Total synthesis of plakortide E and biomimetic synthesis of plakortone B.
نویسندگان
چکیده
The total synthesis of plakortide E (1a) is reported. A novel palladium-catalyzed approach towards 1,2-dioxolanes as well as an alternative substrate-controlled route leading exclusively to cis-highly substituted 1,2-dioxolanes have been developed. A lipase-catalyzed kinetic resolution was employed to provide optically pure 1,2-dioxolane central cores. Coupling of the central cores and side chains was achieved by a modified Negishi reaction. All four isomeric structures of plakortide E methyl ester, namely, 26a-d were synthesized. One of the structures, 26d, was shown to be identical with the natural plakortide E methyl ester on the basis of (1)H, (13)C NMR spectra and specific rotation comparisons. With the plakortide E methyl ester (4S,6R,10R)-(-)-cis-26d and its other three isomers in hand, we successfully converted them into (3S,4S,6R,10R)-plakortone B (2a), and its isomers ent-2a, 2b and ent-2b via an intramolecular oxa-Michael addition/lactonization cascade reaction. Finally, saponification converted 1,2-dioxolane 26d into plakortide E (1a) whose absolute configuration (4S,6R,10R) was confirmed by comparison of spectral and physical data with those reported.
منابع مشابه
Biomimetic synthesis of 1-aryl-2,5-dimethyl pyrroles using egg white nano-ovalbumin at room temperature under solvent-free conditions
Ovalbumin, as the major component of egg-white, is a globular, biocompatible, nontoxic and biodegradable phosphoglyco protein. This protein with the molecular weight of 44.5 kDa, contains 385 residues of amino acids with isoelectric point (pI) of 4.5. Many purification procedures have been reported for egg-white proteins such as gel permeation and anion exchange chromatography. In this study, w...
متن کاملStudies of a Tripodal Biomimetic Siderophore Analog: An Efficient Encapsulation for Fe(III) Ion
A new tris-(2-aminoethyl)amine (TREN) capped tripodal Schiff base ligand has been developed by mimicking structural features of a natural siderophore, Bacillibactin, by substituting the catechol units with salicylaldehyde and employing amino acid as spacer. Synthesis of the ligand N-[2-[bis[2-[[2-[(2-hydroxyphenyl)methylamino]acetyl] amino]ethyl]amino]ethyl]-2-[(2-hydroxyphenyl)methylamino]...
متن کاملBiomimetic total synthesis of litseaverticillols B, E, I, and J and structural reassignment of litseaverticillol E.
[reaction: see text] The first total synthesis of litseaverticillols B (1), E (2), I (4), and J (5) as well as the structural reassignment of litseaverticillol E (2) have been achieved by means of a biomimetic sequence of transformations during which a [4 + 2]-initiated reaction cascade and an ene reaction, both involving singlet oxygen ((1)O(2)), formed key steps. The reassignment of the struc...
متن کاملA biomimetic synthesis of (±)-basiliolide B.
A highly diastereoselective and practical biomimetic total synthesis of (±)-basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (O-methylation and O-acylation) for the unprecedented 7-methoxy-4,5-dihydro-3H-oxepin-2-one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomim...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Chemistry
دوره 17 21 شماره
صفحات -
تاریخ انتشار 2011