E
H. Yamaga, K. Tanino
Letter
Synlett
Entry
9
Ketone
Yield of 13 (%)a
dr of 13d
Cyclization productb
Yield of 14 (%)c
dr of 14d
3:1
57
–
75
Me
O
HO
OTBS
14j
10
86
–
71
–
O
Me
(68% after recystallization)
HO
H
H
OTBS
H
H
H
H
H
BnO
BnO
14k
a Isolated yield of cyclization precursor from the corresponding ketone.
b Reaction conditions: To a solution of Me2CuLi in ether was added cyclization precursor 13 at –78 °C, and the mixture was stirred at 0 °C for 10 min before
quenching with an aqueous NH4Cl solution.
c Isolated yield after purification.
d Determined by 1H NMR spectroscopy of the crude product, relative stereochemistry not assigned.
e Cyclization precursor 13 was added at –20 °C, and the mixture was stirred at –20 °C for 20 min before quenching with an aqueous NH4Cl solution.
(9) (a) Tanino, K.; Arakawa, K.; Satoh, M.; Iwata, Y.; Miyashita, M.
Tetrahedron Lett. 2006, 47, 861. Formation of C–C bonds by
Funding Information
using this method was utilized by other groups: (b) Harada, K.;
Ito, H.; Hioki, H.; Fukuyama, Y. Tetrahedron Lett. 2007, 48, 6105.
(c) Trost, B. M.; Michaelis, D. J.; Malhotra, S. Org. Lett. 2013, 15,
5274.
This work was supported by JSPS KAKENHI Grant Numbers
JP15H05842 in Middle Molecular Strategy and JP18H01970.()
(10) (a) Paterson, I.; Kan, J. S. B.; Gibson, L. J. Org. Lett. 2010, 12, 3724.
(b) Paterson, I.; Paquet, T.; Dalby, S. M. Org. Lett. 2011, 13, 4398.
(c) Kamptmann, S. B.; Brückner, R. Eur. J. Org. Chem. 2013, 6584.
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(b) Gooding, O. W.; Beard, C. C.; Jackson, D. Y.; Wren, D. L.;
Cooper, G. F. J. Org. Chem. 1991, 56, 1083.
Supporting Information
Supporting information for this article is available online at
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(12) Shibuya, M.; Tomizawa, M.; Iwabuchi, Y. Org. Lett. 2008, 10,
4715.
(13) General Procedure (Table 2, Entry 1)
References and Notes
To a cooled (–78 °C) suspension of CuI (609 mg, 3.20 mmol) in
ether (6.4 mL) was added dropwise a 1.17 M ethereal solution of
MeLi (5.47 mL, 6.40 mmol). The mixture was warmed up to 0 °C
and stirred for 10 min. The resulting clear solution was cooled
to –78 °C, and a 1.5:1 diastereomeric mixture of ketone 13b
(264 mg, 0.640 mmol) in ether (6.4 mL) was added. The mixture
was warmed up to 0 °C immediately and stirred for 10 min at
the temperature. The reaction was quenched with a saturated
aqueous NH4Cl solution. The mixture was filtered through a
short pad of Celite, and the aqueous layer was extracted with
ether. Concentration in vacuo and purification by silica gel
column chromatography afforded a 2:1 diastereomeric mixture
of cyclopentenol 14b (136 mg, 0.50 mmol, 79%) as a yellow oil.
1H NMR (500 MHz CDCl3): δ = 5.36 (0.5 H, s), 5.33 (1 H, s), 4.86
(1 H, dt, J = 7.4, 1.7 Hz), 4.14 (0.5 H, d, J = 1.1 Hz), 2.41 (1 H, td,
J = 8.3, 4.6 Hz), 2.16 (0.5 H, t, J = 4.6 Hz), 2.03 (1 H, dt, J = 10.7,
3.6 Hz), 1.90–1.80 (3 H, m), 1.74 (1 H, t, J = 1.4 Hz), 1.72 (3 H, dd,
J = 4.9, 3.7 Hz), 1.70–1.47 (3 H, m), 0.88 (13.5 H, m), 0.07 (3 H, t,
J = 3.2 Hz), 0.05 (6 H, s). 13C NMR (125 MHz, CDCl3): δ = 146.23,
144.46, 131.3, 129.61, 95.6, 93.69, 81.98, 74.89, 61.04, 54.82,
38.28, 36.55, 31.63, 26.52, 26.40, 25.98, 25.93, 25.63, 25.46,
18.33, 11.95, 11.54, –4.50, –4.58, –4.74, –4.91.
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