Fuyuhiko Matsuda

Asymmetric total synthesis of danicalipin A and evaluation of biological activity.

Asymmetric total synthesis of danicalipin A was achieved. The synthesis was characterized by diastereoselective introduction of chlorine atoms. Biological activities with synthetic danicalipin A, its enantiomer, and racemate were also evaluated toward brine shrimp. Both enantiomers of danicalipin A showed almost the same activity.

Stereocontrolled total synthesis of (+)-pederine

Abstract A mild one-pot method for the synthesis of acyclic N-(1-methoxyalkyl)amides starting from carboxylic acid and methyl imidates has been developed and applied to the first total synthesis of (+)-pederine (1), a potent insect poison. Furthermore, the stereocontrolled total synthesis of 1 was also achieved by employing acid catalyzed double alkoxy-exchange reaction of N-(1 -methoxylakyl)amide group as key step.

Synthesis and cytotoxicity of the acyclic (E)- and (Z)-dienediyne systems related to neocarzinostatine chromophore

Abstract Synthesis of the title compounds could be achieved by featuring the Pd-catalyzed coupling reaction of stereo-defined (E)-and (Z)-enol triflates with an acetylene derivative. It was found that the acyclic (Z)-dienediyne system obviously exhibits in vitro cytotoxicity against P388 murine leukemia stronger than that for the corresponding (E)-isomer.

A simple method for synthesis of amides and peptides through acyl chlorides : A rapid synthesis of thyrotropin releasing hormone

Abstract By improvement of the classical SOCl 2 -pyridine method for the preparation of acid chlorides, amides and optically pure peptides were synthesized rapidly in a simple manner from DCHA dicyclohexylammonium) salts of carboxylic acids. This modified SOCl 2 -pyridine method was applied to a rapid synthesis of TRH.

Synthetic studies on virantmycin. 1. Total synthesis of (±)-virantmycin and determination of its relative stereochemistry

Abstract The efficient and stereospecific route to the tetrahydroquinoline ring models 3 and 4 of virantmycin has been developed by means of an intramolecular nitrene addition reaction as a key step. In the NOE experiments of 4 and 3 we revealed that a ring inversion occurs in their piperidine ring system and determined the relative stereochemistry by capturing each half-chair conformer as cyclic carbamates 26 and 27 , respectively. Utilizing this protocol total syntheses of (±)- 1 and its diastereomer (±)- 2 have been accomplished and the relative stereochemistry of virantmycin has been established as shown in 1 .

Total synthesis of natural (+)-sesbanimide a and (-)-sesbanimide b

The first total synthesis of natural (+)-sesbanimide A (1) and (-)-sesbanimide B (2), potent antitumor alkaloids isolated from the seeds of the leguminous plant, Sesbania drummondii, has been accomplished starting from D-(+)-xylose. This total synthesis involves efficient construction of the optically active AB-ring system from D-(+)-xylose, introduction of the C5-unit into the AB-ring system in a form of exo-methylene-γ-lactone, and elaboration of the labile C-ring system at the last stage of the synthesis. The absolute configurations of natural 1 and 2 could be obviously established by our total synthesis.

Total syntheses of (+)-nogarene and (+)-7,8-dihydronogarene

Total syntheses of the title compounds, the simplest and the hitherto unknown novel nogalamycin congeners, were first accomplished by elaborating the CDEF-ring system (5) from the methyl ketone (6) and subjecting 5 to regioselective Diels-Alder reaction with the bistrimethylsilyl keteneacetal (22).

Remote acyclic stereocontrol. Chiral synthesis of (+)-pedamide

Abstract Synthesis of optically active pedamide (3), one of the tetrahydropyran moieties of the potent insect poison pederine (1), has been accomplished through a new, remote controlled asymmetric reduction of a ketone as key step.

Efficient construction of 8-membered ring framework of vinigrol through SmI2-induced coupling cyclization

Abstract The 8-membered ring framework of vinigrol, a unique tricyclic diterpene isolated as a novel antihypertensive compound from a culture of Virgaria nigra , was efficiently synthesized employing an SmI 2 -induced intramolecular coupling. It is particularly noteworthy that the 8-membered carbocycle was cyclized in quantitative yields under non-high-dilution conditions .

Efficient synthesis and antitumor activity of an enantiomeric pair of the sesbanimide AB-ring systems

Abstract An enantiomeric pair of the fully unprotected AB-ring systems of sesbanimide A (1), a potent antitumor alkaloid, was efficiently synthesized from readily available D- and L-xylose. Examination on their in vitro antitumor activity clearly disclosed that the AB-ring system only made a small contribution to the notable cytotoxicity of 1.