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.     

Reaction pathway and stereoselectivity of asymmetric synthesis of chrysanthemate with the aratani C1-symmetric salicylaldimine-copper catalyst

The reaction pathway and the mechanism of asymmetric induction in the synthesis of (+)-trans-(1R,3R)-chrysanthemic acid methyl ester from methyl diazoacetate and 2,5-dimethyl-2,4-hexadiene in the presence of a C(1)-chiral salicylaldimine Cu(I) complex has been probed with the aid of hybrid density functional calculations. The key finding is that the alkoxycarbonyl carbene complex intermediate is intrinsically chiral and that the intramolecular hydrogen bonding in the carbene complex transmits the chirality information from the side chain to the carbene complex. Molecular orbital backgrounds of the structure of the carbene complex and the transition state of the cyclopropanation have been elucidated.     

Competitive potentiometric determination of binding constants between α-cyclodextrin and 1-alkanols

The binding constants of 1-alkanols with α-cyclodextrin (α-CD) were determined by indirect competitive potentiometry, although potentiometry is usually inapplicable to nonionic compounds. This novel method utilizes competitive binding of 1-alkanol and octyltrimethylammonium bromide (OTAB) to α-CD in aqueous media, where the concentration of free OTAB depending on the competitive binding is monitored with an OTAB-selective electrode. Therefore, the concentration of 1-alkanol is indirectly estimated from the observed electromotive force. The binding constants of 1-propapnol, 1-butanol, 1-hexanol, and 1-octanol with α-CD, obtained by this method, are close to the literature values. The implications and limitations of this indirect competitive potentiometry were discussed.     

Large-scale separation of metallic and semiconducting single-walled carbon nanotubes

In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way.