Biomedical subjects

Eiichi Kotani

Publications and source records attributed to Eiichi Kotani.

6 recordsLinked to original sources

PubMed2005

Reactions of 1-naphthols with pi-acceptor p-benzoquinones: oxidative aryl coupling vs. non-oxidative electrophilic arylation.

We investigated the reactions of various 1-naphthols (NPOHs; 1) with p-benzoquinones (Qs), such as 1,4-benzoquinone (BQ) and p-chloranil (CA), as pi-electron acceptors. With electron-rich NPOHs 1a-c, oxidative biaryl coupling and subsequent dehydrogenation reaction took place selectively to give the corresponding 2,2'-binapthyl-1,1'-quinones 3a-c in excellent yield. In the case of electron-deficient NPOHs 1e, f, two different types of reactions occurred in the presence of SnCl4 and ZrO2 under similar conditions: SnCl4 mediated oxidative dimerization and trimerization of NPOH, while ZrO2 promoted electrophilic arylation of Qs with NPOH. The resulting products 3 would be useful synthetic intermediates for naturally occurring diosindigo B, biramentaceone and violet-quinone.

Benzoquinones↗

PubMed2005

Selective allylic hydroxylation of octahydronaphthalene derivatives with a bridgehead double bond using electrochemical method with iron picolinate complexes.

The combination of electrolysis and the Fe(III)(PA)3/O2/CH3CN system was investigated for allylic hydroxylation of octahydronaphthalene derivatives. Substrates with a bridgehead double bond gave the allylic alcohol with alpha-preference, while non-bridgehead olefin did not react smoothly. This system is a useful tool for alpha-selective allylic hydroxylation of octahydronaphthalene derivatives with a bridgehead double bond as model compounds for the AB fused ring of cholesterols.

Cholesterol↗

PubMed2004

A new electrochemical system for stereoselective allylic hydroxylation of cholesteryl acetate with dioxygen induced by iron picolinate complexes.

The oxygenation reaction of cholesteryl acetate 1 was examined with the Fe(III)(PA)(3)/O(2)/MeCN system using an electrochemical method. The constant potential technique gave mainly the 7-hydroxylated product stereoselectively, along with the 7-oxo product. This oxygenation system is mechanistically unique, requiring iron catalyst, dioxygen, and both cathode and anode.

Allyl Compounds↗

PubMed2004

[Development research on oxidase functional model iron complexes].

This paper describes research performed in the Laboratory of Organic Chemistry, Showa Pharmaceutical University. Oxidation reactions involving the oxidase can be divided roughly into two kinds of reactions: The first involves electron removal from an aromatic ring or an active CH-bond. The other reaction involves hydrogen abstraction from an inactive CH-bond. The oxidase models, Fe(DMF)(3)Cl(2)(1+) and Fe(AN)(6)(3+)/AN, which we have synthesized, have been shown to work by the former mechanism, and the models Fe(AN)(6)(3+)-IO(4)(-)/AN, Fe(AN)(6)(2+)-Ac(2)O-H(2)O(2)/AN, Fe(AN)(6)(2+)-2PAH-5Py-Ac(2)O-H(2)O(2)/AN, Fe(PA)(3)(OH(2))-H(2)O(2)/AN and Fe(PA)(3)(OH(2))-O(2)-electrolysis/AN do so by the latter mechanism. Further, we found some iron (II or III)picolinate-H(2)O(2)/AN complexes have the 7 alpha-hydroxylase-like activity.

Acetonitriles↗

PubMed2003

Synthesis of granulatimide positional analogues.

The Stille coupling reaction of the stannylindole 13 with the 5-iodoimidazole derivative 14 (or 27) in the presence of PdCl(2)(PPh(3))(2) gave the corresponding indole-imidazole coupling product 15 (or 28), thereby affording a synthetic approach to 10-methylgranulatimide (7), 15-methylgranulatimide (11), and 10, 15-dimethylgranulatimide (12), as well as 10-methylisogranulatimide B (5).

Alkaloids↗

PubMed2002

New synthetic route to granulatimide and its structural analogues.

The Stille coupling reaction of stannylindole 12 with 4-iodoimidazole 13 (or 24) in the presence of PdCl(2)(PPh(3))(2) gave the corresponding indole-imidazole coupling product 14 (or 25), thereby affording a new synthetic approach to the alkaloid granulatimide (7), isolated from the Brazilian ascidian Didemnum granulatum, as well as its structural analogues, 10-methylgranulatimide (23), 17-methylgranulatimide (30), 10,17-dimethylgranulatimide (31).

Alkaloids↗