Experimental Section
General
methods:
Chemicals
(Aldrich,
Fluka,
Lancaster,
and
Merck) were used without further purification. Diethyl ether
and tetrahydrofuran were dried over sodium. NMR spectra were
recorded on Bruker ARX500, ARX300 and AMX250 spectrometers.
Chemical shifts were referenced to residual solvent protons.
Signal multiplicity as follows: s (singlet), d (doublet), t
(triplet),
achieved
q
via
(quartet),
DEPT90
m
and
(multiplet).
DEPT135
13C
spectra.
assignment
MS
spectra
was
were
recorded on a Finnigan MAT 90 a Varian 711 or a micrOTOF-Q
spektrometer. IR spectra were recorded on a Bruker Vector 22.
General
procedure
1
(GP
1)
–
Addition
of
alkynes
to
α-
chloroketones
Under
nitrogen,
1
eq.
of
the
alkyne
is
dissolved
in
the
specified solvent (THF or Et2O) and the solution is cooled to
-78 °C. After slow addition of 1.05 eq. n-BuLi (1.6 M in
hexane) the solution is stirred for 20 min. Finally 1 eq. of
the chloroketone is added, the cooling bath is removed and the
solution is stirred for 16 h at rt. After the addition of a
saturated solution of NH4Cl, the phases are separated and the
aqueous
phase
is
extracted
twice
with
DCM.
The
combined
organic phases are dried over MgSO4, filtered and purified by
column
chromatography
on
silica
(PE,EA).
Dependent
on
the
substrate, tertiary alcohols X, epoxides Y or both products
are obtained.
General procedure 2 (GP 2) – Conversion of tertiary alcohols X
to epoxides Y:
Under inert atmosphere 1 eq. of alcohol x is dissolved in dry
Et2O (c = 0.4 mol/l). The solution is cooled to 0 °C and 2 eq.
of freshly powdered NaOH are added in small portions. The
reaction
course
is
monitored
by
TLC.
In
some
cases
the
solutions become highly viscous on addition of the base, if so
the
same
amount
of
solvent
should
be
added
again.
After
complete conversion, the suspension is filtered, dried with
MgSO4 and the solvent is removed. The raw products are purified
by column chromatography (SiO2, PE, EA)
General Procedure 3 (GP 3) - Gold catalysis
5 mol% gold catalyst X and 5 mol% AgOTf are stirred in a
mixture of DCM/ MeOH (9/1) for 15 min. After the addition of
the epoxide (c= 0.3 mol/l), the reaction mixture is stirred at
rt
and
the
reaction
is
monitored
by
TLC.
After
complete
consumption of the starting material, the solvent is removed
and
the
residue
is
purified
by
column
chromatography
on
silica (PE, EA).
Preparation of Verbindungsname Praktikant Nr
Chem-Draw Struktur (Campus-Lizenz von Chemdraw verfügbar)
According to GP 1 x.xx g (x.xx mmol) alkyne, x.xx ml Buli (1.6
M, in hexanes, x.xx mmol) and x.xx g (x.xx mmol) Name des
Säurechlorids were converted in
Solvent. After purification
X.xx mg (x.xx mmol, x%) of the alcohol and x.xx mg (x.xx mmol,
x%) of epoxide x were obtained as Farbe/ÖL Feststoff etc after
purification by column chromatography (PE:EA, X:Y).
~
MP.: x°C; Rf (PE:EA, x:x) = x; IR (neat):  = x cm-1, x;
1H
NMR
(Frequenz MHz, solvent): δ = x (Multiplizität, J = x.x Hz,
x H), x;
13C
NMR (Frequenz MHz, solvent): x (Multiplizität), ,;
Masse: wird hier beim Abtippen der Daten näher erklärt:
Preparation of Verbindungsname Praktikant Nr:
Struktur
According to GP 2 x.xx g (x.xx mmol) alcohol x and x.xx g
(x.xx
mmol)
NaOH
were
chromatography (PE: EA,
converted
x:x), x.xx
for
x
h.
After
g (x.xx mmol,
column
x%) were
gained as Farbe/ÖL Feststoff etc.
~
MP.: x°C; Rf (PE:EA, x:x) = x; IR (neat): 
1H
= x cm-1, x,;
NMR (Frequenz MHz, solvent): δ = x (Multiplizität, J = x.x
Hz,
x H),
x;
13C
NMR
(Frequenz
MHz,
solvent):
x
(Multiplizität), ,; Masse: wird hier beim abtippen der Daten
näher erklärt:
Preparation of Verbindungsname Praktikant Nr:
Struktur
According to GP 3 x.xx mg (x.xx µmol) gold catalyst, x.xx mg
(x.xx
µmol)
AgOTf
and
x.xx
mg
(x.xx
mmol)
epoxide
X
were
converted for x h. After column chromatography (PE: EA, x:x),
x.xx g (x.xx mmol, x%) were gained as Farbe/ÖL Feststoff etc.
~
MP.: x°C; Rf (PE:EA, x:x) = x; IR (neat): 
1H
= x cm-1, x,;
NMR (Frequenz MHz, solvent): δ = x (Multiplizität, J = x.x
Hz,
x H),
x;
13C
NMR
(Frequenz
MHz,
solvent):
x
(Multiplizität), ,; Masse: wird hier beim abtippen der Daten
näher erklärt: