45661317 the Integrated Synthesis Course Schlenk Technique Jurgen Heck University of Hamburg Jurgen...
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Transcript of 45661317 the Integrated Synthesis Course Schlenk Technique Jurgen Heck University of Hamburg Jurgen...
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The Integrated Synthesis Course (ISP)
The Integrated Synthesis Course (ISP)
A third year practical course of synthetic inorganic and organic chemistry
in Hamburg
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methodology course2 weeks
Schlenk course3 days
chromatographycourse – 1 day
main course9 weeks
cleaning the lab1 day traditional ISP party
1st report deadline4 weeks later
2nd report deadlineafter 6 weeks
final:oral examinations
after 4 weeks overall time:24 weeks
Schedule of the ISPSchedule of the ISP
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valves, two ways,expensive
combined N2-vacuum line
Equipment needed for Schlenk techniqueEquipment needed for Schlenk technique
„Schlenk rake“
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apparatus
N2-vacuumline
gas disposal
has to be filledwith silicon oil
can be filled with oilto protect the springfrom corrosive gases
screw to tune thereleasing pressure
overpressurereleasing valve
(Stutz type)
Equipment needed for Schlenk techniqueEquipment needed for Schlenk technique
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simple refluxapparatus
nitrogen
nitrogen
Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
simple refluxapparatusnitrogen
nitrogen
fill in airsensitivecompounds
apparatus stays underinert gas atmosphere!
the reflux condensercan be substituted for a
dropping funnel,for example.
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transfer ofcompounds
nitrogen
Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
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nitrogen
simple refluxapparatus
close this valve for refluxing!
Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
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sublimationapparatus
Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
vacuum
heating
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sublimationapparatus
Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
vacuum
heating
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sublimationapparatus
Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
nitrogen
use a spatulato scratch offthe crystals...
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
nitrogen
solvent and drying agent
metal refluxcondenser
main benefit:apparatus dries itself!
solvent dryingapparatus
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
nitrogen
solvent dryingapparatus
nitrogen
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
filtration
nitrogennitrogen
nitrogen
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
filtration
nitrogen
nitrogen/vacuum
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
preparing anIR probe nitrogen
one drop of nujol
2nd NaCl block
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
preparing anIR probe nitrogen
Press together and grind!
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
preparing aNMR probe
nitrogen
nitrogen
Transfer the solution with asyringe or a pasteur pipette
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Standard apparatus utilizing Schlenk techniqueStandard apparatus utilizing Schlenk technique
preparing aNMR probe
nitrogen
nitrogen
Transfer the solution with asyringe or a pasteur pipette
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Olefin MetathesisOlefin Metathesis
2 RuCl3(H2O)x 7 PPh3+ + Ph3P=O + 2 HClPPh3Ru
Cl
ClPPh3
PPh3
2
CRu
Cl
ClPPh3
PPh3
Ph
H
SNH
O
ONS
NH
O
ONH2
O
NaOMe PCy3
1
CRu
Cl
ClPCy3
PCy3
Ph
H
N2
J. Inorg. Nucl. Chem. 1966, 28, 945
TsN Ts
N
- CH2=CH2
cat. RuCl2(=CHPh)(PCy3)2
2
JACS 1996, 118, 100
Org. Let. 2001, 3, 1411
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Jacobsen EpoxidationJacobsen EpoxidationOH OH OH
HCHO, NaOH
92 %
OH
H
OCe(OH)3OOH
94 %
OH-O2C
OH
-O2C
H2NNH2
(+)-tartaric acid
racemic mixture
NH3+
+H3N 1. Mn(OAc)3 x 2H2O,TEA2. NaCl
83 %
NNMn
OOCl
Cat.
75 %
Cat./NaOClO
89 % ee
Synth. Commun. 2001, 31, 2913;Chem. Rev. 2003, 103, 2457
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CBS ReactionCBS Reaction
HN
CO2H
BnN
CO2Me1. MeOH, SOCl22. BnBr, TEA
62 %
PhMgBr, THF
BnN
OH97 %
5 % Pd / C, H2quant.
HN
OHMole sieve,n-Butylboronic acid
quant.N
OB
PhPh
Cat.
BH3 * DMSOH
80 %98 % ee
O
Cat.
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Typical OM compounds prepared in the ISPTypical OM compounds prepared in the ISP
TiCl
Cl
ClTi
Cl
Cl
ClZr(thf)2Cl
Cl ClRu
CO
IOC I
OC IRu
I
COCO
CO
Br
NONCuM
NON
Br
M = Zn, Pb
OO
O OCH3
O OTi Ti
ClCp
CpClCl Cl
P Ni
P
P
NO3
P
NO3
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Typical organic compounds prepared in the ISPTypical organic compounds prepared in the ISP
OO
N
NH
O
OSi
O
OH
HON
N
ON
N
N
Cl
NH2N
O
OTBDMS
TBDMSO
N
N
N
O
BrN
O
OTBDMS
TBDMSO NHO H
PO N
N
NC
O
Br
OAcOAc
AcOOAc
OOAcOAc
AcOOAc
O
Cl3CNH