273929-09-2Relevant academic research and scientific papers
Sequencing pericyclic reactions: The ester dienolate [2,3]-wittig/oxy-cope rearrangement/carbonyl ene reaction, a new access to substituted carbocycles
Hiersemann, Martin
, p. 483 - 491 (2001)
The sequential ester dienolate [2,3]-Wittig/oxy-Cope rearrangement/carbonyl ene reaction has been investigated. Acyclic α,β-unsaturated α-allyloxy-substituted esters 1a-j were transformed into cyclopentane- or cyclohexanecarboxylates 6a-f and 7a-7d. This study presents a domino ester dienolate [2,3]-Wittig/oxy-Cope rearrangement or a domino oxy-Cope rearrangement/carbonyl ene reaction, depending on the substrate structure. The thermal intramolecular type-I carbonyl ene reaction as the terminating ring-closing reaction proceeds with high simple diastereoselectivity, but low induced diastereoselectivity. The corresponding type-II ene reaction afforded the cyclohexanecarboxylates 7a-d in high yield with complete simple and induced diastereoselectivity. Unfortunately, an attempted auxiliary-controlled enantio-selective sequence was inefficient.
The sequential ester dienolate [2,3]-Wittig/3-oxy-cope rearrangement. New access to substituted α-keto esters
Hiersemann, Martin
, p. 415 - 417 (2007/10/03)
The dienolate [2,3]-Wittig rearrangement of 2-allyloxy-substituted α,β-unsaturated esters 1a-h afforded 3-alkoxycarbonyl-3-hydroxy-substituted 1,5-hexadienes 4a-h which were transformed to α-keto esters 5a-h via a thermal or Pd(II)-catalyzed oxy-Cope rear
