Stereochemical Requirements of Oxidative Cyclizations in Extended Iterative Organoiron-Mediated Routes to Alkaloids
journal contributionposted on 2012-11-02, 00:00 authored by G. Richard Stephenson, Caroline Roe, Christopher E. Anson
Oxidative cyclization by reaction of benzylic and phenolic OH groups on tricarbonyl(η4-cyclohexa-1,3-diene)iron(0) complexes has been achieved with the hypervalent iodine oxidant PIFA which was shown to be compatible with the tricarbonyliron complex. The reaction proceeds with substrates with the nucleophilic substituent on the opposite face of the ligand to the iron. IBX gives efficient oxidation of the benzyl alcohol to the aldehyde in the presence of the Fe(CO)3 group. Reduction of 1-arylcyclohexadienyliron(1+) complexes with sodium borohydride to access the endo series also gave a novel rearranged 2-aryl reduction product with a 5-endo OMe group. The cis relative stereochemistry of the oxidative cyclization product, the exo delivery of hydride to the 1-arylcyclohexadienyliron(1+) complex, and the 2-aryl-5-endo-methoxy relative stereochemistry of the rearranged product were proved by X-ray crystallography.
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Oxidative CyclizationsIBXnucleophilic substituentStereochemical Requirementsphenolic OH groupshypervalent iodine oxidant PIFAendo seriescomplexoxidative cyclization productarylcyclohexadienylironreaction proceedsarylbenzyl alcoholsodium borohydrideAlkaloidsOxidative cyclizationstereochemistryexo delivery