Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/12952
Title: Alkene cyclopropanation catalyzed by Halterman iron porphyrin : participation of organic bases as axial ligands
Authors: Lai, TS
Chan, FY
So, PK
Ma, DL
Wong, KY 
Che, CM
Issue Date: 2006
Publisher: Royal Society of Chemistry
Source: Dalton transactions : an international journal of inorganic chemistry, 2006, no. 40, p. 4845-4851 How to cite?
Journal: Dalton transactions : an international journal of inorganic chemistry 
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.
URI: http://hdl.handle.net/10397/12952
ISSN: 1477-9226
EISSN: 1477-9234
DOI: 10.1039/b606757c
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