45661317 the Integrated Synthesis Course Schlenk Technique Jurgen Heck University of Hamburg Jurgen...

The Integrated Synthesis Course (ISP)

The Integrated Synthesis Course (ISP)

A third year practical course of synthetic inorganic and organic chemistry

in Hamburg

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

valves, two ways,expensive

combined N2-vacuum line

Equipment needed for Schlenk techniqueEquipment needed for Schlenk technique

„Schlenk rake“

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

simple refluxapparatus

nitrogen

nitrogen

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.

transfer ofcompounds

nitrogen


nitrogen

simple refluxapparatus

close this valve for refluxing!


sublimationapparatus


vacuum

heating

sublimationapparatus


nitrogen

use a spatulato scratch offthe crystals...


nitrogen

solvent and drying agent

metal refluxcondenser

main benefit:apparatus dries itself!

solvent dryingapparatus


nitrogen

solvent dryingapparatus

nitrogen


filtration

nitrogennitrogen

nitrogen


filtration

nitrogen

nitrogen/vacuum


preparing anIR probe nitrogen

one drop of nujol

2nd NaCl block


preparing anIR probe nitrogen

Press together and grind!


preparing aNMR probe

nitrogen

nitrogen

Transfer the solution with asyringe or a pasteur pipette

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

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

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.

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

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

45661317 the Integrated Synthesis Course Schlenk Technique Jurgen Heck University of Hamburg Jurgen...

Documents

Transcript of 45661317 the Integrated Synthesis Course Schlenk Technique Jurgen Heck University of Hamburg Jurgen...