A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh₂(S-^tertPTTL)₄] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh₂(S-^tertPTTL)₄] was found to be comparable to that of [Rh₂(S-PTAD)₄] (up to >99 % ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.

Item Type:	Refereed Article
Keywords:	catalysis, organometallic
Research Division:	Chemical Sciences
Research Group:	Inorganic Chemistry
Research Field:	Transition Metal Chemistry
Objective Division:	Manufacturing
Objective Group:	Industrial Chemicals and Related Products
Objective Field:	Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:	Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:	107801
Year Published:	2016
Web of Science® Times Cited:	22
Deposited By:	Chemistry
Deposited On:	2016-03-24
Last Modified:	2018-03-14
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