Adam R. Johnson Department of Chemistry

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Presentation transcript:

Catalytic asymmetric reactions with chiral titanium amide-alkoxide complexes Adam R. Johnson Department of Chemistry Harvey Mudd College, Claremont, CA 91711

Modular ligand synthesis 1st generation, R’ = H 2nd generation, R’ = alkyl

Ligand nomenclature Can’t be made … 1st generation 2nd generation

Initial hydroamination results 10 mol % cat., 135˚ C 10 mol % cat., 110˚ C All 1st generation ligands ee’s by chiral GC of benzamide derivative “blue” ee’s are opposite enantiomer (lower Rf found with D-ligands) Organometallics, 2004, 4614

Hydroamination with bulkier L 5 mol % cat., 135˚ C Overnight reaction, >95% completion, single product 2nd generation ligands ee’s by chiral shift NMR using R-O-acetylmandelic acid “red” isomers (more downfield shift) correspond to same enantiomer as before (longer Rf by GC)

Benzaldehyde alkylation -78° to room temperature overnight Same reaction conditions for titanium complexes: 1.1 eq Et2Zn 5 mol% ligand 5 mol% Ti(OiPr)4

Alkylation data highlights 85-98% conversion; some reduction R product favored with L-amino alcohols Increase in %ee using Ti, but same enantiomer (in almost all cases)

Acknowledgements ACS-PRF, NSF-RUI, NSF-REU Undergraduate co-workers: Benzaldehyde alkylation: Casey Jones (Reed, ‘05), Hanhan Li (HMC, ‘05), Joanne Redford (HMC ‘09), Sam Sobelman (HMC ‘08), Drew Kouzelos (HMC ‘07), Ryan Pakula (HMC ‘09) Hydroamination: Amanda Hickman (HMC ‘07), Lauren Hughs (HMC ‘09) New directions: Dianna McAnnally-Linz (Agnes Scott, ‘08), Minh Nguyen (U. La Verne, ‘08), Andrew Stewart (HMC, ‘08)