Low-Valent Iron-Catalyzed Transformations of Unsaturated

Low-Valent Iron-Catalyzed Transformations of Unsaturated Hydrocarbons

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Tobias Ritter, Harvard University Project goals: (1) Develop Fe-catalyzed transformations to access value-added building blocks from commodity chemicals such as dienes (2) Improve understanding of carbonyl-free Fe catalysis Iron Catalysis R

HSiR3

Me R3Si

NMe2

R

> 95:5 regioselectivity > 99:1 E/Z selectivity

Me

pyridine

FeCl2

Me

Li

N

N Fe N Me Me

A Strategy for the Synthesis of Well-Defined Iron Catalysts and Application to Regioselective Diene Hydrosilylation J. Am. Chem. Soc. 2010, 132, 13214–13216.

i-Pr

2 Me Me

- Development of a well-defined Fe precatalyst that generates low-valent Fe catalysts via reductive elimination upon addition of ligand - Isolation and characterization of Fe-iminopyridine complex; kinetic analysis using Fe-iminopyridine precatalyst - Development of regio- and stereoselective 1,4-hydrosilylation of 1,3-dienes

51% yield, (1.68 g)

2 equiv.

N

N

N

i-Pr

N

Ar

N N N

N Me

N Fe

NMe2

Fe

N

Ar

Me Me2N

Pre-Catalyst

Reductive Elimination

For more references, see: Iron-Catalyzed 1,4-Addition of α-Olefins to 1,3-Dienes. Org. Lett. 2009, 11, 337–339. Iron-Catalyzed 1,4-Hydroboration of 1,3-Dienes. J. Am. Chem. Soc. 2009, 131, 12915–12917.

48% yield X-Ray, NMR, Mšssbauer