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. 2006 Sep 25;25(20):4731-4733.
doi: 10.1021/om0606791.

Zirconium Bis(Amido) Catalysts for Asymmetric Intramolecular Alkene Hydroamination

Donald A Watson  1 , Melanie Chiu, Robert G Bergman
Affiliations

Zirconium Bis(Amido) Catalysts for Asymmetric Intramolecular Alkene Hydroamination

Donald A Watson et al. Organometallics. .

Abstract

In situ combination of diphosphinic amides and Zr(NMe(2))(4) results in the formation of chiral zirconium bis(amido) complexes. The complexes are competent catalysts for intramolecular asymmetric alkene hydroamintion, providing piperidines and pyrrolidines in up to 80% ee and high yield. This system utilizes an inexpensive zirconium precatalyst and readily prepared ligands and is the first asymmetric alkene hydroamination catalyst based upon a neutral zirconium bis(amido) complex.

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Figures

(1)
(1)
Figure 1
Figure 1
Structures of ligands examined.
Figure 2
Figure 2
ORTEP representation of the solid state structure of 21a. Arenes connected to P29 have been truncated for clarity. Thermal ellipsoids are shown at 50% probability.
Scheme 1
Scheme 1
Products from the reaction of diphosphinic amide ligands and Zr(NMe2)4.
Scheme 2
Scheme 2
Proposed catalytic cycle and catalyst decomposition.
See this image and copyright information in PMC

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