Document Type
Article
Language
eng
Format of Original
10 p.
Publication Date
1-2003
Publisher
American Chemical Society
Source Publication
Journal of Organic Chemistry
Source ISSN
0022-3263
Original Item ID
DOI: 10.1021/jo020421u
Abstract
The addition of stabilized carbon nucleophiles to tricarbonyl(1-methoxycarbonylpentadienyl)iron(1+) cation (1a) proceeds via attack at C2 on the face of the ligand opposite the Fe(CO)3 group to generate tricarbonyl(pentenediyl)iron complexes 2. Oxidation of complexes 2 affords vinylcyclopropanecarboxylates in good yield. In general, the relative stereochemistry about the cyclopropane ring reflects reductive elimination with retention of configuration. In cases where the C2 substituent is bulky (i.e., 2b) the major cyclopropane product 9b represents ring closure with inversion at C3. A mechanism involving π−σ−π rearrangement of the initially oxidized (pentenediyl)iron species is proposed to account for these results. Experiments which probe the stereochemistry of deuterium labeling in the vinyl group of the vinylcyclopropanecarboxylate products were carried out, and these results are consistent with the proposed mechanism. This methodology for the preparation of vinylcyclopropanecarboxylates was applied to the synthesis of 2-(2‘-carboxycyclopropyl)glycines (+)-22 and (−)-23 and the cyclopropane triester (−)-26.
Recommended Citation
Yun, Young K.; Godula, Kamil; Cao, Yeyu; and Donaldson, William A., "Iron-mediated Preparation of Vinylcyclopropanes. Scope, Mechanism, and Applications" (2003). Chemistry Faculty Research and Publications. 81.
https://epublications.marquette.edu/chem_fac/81
Comments
Accepted version. Journal of Organic Chemistry , Volume 68, No. 3 (2003), DOI. © 2003 American Chemical Society. Used with permission.