A first asymmetric total synthesis of (-)-isoschizogamine has been accomplished. Our synthesis features the facile construction of the carbon framework of the natural product through a Wagner-Meerwein rearrangement, a tandem metathesis, a stereoselective rhodium-mediated 1,4-addition of an arylboronic acid, and a ring-closing metathesis via a hemiaminal ether.
A formal total synthesis
of pactamycin (1) has been
accomplished by face-selective and regioselective nitroso Diels–Alder
(NDA) reaction of acyl nitroso compound 14, which contains
a camphorsultam chiral auxiliary, and chiral cyclopentadiene 12. Construction of the chiral secondary alcohol of 12 was performed by (S,S)-Ts-DENEB catalyst-mediated reduction, and the NDA adduct 15a was readily converted to Johnson’s intermediate 21.
An alternative synthetic route toward a key intermediate in the total synthesis of isoschizogamine is described. The Claisen-Johnson rearrangement stereoselectively constructed a quaternary carbon. Trifluoroperacetic acid mediated the Baeyer-Villiger oxidation to form a bicyclic lactone. The Mukaiyama-Matsuo protocol converted the lactone into an α,β-unsaturated lactone, that was used as the substrate for the rhodium-mediated 1,4-addition of an arylboronic acid.
Stereoselective construction of the cyclopentane core 21 of pactamycin (1) was achieved from symmetric cyclohexadiene 7. Our synthetic strategy features catalytic Rh-mediated desymmetric aziridination of the cyclohexadiene derivative, selective ring-opening reaction at the C2 position of sulfonylaziridine with NaN 3 , ring-contraction of cyclohexene 9 by ozonolysis followed by intramolecular aldol reaction via ena-Eur.
491in the protected derivatives 27. Therefore, we selected less hindrance epoxy derivatives 15c .
Since the wear of front-rod bearings of railroad switches induce the switch failure, wear evaluation is indispensable. On the other hand, the various parts of railroad switches are adjusted so as to avoid derailment. For example, the attachment position of the adjustment nut of switch adjuster rod could enlarge the contact force between tongue rail and stock rail. The extension of front rod is also used to eliminate the gap between the toe of tongue rail and stock rail. In this paper, the bearing wear during the switching operation is estimated by multi-body dynamics simulation. The effects of the attachment position of adjustment nut and the extension of front rod are also evaluated. When the switch moves rightward, the driving force of electric point machine is transmitted to switch rod through switch adjuster rod. Then, the force is transmitted to right tongue rail through right switch rod bracket which connects switch rod and right tongue rail. Although the attachment position of adjustment nut controls the contact force between tongue rail and stock rail, that does not change the path of force transmission and the force acting on the bearing. Therefore, the attachment position does not affect the bearing wear. On the other hand, the extension of front rod changes the path of force transmission. The most of driving force of electric point machine is transmitted to the left switch rod bracket, front rod and right tongue rail in order. Therefore, the increase in the force acting on the bearing increases its wear. In the case of 6 mm extension of front rod, the estimated amount of wear is 3.44 μm, which is 3 times larger than the case of no extension.
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