Total Synthesis Of Tetrodotoxin Research Articles

Total Synthesis of Tetrodotoxin

Key words tetrodotoxin - Diels–Alder cycloaddition - photooxygenation - dipolar cycloaddition

Total Synthesis of Tetrodotoxin

AbstractA total synthesis of tetrodotoxin was accomplished. A Diels–Alder reaction between a known enone and a siloxy diene gave a tricyclic product, the steric bias of which was used to construct the remaining stereogenic centers. A nitrogen atom was introduced either by a four‐step sequence involving a Curtius rearrangement, or a three‐step sequence featuring a newly developed transformation of a terminal alkyne into a nitrile. Introduction of the guanidine moiety followed by the formation of the heterocyclic system by cascade reactions led to tetrodotoxin.

Total Synthesis of Tetrodotoxin.

A total synthesis of tetrodotoxin was accomplished. A Diels-Alder reaction between a known enone and a siloxy diene gave a tricyclic product, the steric bias of which was used to construct the remaining stereogenic centers. A nitrogen atom was introduced either by a four-step sequence involving a Curtius rearrangement, or a three-step sequence featuring a newly developed transformation of a terminal alkyne into a nitrile. Introduction of the guanidine moiety followed by the formation of the heterocyclic system by cascade reactions led to tetrodotoxin.

S-3 Total Synthesis of Tetrodotoxin : Stereochemistry Control in Organic Synthesis

S-3 Total Synthesis of Tetrodotoxin : Stereochemistry Control in Organic Synthesis

Toward the total synthesis of tetrodotoxin: stereoselective construction of the 7-oxanorbornane intermediate

The stereoselective synthesis of 7-oxanorbornane regarding as a key synthetic intermediate of tetrodotoxin (TTX) is reported. The bicyclo ring bearing various functional groups was successfully elaborated by a furan Diels–Alder (DA) reaction. The stereoselective installation of a quaternary amino carbon center to the DA product was achieved with the Tsuji–Trost allylation. The stereochemistry was unambiguously confirmed with X-ray.

ChemInform Abstract: Total Synthesis of Chiriquitoxin, an Analogue of Tetrodotoxin Isolated from the Skin of a Dart Frog.

The first total synthesis of chiriquitoxin, the most structurally complex analogue of tetrodotoxin isolated from a Costa Rican dart frog, has been accomplished from a newly designed intermediate for a variety of tetrodotoxin derivatives. The synthesis includes the third total synthesis of tetrodotoxin in this laboratory, and its intermediate was transformed into chiriquitoxin by a stereocontrolled aldol reaction with a D-camphor-derived lactone for installation of the unique side chain, and a new deprotection of methylthiomethyl (MTM) ether by using a Pummerer rearrangement.

Total Synthesis of Chiriquitoxin, an Analogue of Tetrodotoxin Isolated from the Skin of a Dart Frog

The first total synthesis of chiriquitoxin, the most structurally complex analogue of tetrodotoxin isolated from a Costa Rican dart frog, has been accomplished from a newly designed intermediate for a variety of tetrodotoxin derivatives. The synthesis includes the third total synthesis of tetrodotoxin in this laboratory, and its intermediate was transformed into chiriquitoxin by a stereocontrolled aldol reaction with a D-camphor-derived lactone for installation of the unique side chain, and a new deprotection of methylthiomethyl (MTM) ether by using a Pummerer rearrangement.

An Efficient Total Synthesis of Optically Active Tetrodotoxin from Levoglucosenone

Tetrodotoxin, a toxic principal of puffer-fish poisoning, is one of the most famous marine natural products, and has been known as a formidable synthetic target in synthesis owing to its multifunctional structure and unusual chemical properties. From the perspective of supplying tetrodotoxin derivatives such as labeled molecules for biochemical research, we have completed our second total synthesis of tetrodotoxin from a synthetic intermediate for 11-deoxytetrodotoxin, which was previously prepared from levoglucosenone as a chiral starting material in this laboratory. This paper discloses the details of the total synthesis with special reference to significant influences on the neighboring functional groups found in the installation of guanidine. The established route should allow us to prepare the tetrodotoxin-related compounds required for biochemical studies.