This invention provides illudin derivatives, intermediates, preparation methods, pharmaceutical compositions and uses thereof. Specific examples include novel synthetic routes to prepare illudin derivatives and an illudin derivative having a positive optical rotation, which has therapeutic value.

Compositions of manganese accumulating plants.

Compositions of manganese accumulating plants.

The present invention provides a process for preparing a (1,2-dimethyl-3-methylenecyclopentyl)acetate compound of the following general formula (3), wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms, the process comprising subjecting a haloacetaldehyde alkyl 2,3-dimethyl-2-cyclopentenyl acetal compound of the following general formula (1), wherein R is as defined above, and Y represents a halogen atom, to a dehydrohalogenation reaction in the presence of a base, followed by a rearrangement reaction to obtain a (1,2-dimethyl-2-cyclopentenyl)acetate compound of the following general formula (2), wherein R is as defined above, and subjecting the (1,2-dimethyl-2-cyclopentenyl)acetate compound (2) to an epoxidation reaction, followed by an isomerization reaction and then a methylenation reaction to obtain the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound of the following general formula (3). The present invention also provides a process for preparing (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde of the following formula (4), the process comprising the aforesaid process for preparing the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound (3), and converting an alkoxycarbonylmethyl group (i.e., —CH.sub.2C(═O)OR) of the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound (3) to a formylmethyl group (i.e., —CH.sub.2CHO) to obtain (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde (4). ##STR00001##

The present invention provides a process for preparing a (1,2-dimethyl-3-methylenecyclopentyl)acetate compound of the following general formula (3), wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms, the process comprising subjecting a haloacetaldehyde alkyl 2,3-dimethyl-2-cyclopentenyl acetal compound of the following general formula (1), wherein R is as defined above, and Y represents a halogen atom, to a dehydrohalogenation reaction in the presence of a base, followed by a rearrangement reaction to obtain a (1,2-dimethyl-2-cyclopentenyl)acetate compound of the following general formula (2), wherein R is as defined above, and subjecting the (1,2-dimethyl-2-cyclopentenyl)acetate compound (2) to an epoxidation reaction, followed by an isomerization reaction and then a methylenation reaction to obtain the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound of the following general formula (3). The present invention also provides a process for preparing (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde of the following formula (4), the process comprising the aforesaid process for preparing the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound (3), and converting an alkoxycarbonylmethyl group (i.e., —CH.sub.2C(═O)OR) of the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound (3) to a formylmethyl group (i.e., —CH.sub.2CHO) to obtain (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde (4). ##STR00001##

A tetracarbonyl cyclobutene dihydrate compound, having a chemical formula (1).

##STR00001##

A method of synthesizing the tetracarbonyl cyclobutene dihydrate compound, includes: a synthesis step, a separation step, and a purification step. The synthesis step includes: collecting and dissolving 0.5728 g of squaric acid, 2.7948 g of ammonium formate, and 0.0480 g of the palladium complex in 100 mL of anhydrous methanol, heating and stirring a resulting mixture to reflux for 48 hrs, and stopping the reaction. The separation step includes: performing column chromatography analysis on reaction products according to a volume ratio of dichloromethane to anhydrous methanol of 8:2, to obtain a target product. A method of using the tetracarbonyl cyclobutene dihydrate compound, includes: using tetracarbonyl cyclobutene dihydrate compound as a catalyst in addition reaction between ethyl pyruvate and nitromethane, where a conversion rate of ethyl pyruvate reaches 96.1%.

A tetracarbonyl cyclobutene dihydrate compound, having a chemical formula (1).

##STR00001##

A method of synthesizing the tetracarbonyl cyclobutene dihydrate compound, includes: a synthesis step, a separation step, and a purification step. The synthesis step includes: collecting and dissolving 0.5728 g of squaric acid, 2.7948 g of ammonium formate, and 0.0480 g of the palladium complex in 100 mL of anhydrous methanol, heating and stirring a resulting mixture to reflux for 48 hrs, and stopping the reaction. The separation step includes: performing column chromatography analysis on reaction products according to a volume ratio of dichloromethane to anhydrous methanol of 8:2, to obtain a target product. A method of using the tetracarbonyl cyclobutene dihydrate compound, includes: using tetracarbonyl cyclobutene dihydrate compound as a catalyst in addition reaction between ethyl pyruvate and nitromethane, where a conversion rate of ethyl pyruvate reaches 96.1%.

A tetracarbonyl cyclobutene dihydrate compound, having a chemical formula (1).

##STR00001##

A method of synthesizing the tetracarbonyl cyclobutene dihydrate compound, includes: a synthesis step, a separation step, and a purification step. The synthesis step includes: collecting and dissolving 0.5728 g of squaric acid, 2.7948 g of ammonium formate, and 0.0480 g of the palladium complex in 100 mL of anhydrous methanol, heating and stirring a resulting mixture to reflux for 48 hrs, and stopping the reaction. The separation step includes: performing column chromatography analysis on reaction products according to a volume ratio of dichloromethane to anhydrous methanol of 8:2, to obtain a target product. A method of using the tetracarbonyl cyclobutene dihydrate compound, includes: using tetracarbonyl cyclobutene dihydrate compound as a catalyst in addition reaction between ethyl pyruvate and nitromethane, where a conversion rate of ethyl pyruvate reaches 96.1%.

The present invention provides a novel cationic ruthenium complex which is easy to produce and handle and can be procured at a relatively low cost and a production method for the ruthenium complex, a method for producing an alcohol or the like using the ruthenium complex as a catalyst, a method for producing a carbonyl compound using the ruthenium complex as a catalyst, and a method for producing a N-alkylamine compound using the ruthenium complex as a catalyst. The present invention pertains to a ruthenium complex represented by general formula (1): [RuX(CO).sub.2(PNP)]Y (wherein, X represents a monovalent anionic monodentate ligand, Y represents a counter anion, PNP represents a tridentate ligand, and CO represents carbon monoxide), a production method for the ruthenium complex, a catalyst containing the ruthenium complex, and a production method for various organic compounds using the catalyst.

The present invention provides a novel cationic ruthenium complex which is easy to produce and handle and can be procured at a relatively low cost and a production method for the ruthenium complex, a method for producing an alcohol or the like using the ruthenium complex as a catalyst, a method for producing a carbonyl compound using the ruthenium complex as a catalyst, and a method for producing a N-alkylamine compound using the ruthenium complex as a catalyst. The present invention pertains to a ruthenium complex represented by general formula (1): [RuX(CO).sub.2(PNP)]Y (wherein, X represents a monovalent anionic monodentate ligand, Y represents a counter anion, PNP represents a tridentate ligand, and CO represents carbon monoxide), a production method for the ruthenium complex, a catalyst containing the ruthenium complex, and a production method for various organic compounds using the catalyst.