Asymmetric  Iridium-Catalysed Hydrogenation
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Asymmetric Iridium-Catalysed Hydrogenation New Ligands, New Substrates . Pher G. Andersson Uppsala University. Asym hydrogenation of olefins. Rh Ru. Asym hydrogen non-functionalized olefines. Ru (II) - BINAP. Rh (I) - BINAP. Takaya 1995. Buchwald 1993.

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Asymmetric Iridium-Catalysed Hydrogenation New Ligands, New Substrates .

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Asymmetric iridium catalysed hydrogenation new ligands new substrates

Asymmetric Iridium-Catalysed Hydrogenation

New Ligands, New Substrates.

Pher G. AnderssonUppsala University


Asym hydrogenation of olefins

Asym hydrogenation of olefins

Rh Ru


Asym hydrogen non functionalized olefines

Asym hydrogen non-functionalized olefines

Ru (II) - BINAP

Rh (I) - BINAP

Takaya 1995

Buchwald 1993

Halterman Comprehensive Asymmetric Catalysis Springer 1999, vol.1, 183-195.


Asym hydrogenation mechanism

Asym hydrogenation, mechanism

Rh

? Ru ?

? Ir ?

Landis & Halpern J. Am. Chem. Soc. 1987, 109, 1746.


Dft study of ir hydrogenation

DFT study of Ir-hydrogenation

B3LYP/LANL2DZ

Chem. Eur. J. 2003, 9, 339.


Computational chemistry

Computational chemistry

axup

eqt-P

eqt-N

Olefin

axdown


X ray structure vs dft

X-Ray structure vs DFT


Dft results

DFT results

B3LYP/LANL2DZ

Chem. Eur. J. 2003, 9, 339.


Dft results1

DFT results


Proposed catalytic cycle

Proposed catalytic cycle

Chem. Eur. J. 2003, 9, 339.


Coupled mi and ox add

Coupled MI and Ox Add


New ligand structures

New ligand structures

Synthesis should be:

  • short and efficient

  • allow preparation of both enantiomeres


Ligand structure and synthesis

Ligand structure and synthesis


Synthesis

Synthesis


Preparation of catalysts

Preparation of catalysts


Evaluation of catalysts

Evaluation of catalysts


Asymmetric iridium catalysed hydrogenation new ligands new substrates

Substrate study

J. Am. Chem. Soc.2004,126, 14308.


Further improvements of the ligand strucure

Further improvements ofthe ligand strucure

?

?


Oxazole vs thiazole

Oxazole vs Thiazole


Ligand synthesis ii

Ligand synthesis II


Ligand absolute configuration

Ligand, absolute configuration


Ligand evaluation

Ligand evaluation


Results

Results


Ligand synthesis iii

Ligand synthesis III


Ligand synthesis iii1

Ligand synthesis III

Adv.Synth.Cat. 2008, 350, 1168.


Separation of the enantiomeres by chiralcel od

Separation of the enantiomeresby ChiralCel OD


A new class of ligands

A new class of ligands


Ligand synthesis iv

Ligand synthesis IV

Org.Lett. 2004, 6, 3825. Chem. Eur. J. 2006, 12, 2318.


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