0000000000048542
AUTHOR
Luisa Lahoz
Synthesis of Elemane Bis-Lactones from Santonin – Synthesis of the Reported Structure ofseco-Isoerivanin Pseudo Acid and Formal Synthesis of (+)-8-Deoxyvernolepin
The synthesis of the reported structure for seco-isoerivanin pseudo acid (1) and of an elemane bis-lactone 5 from santonin (4) through a common vinylic precursor 12 is described. Compound 5 is a known intermediate in a previous synthesis of the antitumor compound (+)-8-deoxyvernolepin (3). The vinyl group of 12 underwent a regio- and diastereoselective anti addition of an external electrophile and an intramolecular condensation to yield either the selenolactone 13 or the hydroxylactone 17. The lactones 13 and 17 served as key intermediates in the total synthesis of 1 and 5 respectively. A revision of the structure of seco-isoerivanin pseudo acid to the C-10 epimer is suggested on the basis …
ChemInform Abstract: The Reduction of α,β-Unsaturated Nitriles and α- Halonitriles with Sodium Hydrogen Telluride.
Abstract Sodium hydrogen telluride reacts chemoselectively with α,β-unsaturated nitriles and α-halonitriles linked to aromatic and aliphatic substituents to give the corresponding saturated nitriles with good yields.
ChemInform Abstract: Synthesis of Elemane Bis-lactones Structurally Related to Vernolepin.
Abstract The chemical transformation of santonin into an elemane bis -lactone structurally related to the antitumour compound vernolepin is reported. The transformation of ring A of santonin into a hemiacetal δ-lactone was achieved in eleven steps. The spectroscopic characteristics of the synthetic product obtained in this way revealed that the proposed structure for the natural product should be revised.
ChemInform Abstract: Synthesis of Elemane Bis-lactones from Santonin - Synthesis of the Reported Structure of seco-Isoerivanin Pseudo Acid and Formal Synthesis of (+)-8-Deoxyvernolepin.
The synthesis of the reported structure for seco-isoerivanin pseudo acid (1) and of an elemane bis-lactone 5 from santonin (4) through a common vinylic precursor 12 is described. Compound 5 is a known intermediate in a previous synthesis of the antitumor compound (+)-8-deoxyvernolepin (3). The vinyl group of 12 underwent a regio- and diastereoselective anti addition of an external electrophile and an intramolecular condensation to yield either the selenolactone 13 or the hydroxylactone 17. The lactones 13 and 17 served as key intermediates in the total synthesis of 1 and 5 respectively. A revision of the structure of seco-isoerivanin pseudo acid to the C-10 epimer is suggested on the basis …
Oxygen atom transfer reaction involving oxomolybdenum complexes with sterically bulky thiocarboxylate ligands and biochemical interesting substrates in methanol at neutral pH
Abstract Oxidation–reduction reactions of substrates in systems containing the complex [Mo VI O 2 (O 2 CC(S)CH 3 Ph) 2 ] 2− in methanol have been investigated as models of oxo-transfer reactions. At neutral pH, the [Mo VI O 2 (O 2 CC(S)CH 3 Ph) 2 ] 2− reacts with Me 2 PhP or n -butanethiol to yield a [Mo IV O(O 2 CC(S)CH 3 Ph) 2 ] 2− species and Me 2 PhPO or disulfide, respectively. The Mo IV O complex reduces a variety of substrates XO = Me 2 SO and pyridine N-oxide conducing formation of X = Me 2 S and pyridine. The occurrence of these reactions produces a catalytic system Me 2 PhP + XO → Me 2 PhPO + X and 2BuSH + XO → [BuS] 2 + X + H 2 O. In this work we have also included the study of …
ChemInform Abstract: Synthesis of Plagiochiline N from Santonin.
This article reports the transformation of O-acetylisophotosantonin, obtained by photochemical rearrangement of santonin, into plagiochiline N, an ent-2,3-secoaromadendrane isolated from Plagiochila ovalifolia. The synthesis was carried out in a sequence involving as the key steps (a) the substitution of the lactone moiety by a gem-dimethylcyclopropane ring through a synthetic intermediate having a C(6)-C(7) double bond and (b) the ozonolysis of the C(2)-C(3) bond followed by cyclization to the dihydropyran ring characteristic of plagiochiline N. Spectroscopic data of the synthetic product fully coincided with the reported data for the natural product.
Synthesis of elemane bis-lactones structurally related to vernolepin
Abstract The chemical transformation of santonin into an elemane bis -lactone structurally related to the antitumour compound vernolepin is reported. The transformation of ring A of santonin into a hemiacetal δ-lactone was achieved in eleven steps. The spectroscopic characteristics of the synthetic product obtained in this way revealed that the proposed structure for the natural product should be revised.
Synthesis of plagiochiline N from santonin.
This article reports the transformation of O-acetylisophotosantonin, obtained by photochemical rearrangement of santonin, into plagiochiline N, an ent-2,3-secoaromadendrane isolated from Plagiochila ovalifolia. The synthesis was carried out in a sequence involving as the key steps (a) the substitution of the lactone moiety by a gem-dimethylcyclopropane ring through a synthetic intermediate having a C(6)-C(7) double bond and (b) the ozonolysis of the C(2)-C(3) bond followed by cyclization to the dihydropyran ring characteristic of plagiochiline N. Spectroscopic data of the synthetic product fully coincided with the reported data for the natural product.