Syntheses of polyurethanes derived from oximes and their photodegradation

Polyoxime-urethanes have been synthesized from dioximes and diisocyanates, and their structures have been ascertained by elemental analysis and infrared spectroscopy. They can be represented by the general formula: These polymer films were photolyzed by using a high-pressure 100-W mercury lamp, and the rate of decomposition of the N? O bond was determined by use of ultraviolet and infrared spectra, or comparing the photochemical behavior with that of corresponding model compounds. Upon irradiating these polymers in the presence or absence of sensitizers or a hydrogen donor, there were obtained photolyzed polymers of low molecular weight, of which the molecular weights were estimated by observing the viscosity changes. To deduce the mechanism of photodegradation of polyoxime-urethane, photolysis of benzophenone oxime-phenyl urethane was investigated as a model compound.     

Neighboring effect of thiol group in acyl transfer reaction on a polymer with a lipoic acid structure

Reductive S-monoacylation of lipoamide with some carboxylic acids and tri-n-butylphosphine was carried out in acetonitrile to obtain the corresponding S-monoacylated compounds in excellent yield. This method was applied to the preparation of S-monoacylated dihydrolipoyl polymer with a neighboring thiol group. The acyl transfer from the polymer to cyclohexylamine was enhanced as much as 64 times by adding silver perchlorate.     

New methods and reagents in organic synthesis. 56. Total syntheses of patellamides B and C,cytotoxic cyclic peptides from a tunicate 2. Their real structures have been determined by their syntheses.

The proposed structures of patellamides B and C, cytotoxic lipophilic cyclic peptides from a marine tunicate, have been revised on the basis of the spectral data of their partial hydrolysates, and their revised structures have been synthetically confirmed by the use of diphenyl phosphorazidate(DPPA) and diethyl phosphorocyanidate(DEPC).     

Synthesis of a novel silicon-bridged [2.2]metacyclophan-9-ene and its photolytic transannular reaction

A novel [2.2]metacyclophane in which two benzene rings are linked together with a carbon-carbon double bond and a disilane unit was prepared. Photolysis of the cyclophane in the presence of oxygen afforded the 4,5-dihydro-4,5-disilapyrene derivative via a transannular dehydrogenation reaction.     

Spongistatin synthetic studies. An efficient, second-generation construction of an advanced ABCD intermediate

[reaction: see text] A short, efficient, and stereocontrolled synthesis of (-)-4, an advanced ABCD subunit of the spongistatins, has been achieved. Central to the synthetic strategy is the multicomponent linchpin union of silyl dithianes with epoxides to access both the AB and CD fragments. Fragment coupling was then achieved via an efficient stereoselective aldol reaction. The linear sequence required 22 steps and proceeded in 4.0% overall yield.     

Zooxanthellamide Cs: vasoconstrictive polyhydroxylated macrolides with the largest lactone ring size from a marine dinoflagellate of Symbiodinium sp

Zooxanthellamide Cs (ZAD-Cs), C(128)H(220)N(2)O(53)S(2) (ca. 2.7 kDa), was obtained from a cultured marine dinoflagellate of the genus Symbiodinium as an inseparable isomeric mixture of polyhydroxylated 61- to 66-membered macrolides. The chemical structures of the components were clarified by detailed 2D NMR analysis to be the macrolactonized analogues of zooxanthellamide A (ZAD-A), which had been previously isolated from the same microalgae. Chemical lability of ZAD-Cs suggests that ZAD-A is an artifact derived from ZAD-Cs during the isolation steps. Three of the components possess the largest (63-, 64-, and 66-membered) ring sizes found to date among the natural macrolides. ZAD-Cs exhibited higher vasoconstrictive activity than that of the zooxanthellatoxins, the first vasoconstrictive macrolides from Symbiodinium sp. The structure-activity relationship suggests that the huge macrolactone structure is important for biological activity. The relationship between the structures of the polyol metabolites and the phylogenetic systematics of Symbiodinium sp. is also discussed.