Interesting ChemistryAnimationChemical BondCondensationDemjanov RearrangementChemical Sciences

A tutorial problem in stereoelectronic control. A Grob alternative to the Tiffeneau-Demjanov rearrangement?

https://doi.org/10.59350/6yszr-hpw54
Published in Henry Rzepa's Blog

In answering tutorial problems, students often need skills in deciding how much time to spend on explaining what does not happen, as well as what does. Here I explore alternatives to the mechanism outlined in the previous post to see what computation has to say about what does (or might) not happen.

References

Inorganic ChemistryOrganic ChemistryPhysical and Theoretical ChemistryDrug DiscoveryBiochemistry

Die 1,4‐Eliminierung unter Fragmentierung

https://doi.org/10.1002/hlca.19550380306
Published in Helvetica Chimica Acta
Authors C. A. Grob, W. Baumann

AbstractA number of 1,4‐elimination reactions proceeding with concomitant fragmentation according to scheme (1) are reviewed. It is pointed out that one of the simplest cases of this mechanistic type has hitherto remained unnoticed, viz. the elimination of halogen from saturated 1,4‐dihalides with formation of two olefinic bonds according to scheme (11).

InChI=1S/C8H13N2O4.Cl/c9-10-7-3-1-6(12)14-5(3)2-4(11)8(7)13;/h3-8,11-13H,1-2H2;/t3-,4-,5-,6-,7-,8-;/m1./s1FONNGUZMZSNFNR-YEIVJAOWSA-N

C 8 H 13 Cl 1 N 2 O 4

https://doi.org/10.14469/ch/191653
Published
Authors Henry S Rzepa, Imperial College London, Imperial College London, Henry S Rzepa

# opt(calcall,ts,noeigentest,cartesian) wb97xd/6-311g(d,p) scrf=(cpcm,

InChI=1S/C8H13N2O4.Cl/c9-10-7-3-1-6(12)14-5(3)2-4(11)8(7)13;/h3-8,11-13H,1-2H2;/t3-,4-,5-,6-,7-,8-;/m1./s1FONNGUZMZSNFNR-YEIVJAOWSA-N

C 8 H 13 Cl 1 N 2 O 4

https://doi.org/10.14469/ch/191654
Published
Authors Henry S Rzepa, Imperial College London, Imperial College London, Henry S Rzepa

# opt=(calcall,ts,noeigentest,cartesian) wb97xd/6-311g(d,p) scrf=(cpcm