N-(4-[2.2]paracyclophanyl)-2 '-Hydroxyacetophenone Imine: An Effective Paracyclophane Schiff-Base Ligand for use in Catalytic Asymmetric Cyclopropanation Reactions
Document Type
Article
Publication Date
9-1-2012
Department
Chemistry and Biochemistry
School
Mathematics and Natural Sciences
Abstract
The synthesis of planar chiral N-(4-[2.2]paracyclophanyl)-2′-hydroxyacetophenone imine (5) and its use as a ligand for the copper(II) catalyzed cyclopropanation of styrene and stilbene derivatives using diazoesters is presented. Catalyst loadings of 0.1 mol% gave conversions of >80% (turnover numbers approaching 1000) for styrene and its derivatives. When enantiomerically enriched (R)-5 was used to form the catalyst for cyclopropanation of styrene using ethyldiazoacetate, the cyclopropane products were obtained in a trans/cis ratio of 1.9–1 and 75.8% and 60.5% ee (corrected), respectively. The use of t-butyldiazoacetate resulted in an increased trans/cis ratio of 4.6–1 and 88.2% and 77.9% ee, respectively. Enantioselectivities of up to 95% ee were observed. These are among the highest enantioselectivities observed for asymmetric reactions using catalysts where chirality is solely derived from the paracyclophanyl moiety. When compared to its non-methylated analog, the simple presence of a methyl group on the carbon of the imine moiety in 5 resulted in an average increase in enantioselectivity of ca. 60% ee for a variety of substrates. The origin of this dramatic improvement in selectivity is discussed.
Publication Title
Journal of Molecular Catalysis A-Chemical
Volume
361
First Page
111
Last Page
115
Recommended Citation
Masterson, D. S.,
Shirley, C.,
Glatzhofer, D. T.
(2012). N-(4-[2.2]paracyclophanyl)-2 '-Hydroxyacetophenone Imine: An Effective Paracyclophane Schiff-Base Ligand for use in Catalytic Asymmetric Cyclopropanation Reactions. Journal of Molecular Catalysis A-Chemical, 361, 111-115.
Available at: https://aquila.usm.edu/fac_pubs/8870