Issue 3, 2019

Mild complexation protocol for chiral CpxRh and Ir complexes suitable for in situ catalysis

Abstract

A practical complexation method for chiral cyclopentadienyl (Cpx) iridium and rhodium complexes is described. The procedure uses the free CpxH with stable and commercially available rhodium(I) and iridium(I) salts without base or additive. The conditions are mild and do not require the exclusion of air and moisture. A salient feature is the suitability for in situ complexations enhancing the user-friendliness of Cpx ligands in asymmetric catalysis. DFT-calculations confirm an intramolecular proton abstraction pathway by either the bound acetate or methoxide. Furthermore, the superior facial selectivity of the proton abstraction step enabled the development of TMS-containing trisubstituted Cpx ligands which display improved enantioselectivities for the benchmarking dihydroisoquinolone synthesis.

Graphical abstract: Mild complexation protocol for chiral CpxRh and Ir complexes suitable for in situ catalysis

Supplementary files

Article information

Article type
Edge Article
Submitted
03 10 2018
Accepted
29 10 2018
First published
31 10 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 781-787

Mild complexation protocol for chiral CpxRh and Ir complexes suitable for in situ catalysis

B. Audic, M. D. Wodrich and N. Cramer, Chem. Sci., 2019, 10, 781 DOI: 10.1039/C8SC04385J

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