References and Notes
1 New address: A. D. Gee, Division of
Imaging Sciences, School of Medicine, King’s College London,
The Rayne Institute, 4th Floor Lambeth Wing, St Thomas’ Hospital, Lambeth
Palace Rd., London, SE1 7EH, UK.
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6 For a report on oxidative homocoupling
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14 Compounds (E)-2a and (Z)-2a were stable towards isomerization under
the reaction conditions implying that the observed diastereoselectivity
is under kinetic control.
15
General Procedure
for Rearrangement-Fluorination Process
Selectfluor
(2 equiv), SIPrAuCl (5 mol%), and silver trifluoromethanesulfonate
(12.5 mol%) were added to a solution of the propargyl acetate
(1 equiv) in MeCN (0.05 M). The mixture was stirred at r.t. or 40 ˚C
until TLC showed consumption of the propargyl acetate (1.5-72
h). H2O was added, and the mixture was extracted with
EtOAc (3×). The combined organic fractions were washed
with brine, dried with anhyd MgSO4, filtered, and the
solvents removed in vacuo. The crude mixture was purified by column
chromatography on silica gel.
Preparation
of 2a
The general procedure was followed using 1a (500 mg, 1.94 mmol), Selectfluor (1.37
g, 3.87 mmol), SIPrAuCl (60 mg, 0.10 mmol), and AgOTf (62 mg, 0.24
mmol) in MeCN (39 mL). The reaction was stirred for 48 h at r.t. ¹9F
NMR analysis on the crude reaction mixture indicated an E/Z ratio of
12.5:1. Purification by column chromatography on silica gel (hexane-Et2O = 20:1)
afforded the product (E)-2a as
a yellow oil (290 mg, yield 64%) as well as (Z)-2a as a yellow solid
(24 mg, yield 6%).
(
E
)-2-Fluoro-1-phenylnon-1-en-3-one [(
E
)-2a]
R
f
= 0.50
(hexane-Et2O = 9:1). ¹H
NMR (400 MHz, CDCl3): δ = 7.60-7.64
(m, 2 H), 7.35-7.40 (m, 3 H), 6.70 (d, 1 H, J = 25.3 Hz),
2.65 (dt, 2 H, J = 7.1,
3.5 Hz), 1.63 (tt, 2 H, J = 7.3,
7.1 Hz), 1.27-1.36 (m, 6 H), 0.90 (dd, 3 H, J = 6.8, 6.5
Hz). ¹³C NMR (101 MHz, CDCl3): δ = 195.6
(d, J = 38 Hz),
153.1 (d, J = 258
Hz), 130.9 (d, J = 10
Hz), 130.0 (d, J = 2
Hz), 129.2, 128.2, 119.7 (d, J = 27
Hz), 40.2 (d, J = 2 Hz),
31.6, 28.8, 23.2 (d, J = 2
Hz), 22.5, 14.0. ¹9F NMR (377 MHz, CDCl3): δ = -114.9
(dt, J = 25,
4 Hz). IR (neat): 1708 (C = O). HRMS
(ESI+): m/z calcd
for C15H19FNaO+ [M + Na]+:
257.1314; found: 257.1312.
(
Z
)-2-Fluoro-1-phenylnon-1-en-3-one [(
Z
)-2a]
Mp 30 ˚C.
R
f
= 0.42 (hexane-Et2O = 9:1). ¹H
NMR (400 MHz, CDCl3): δ = 7.66-7.70
(m, 2 H), 7.38-7.44 (m, 3 H), 6.83 (d, 1 H, J = 36.9 Hz),
2.74 (dt, 2 H, J = 7.3,
2.3 Hz), 1.69 (tt, 2 H, J = 7.5,
7.3 Hz), 1.27-1.41 (m, 6 H), 0.91 (dd, 3 H, J = 7.0, 6.8
Hz). ¹³C NMR (101 MHz, CDCl3): δ = 195.1
(d, J = 32
Hz), 154.1 (d, J = 272
Hz), 131.2 (d, J = 4 Hz),
130.6 (d, J = 9
Hz), 129.7 (d, J = 3
Hz), 128.8, 114.9 (d, J = 6
Hz), 38.0, 31.6, 28.8, 23.5 (d, J = 2
Hz), 22.5, 14.0. ¹9F NMR (377 MHz, CDCl3): δ = -125.0
(d, J = 37
Hz). IR (CH2Cl2): 1697 (C = O).
HRMS (FI+): m/z calcd
for C15H19FO [M]+:
234.1420; found: 234.1414.
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19 Allenyl acetate 4l was
isolated as the only acetylated product during the attempted preparation
of the corresponding propargyl acetate 1l according
to the procedure of ref. 11a. This compound is presumably formed
via a spontaneous
3,3-sigmatropic rearrangement of 1l.
20
de Haro T.
Nevado C.
Chem. Commun.
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press; DOI: 10.1039/c002679d
