Alkene cyclopropanation catalyzed by Halterman iron porphyrin: Participation of organic bases as axial ligands

Tat Shing Lai, Fung Yi Chan, Pui Kin So, Dik Lung Ma, Kwok Yin Wong, Chi Ming Che

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Abstract

With the iron(iii) complex of the Halterman iron porphyrin [P*Fe(Cl)] and ethyl diazoacetate (EDA) as catalyst and carbene source, respectively, styrene-type substrates were converted to cyclopropyl esters with high trans/cis ratio (not less than 12) and high enantioselectivity for the trans-isomers (74-86% ee). The isomeric distribution of the cyclopropyl esters so obtained is akin to that obtained from the previously reported Ru(ii) counterpart [P*Ru(CO)]. A linear Hammett correlation log(kX/kH) = σ+ρ was observed with ρ = -0.57 suggesting the involvement of an electrophilic cyclopropanating species derived from the iron(ii) center as the reactive intermediate in the catalytic cycle. This is further supported by a dramatic decrease in the enantioselectivity and trans/cis ratio observed in an experiment of styrene cyclopropanation when the reaction mixture was deliberately exposed to air. Axial ligand effects on the selectivities was also investigated. Substantial improvement in trans/cis ratios could be achieved by addition of organic bases such as pyridine (py) and 1-methylimidazole (MeIm) to the catalytic reaction. The existence of axially ligated iron carbene moieties, [P*Fe(CHCO2Et)(py)] and [P*Fe(CHCO2Et)(MeIm)], was established by electrospray mass spectrometry. Study of secondary kinetic isotope effect indicated that a more product-like transition state was generated by addition of MeIm.
Original languageEnglish
Pages (from-to)4845-4851
Number of pages7
JournalDalton Transactions
Issue number40
DOIs
Publication statusPublished - 19 Oct 2006

ASJC Scopus subject areas

  • Inorganic Chemistry

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