[1b]
5459Ϫ5462. Ϫ
B. M. Trost, R. J. Kulawiec, J. Am. Chem.
[1c]
General Procedure for the Isomerization of Allylic Alcohols to Cor-
responding Ketones with Catalyst 16: To a mixture of (PPh3)3RuCl2,
(48 mg, 0.05 mmol, 5 mol %) and AgPF6 (13 mg, 0.05 mmol) in a
Schlenk tube was added 5Ϫ10 mL of freshly distilled MeOH and
refluxed in the dark, under an atmosphere of nitrogen, for 2 hours.
The reaction mixture was cooled to room temperature during
which time the precipitated silver salts settled. The supernatant so-
lution was filtered through a small Celite pad under nitrogen using
Schlenk equipment. To the filtrate was added allylic alcohol (154
µL, 1 mmol) in MeOH (3 mL) and refluxed under a nitrogen atmo-
sphere. The progress of the reaction was monitored by thin layer
chromatography and upon completion, the reaction mixture was
cooled to room temperature. Removal of MeOH under reduced
pressure and column chromatography (silica gel, pentane/ether, 9:1)
afforded pure octan-3-one.
Soc. 1993, 115, 2027Ϫ2036. Ϫ
Tetrahedron. Lett. 1974, 47, 4133Ϫ4136. Ϫ
Y. Sasson, G. L. Rempel,
[1d]
D. Baudry, M.
Ephritikhine, H. Felkin, Nouv. J. Chim. 1978, 2, 355Ϫ356. Ϫ
[1e] R. Damico, T. J. Logan, J. Org. Chem. 1967, 32, 2356Ϫ2358.
[1f]
Ϫ
R. W. Goetz, M. Orchin, J. Am. Chem. Soc. 1963, 85,
[1g]
1549Ϫ1550. Ϫ
C. Slugovc, E. Rüba, R. Schmid, K.
Kirchner, Organometallics 1999, 18, 4230Ϫ4233. Ϫ [1h] N. Iran-
poor, E. Mottaghinejad, J. Organomet. Chem. 1992, 423,
399Ϫ404 and references therein.
[2a] K. Tani, Pure and Appl. Chem. 1985, 57, 1845Ϫ1854. Ϫ
[2]
[2b]
S. Otsuka, K. Tani, Synthesis 1991, 665Ϫ680. Ϫ [2c] K. Tanaka,
S. Qiao, M. M.-C. Lo, G. C. Fu, J. Am. Chem. Soc. 2000, 122,
[2d]
9870Ϫ9871. Ϫ
A kinetic resolution of an allylic alcohol
has been studied by Noyori, see ref.[2e]
Ϫ
M. Kitamura, K.
[2e]
Manabe, R. Noyori, Tetrahedron Lett. 1987, 28, 4719Ϫ4720. Ϫ
[2f] Very good results were also obtained for the enantioselective
[2g]
isomerization of allylic amines by Noyori, see ref.[2g]) Ϫ
R.
Ϫ1
Noyori, H. Takaya, Acc. Chem. Res. 1990, 23, 345Ϫ350.
˜
(E)-1-Phenyldec-1-en-4-yn-3-ol (29): FT-IR (neat): ν ϭ 3350 cm
[3]
[4]
[5]
1
S. H. Bergens, B. Bosnich, J. Am. Chem. Soc. 1991, 113,
958Ϫ967.
(OH), 2235, 1947, 1877, 1802, 1599, 1495, 1451. Ϫ H NMR: δ ϭ
0.90 (t, J ϭ 7.1 Hz, 3 H, CH3), 1.27Ϫ1.42 (m, 4 H, CH2), 1.54
(pent, J ϭ 7.2 Hz, 2 H, CH2), 2.23 (br. s, 1 H, OH), 2.25 (dt, J ϭ
2.0, 7.1 Hz, 2 H, CH2-CC), 5.04 (br. s, 1 H, CHOH), 6.29 (dd, J ϭ
6.1, 15.8 Hz, 1 H, CHϪCH-OH), 6.74 (br. d, J ϭ 15.8 Hz, 1 H,
CHϭCHϪCHOH), 7.22Ϫ7.41 (m, 5 H, Ph). Ϫ 13C NMR: δ ϭ
14.0, 18.8, 22.2, 28.3, 31.1, 63.1, 79.1, 87.5, 126.8, 128.0, 128.6,
128.8, 131.4, 136.2. Ϫ HRMS (m/z) calcd. for C16H20O: 228.1514;
found 228.1520.
