Shape and Stereoselective Cyclopropanation of Alkenes Catalyzed by Iron Porphyrins

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1995-09-01
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Robbins Wolf, Jennifer
Hamaker, Christopher
Djukic, Jean-Pierre
Kodadek, Thomas
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Chemistry

The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

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The Department of Chemistry was founded in 1880.

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Abstract

Iron porphryin complexes are active catalysts for the cyclopropanation of alkenes by ethyl diazoacetate. Fe(TIP) (TIP = meso-tetra-p-tolylporphyrin), an isolated iron(II) porphyrin complex, can be used as the catalyst, or the iron(III) complexes of several porphyrins can be reduced in situ. The reactions produce synthetically useful excesses of the trans cyclopropyl ester products. This stereoselectivity exhibits a modest solvent dependence, with donor solvents giving higher ratios of the trans cyclopropane products. The diastereoselectivity exhibits only a modest dependence on the steric bulk of the porphyrin. The reactions are selective for 1-alkenes and 1, 1-disubstituted alkenes. Conjugated substrates and enol ethers react more rapidly than simple aliphatic alkenes. A mechanistic model for the iron-mediated reactions is proposed which is consistent with the data presented herein.

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Reprinted (adapted) with permission from Journal of the American Chemical Society 117 (1995): 9194, doi:10.1021/ja00141a011. Copyright 1995 American Chemical Society.

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Sun Jan 01 00:00:00 UTC 1995
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