Convergent asymmetric synthesis of (+)-aureothin employing an oxygenase-mediated resolution step
Need an enzymatic push? The desymmetrization of α,α'-dimethoxy- γ-pyrone allows the convergent and rapid preparation of the complete carbon skeleton of (+)-aureothin (see scheme). The final step in the synthesis of the target molecule is the regiodivergen
Henrot, Matthias,Richter, Martin E.A.,Maddaluno, Jacques,Hertweck, Christian,De Paolis, Micha?l
Absolute configuration of (+)-aureothin: A toxic metabolite possessing γ-pyrone unit
The absolute configuration of aureothin (1) has been determined by synthesis of (-)-aureonone (4) bearing R-configuration. X-Ray single crystallographic analysis of 21 guaranteed the stereochemistry of the chiral center introduced by Sharpless asymmetric epoxidation, as well as that of isoaureothin (3) which was previously synthesized in a similar pathway. Aureothin (1) itself was also synthesized, although Wittig coupling reaction of 4 under basic conditions, caused a partial epimerization of the chiral center.
Flexible Total Synthesis of (±)-Aureothin, a Potent Antiproliferative Agent
Amenable to late-stage preparation of analogues, a flexible and convergent total synthesis of (±)-aureothin is presented. The strategy was based on a desymmetrization of α,α′-dimethoxy-γ-pyrone by a process combining 1,4-addition and alkylation of vinylogous enolate to stereoselectively reach the backbone of the target. Palladium-catalyzed cyanation of an elaborated and isomerizable E,Z dienyl motif followed by Pinner cyclization enabled the construction of the tetrahydrofuran motif while a first approach based on a late-stage oxidation was unsuccessful.
Henrot, Matthias,Jean, Alexandre,Peixoto, Philippe A.,Maddaluno, Jacques,De Paolis, Micha?l
p. 5190 - 5201
(2016/07/06)
Structural fine-tuning of a multifunctional cytochrome P450 monooxygenase
AurH is a unique cytochrome P450 monooxygenase catalyzing the stepwise formation of a homochiral oxygen heterocycle, a key structural and pharmacophoric component of the antibiotic aureothin. The exceptional enzymatic reaction involves a tandem oxygenatio
Zocher, Georg,Richter, Martin E. A.,Mueller, Uwe,Hertweck, Christian
supporting information; experimental part
p. 2292 - 2302
(2011/04/23)
Sequential asymmetric polyketide heterocyclization catalyzed by a single cytochrome p450 monooxygenase (AurH)
(Chemical Equation Presented) Two in one: In vitro biotransformations with the cytochrome P450 monooxygenase AurH from the aureothin (1) biosynthetic pathway provided direct experimental evidence that a single monooxygenase can install two C-O bonds sequentially to form a tetrahydrofuran ring. Structural elucidation of the intermediate 2 revealed the order of bond formation and the stereochemical course of this unprecedented oxygenation-heterocyclization reaction.
Richter, Martin E. A.,Traitcheva, Nelly,Knuepfer, Uwe,Hertweck, Christian
supporting information; experimental part
p. 8872 - 8875
(2009/05/26)
The biomimetic synthesis of SNF4435C and SNF4435D, and the total synthesis of the polyene metabolites aureothin, N-acetyl-aureothamine and spectinabilin
Full details of the biomimetic conversion of polyene metabolite spectinabilin (5) into the isomeric natural products SNF4435C (1) and SNF4435D (2) by a cascade of E/Z-isomerizations and electrocyclizations are reported. Additionally, short total syntheses
Jacobsen, Mikkel F.,Moses, John E.,Adlington, Robert M.,Baldwin, Jack E.
p. 1675 - 1689
(2007/10/03)
A short total synthesis of aureothin and N-acetylaureothamine
(Chemical Equation Presented) The total synthesis of the nitrophenyl pyrones, (±)-aureothin and (±)-N-acetylaureothamine, starting from known 2-ethyl-6-methoxy-3,5-dimethyl-4H-pyran-4-one are described. The key steps involved in the synthesis are the cons
Jacobsen, Mikkel F.,Moses, John E.,Adlington, Robert M.,Baldwin, Jack E.
p. 641 - 644
(2007/10/03)
Stereoselective Syntheses of the Bioactive Polypropionates Aureothin, N-Acetylaureothamine, and Aureonitrile
Concise total syntheses of the bioactive polypropionates aureothin, N-acetylaureothamine, and aureonitrile are described.
Liang, Guangxin,Seiple, Ian B.,Trauner, Dirk
p. 2836 - 2839
(2007/10/03)
More Articles about upstream products of 1400-44-8
Get Best Price for1400-44-82-methoxy-3,5-dimethyl-6-{(2R,5Z)-5-[(2E)-2-methyl-3-(4-nitrophenyl)prop-2-en-1-ylidene]tetrahydrofuran-2-yl}-4H-pyran-4-one