´
´
C. Crevisy, M. Wietrich, V. Le Boulaire, R. Uma, R. Gree,
Tetrahedron Lett. 2001, 42, 395Ϫ398.
G. J. Boons, H. Burton, S. Isles, Chem. Commun. 1996,
141Ϫ142.
[6] [6a]
S. E. Diamond, F. Mares, J. Organomet. Chem. 1977, 142,
[6b]
C55ϪC57. Ϫ
F. Shriver, Inorg. Chem. 1978, 17, 3064Ϫ3068. Ϫ
Dewhirst, W. Keim, C. A. Reilly, Inorg. Chem. 1968, 7,
S. H. Strauss, S. E. Diamond, F. Mares, D.
[6c]
D. K C.
[6d]
546Ϫ552. Ϫ
W. Keim, J. Organomet. Chem. 1967, 8,
P25ϪP26. Ϫ [6e] M. Michman, M. Balog, J. Organomet. Chem.
(E)-1-Methoxy-1-phenyldec-2-en-4-yne [(E)-38a], (Z)-1-Methoxy-1-
phenyldec-2-en-4-yne [(Z)-38a] and (E)-3-Methoxy-1-phenyldec-1-
1971, 31, 395Ϫ402. Ϫ [6f] W. Keim, J. Organomet. Chem. 1968,
[6g]
1
14, 179Ϫ184. Ϫ
L. S. Hegedus, S. M. Lo, D. E. Bloss, J.
en-4-yne (38b). ؊ Compound (E)-38a: H NMR: δ ϭ 0.88 (t, J ϭ
Am. Chem. Soc. 1973, 95, 3040Ϫ3042.
7.1 Hz, 3 H, CH3), 1.23Ϫ1.62 (m, 6 H, CH2), 2.26 (dt, J ϭ 7.0,
2.3 Hz, 2 H, CCϪCH2), 3.31 (s, 3 H, OCH3), 4.62 (br. d, J ϭ
6.8 Hz, 1 H, CHϪOCH3), 5.71 (ddt, J ϭ 16.0, 2.3, 1.3 Hz, 1 H,
CHϭCH-CC), 6.08 (dd, J ϭ 16.0, 6.8 Hz, 1 H, CH(OCH3)ϪCHϭ
CH), 7.22Ϫ7.41 (m, 5 H, Ph).
[7] [7a]
The reaction was performed from commercial rhodium
complex and according to a modified version of the procedure
[7b]
described by Strohmeier, see ref.[7b]
Ϫ
W. Strohmeier, L.
Weigelt, J. Organomet. Chem. 1975, 86, C17ϪC19.
S. G. Davies, J. P. McNally, A. J. Smallridge, Adv. Organomet.
Chem. 1990, 30, 1Ϫ75.
[8]
[9]
Compound (Z)-38a: 1H NMR: δ ϭ 0.91 (t, J ϭ 7.3 Hz, 3 H, CH3),
1.23Ϫ1.62 (m, 6 H, CH2), 2.38 (dt, J ϭ 6.9, 2.3 Hz, 2 H,
CCϪCH2), 3.38 (s, 3 H, OCH3), 5.28 (br. d, J ϭ 9.0 Hz, 1 H,
CHϪOCH3), 5.65 (ddt, J ϭ 10.5, 2.3, 0.8 Hz, 1 H, CHϭCH-CC),
5.88 (dd, J ϭ 10.5, 9.0 Hz, 1 H, CH(OCH3)ϪCHϭCH), 7.22Ϫ7.41
(m, 5 H, Ph).
[9a] When catalyst 9 is prepared according to the procedure de-
scribed by Wells (see ref.[9b]), it performs the desired isomeriz-
ation reaction. Nevertheless, due to the large excess (20 equiv.)
of triethylamine used for its preparation, it cannot be used for
other reactions, for example it is not able to perform any
[9b]
isomerizationϪaldol condensation (see ref.[9c]). Ϫ
B. Hud-
Eur. J. Org. Chem. 2001, 3141Ϫ3146
3145