Pyrrole-based Organocatalysts for Chemical Rearrangements

We developed the first synthesis of dipyrromethanes with chiral centers installed adjacent to both nitrogens with 99% enantioselectivity to expand...
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Pyrrole-based Organocatalysts for Chemical Rearrangements and Living Polymerizations Catharine H. Larsen, Department of Chemistry, University of California, Riverside Dipyrromethanes constitute half a porphyrin, or an iron-free heme, leading to a wide range of applications. The high interest in the fundamental properties and intrinsic reactivity of achiral dipyrrin and dipyrromethane complexes of iron, zinc, copper, boron, nickel, and more is due to their establishment as: ¥ water-stable environmental sensors ¥ light-harvesting architectures ¥ materials for metal-organic frameworks ¥ imaging agents in living cells ¥ atom-transfer catalysts ¥ redox-active ligands

R

NH

R

H

R

NH HN

N

dipyrrin

R

NH HN

dipyrromethanes

Ph Mes

Me

Me

Me

Me

N

N

N

N

CH2NR2 N N

N Fe

t-Bu O

Cl

N Cu N

N

N

t-Bu

B

Me

Mes

N

F

F

N

Me

Mes

Ni

Mes N

N

Mes

Fe N

Ph

We developed the first synthesis of dipyrromethanes with chiral centers installed adjacent to both nitrogens with 99% enantioselectivity to expand dipyrrin systems and as backbones for new ligands. Ph asymmetric dipyrrin complexes

H

Ph

future

Me

H O

2 steps O HO

OH

Me

O

NH HN work

Me

Me

N H

asymmetric redox-active ligands

NH HN 2 steps Ph HO

OH