A tutorial problem in stereoelectronic control. The Tiffeneau-Demjanov rearrangement as part of a prostaglandin synthesis.

DOI: 10.14469/hpc/8067 Metadata

Created: 2021-04-04 07:16

Last modified: 2021-04-06 08:55

Author: Henry Rzepa

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)

Description

This reaction emerged a few years ago (thanks Alan!) as a tutorial problem in organic chemistry, in which students had to devise a mechanism for the reaction and use this to predict the stereochemical outcome at the two chiral centres indicated with *. It originates in a brief report from R. B. Woodward’s group in 1973 describing a prostaglandin synthesis,[1] the stereochemical outcome being crucial. Here I take a look at this mechanism using computation.

Files

FilenameSizeTypeDescription
IRC.svg 100KB image/svg+xml Gaussian IRC computation
IRC.gif 2MB image/gif IRC Animation
IRC.gjf 1KB chemical/x-gaussian-input Gaussian input file
IRC.log 1MB chemical/x-gaussian-log Gaussian output file

Member of collection / collaboration

DOIDescription
10.14469/hpc/177 Computation data for Henry Rzepa's blog

Associated DOIs

Current dataset ...DOIDescription
References 10.14469/hpc/8066 A tutorial problem in stereoelectronic control. The Tiffeneau-Demjanov rearrangement as part of a prostaglandin synthesis.

Subject Keywords

KeywordValue
inchi InChI=1S/C8H12O4.ClH.N2/c9-3-5-4-1-8(11)12-7(4)2-6(5)10;;1-2/h3-8,10-11H,1-2H2;1H;/t4-,5-,6-,7+,8-;;/m1../s1
inchikey IJELMZKJKRGLDY-WTUBXSMSSA-N

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