65093-64-3Relevant academic research and scientific papers
Chemo-Enzymatic Oxidative Rearrangement of Tertiary Allylic Alcohols: Synthetic Application and Integration into a Cascade Process
Brenna, Elisabetta,Crotti, Michele,De Pieri, Matteo,Gatti, Francesco G.,Manenti, Gabriele,Monti, Daniela
supporting information, p. 3677 - 3686 (2018/06/04)
A chemo-enzymatic catalytic system, comprised of Bobbitt's salt and laccase from Trametes versicolor, allowed the [1,3]-oxidative rearrangement of endocyclic allylic tertiary alcohols into the corresponding enones under an Oxygen atmosphere in aqueous media. The yields were in most cases quantitative, especially for the cyclopent-2-en-1-ol or the cyclohex-2-en-1-ol substrates without an electron withdrawing group (EWG) on the side chain. Transpositions of macrocyclic alkenols or tertiary alcohols bearing an EWG on the side chain were instead carried out in acetonitrile by using an immobilized laccase preparation. Dehydro-Jasmone, dehydro-Hedione, dehydro-Muscone and other fragrance precursors were directly prepared with this procedure, while a synthetic route was developed to easily transform a cyclopentenone derivative into trans-Magnolione and dehydro-Magnolione. The rearrangement of exocyclic allylic alcohols was tested as well, and a dynamic kinetic resolution was observed: α,β-unsaturated ketones with (E)-configuration and a high diastereomeric excess were synthesized. Finally, the 2,2,6,6-tetramethyl-1-piperidinium tetrafluoroborate (TEMPO+BF4?)/laccase catalysed oxidative rearrangement was combined with the ene-reductase/alcohol dehydrogenase cascade process in a one-pot three-step synthesis of cis or trans 3-methylcyclohexan-1-ol, in both cases with a high optical purity. (Figure presented.).
Model Studies to Access the [6,7,5,5]-Core of Ineleganolide Using Tandem Translactonization-Cope or Cyclopropanation-Cope Rearrangements as Key Steps
Roizen, Jennifer L.,Jones, Amanda C.,Smith, Russell C.,Virgil, Scott C.,Stoltz, Brian M.
, p. 13051 - 13067 (2017/12/26)
Recently, we reported a convergent cyclopropanation-Cope approach to the core of ineleganolide, which was the first disclosed synthesis of the core of the norditerpene natural product ineleganolide. In this complementary work, a model system for the core
Novel PDC catalyzed oxidative rearrangement of tertiary allylic alcohols to β-substituted enones
Matsunaga, Kazuma,Hirajima, Hironori,Kishida, Atsushi,Takatori, Kazuhiko,Nagaoka, Hiroto
, p. 5941 - 5944 (2015/11/02)
Novel pyridinium dichromate (PDC) catalyzed oxidative rearrangement for the conversion of tertiary allylic alcohols to ?-substituted enones is described. Using a catalytic amount of PDC with PhI(OAc)2 as a co-oxidant in the presence of magnesium sulfate and water under oxygen was found effective for this rearrangement.
Efficient addition of cerium(III) enolate of ethyl acetate to ketones: application to the synthesis of β-ethoxycarbonylmethyl α,β-unsaturated ketones
Liu, Hsing-Jang,Zhu, Bing-Yan
, p. 2008 - 2013 (2007/10/02)
The cerium(III) enolate derived from ethyl acetate was shown to undergo facile addition with ketones.With conjugated enones, 1,2-addition products were formed exclusively.Oxidative 1,3-oxygen transportation of these products provides an efficient route to
