Kuraray Co., Ltd.

Nippon Zeon Company, Ltd.

Takeda Chemical Industries, Inc.

Ube Industries, Inc.

Mitsubishi Petrochemical Company Limited

Takasago International Corporation

Jiro Tsuji

Takashi Takahashi

Naoshi Nakagawa

Tetsuo Takigawa

Masao Tsuji

Toshiro Yamada

Kuniaki Goto

Tadakatsu Mandai

Hideaki Kataoka

Isao Shimizu

Manzo Shiono

A process for producing an optically active olefin represented by a formula ##STR1## wherein R.sup.1 represents an organic group and X represents a polycyclic carbon ring group, by reacting a corresponding optically active ester derivative represented by a formula ##STR2## wherein R.sup.1 and X are as defined above and R represents a hydrogen atom, an alkoxy group, an alkenyloxy group or a substituted or unsubstituted aralkyloxy group, with formic acid or a salt thereof in the presence of a catalyst comprising a palladium salt and a tertiary phosphine. Said process makes it possible to produce, at a high yield at a high selectivity, an optically active olefin which has a physiological activity and is useful as a medicine or is useful as an intermediate for the synthesis of physiologically active steroids. Further, said process uses no harmful reagent such as mercury or the like. Thus, it is advantageous as an industrial process.

Process for producing optically active olefin

There are provided pregnane derivatives represented by formula ##STR1## wherein A.sup.1 represents a hydrogen atom or a hydroxyl group, A.sup.2 represents a substituent such as a hydroxyl group when A.sup.1 represents a hydrogen atom, or A.sup.2 represents a hydrogen atom when A.sup.1 represents a hydroxyl group, or A.sup.1 and A.sup.2 are combined together to form an oxo group; D.sup.1 represents a substituent such as a hydroxyl group, and D.sup.2 represents a hydrogen atom, or D.sup.1 and D.sup.2 are combined together to form an epoxy group or a single bond; D.sup.3, D.sup.5 and D.sup.7 each represents a hydrogen atom, D.sup.4 represents a hydroxyl group, and D.sup.6 represents a substituent such as a hydroxyl group, or D.sup.3 and D.sup.4 may be combined together to form an epoxy group or a single bond, or D.sup.4 and D.sup.5 may be combined together to form a single bond, or D.sup.5 and D.sup.6 may be combined together to form an epoxy group or a single bond, or D.sup.6 and D.sup.7 may be combined together to form a single bond; and X.sup.1 and X.sup.2 each represents a lower alkoxyl group or, when combined together, they represent a lower alkylenedioxy or oxo group, and a process for their preparation. The pregnane derivatives are useful as intermediates for synthesizing vitamin D.sub.3 derivatives having a hydroxyl group in the 1.alpha.-position.

Pregnane derivatives and processes for production thereof

A process for preparing an azetidin-2-one derivative represented by formula (2): ##STR1## wherein R.sup.4 and R.sup.5, which may be the same or different, each represents a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, or an alkyl group having from 1 to 8 carbon atoms substituted with an alkoxy group, an acyl group, or an alkoxycarbonyl group; R.sup.6 represents a protective group for an amino group; and R.sup.7 represents a vinylidene group of formula ##STR2## or an acetylene group of formula ##STR3## wherein R.sup.2 and R.sup.3, which may be the same or different, each represents a hydrogen atom or an alkyl group having from 1 to 8 carbon atoms; and R.sup.8 represents an alkyl group having from 1 to 8 carbon atoms corresponding to R.sup.2 or R.sup.3, which comprises reacting a propargyl alcohol derivative represented by formula (1): ##STR4## wherein R.sup.1 represents an alkyl group having from 1 to 6 carbon atoms, a phenyl group, or a halogen-substituted phenyl group; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as defined above, with carbon monoxide in the presence of a palladium complex. The compound (2), an intermediate of penem antibiotics, can be obtained through one reaction step in good yield.

Process for preparing azetidin-2-one derivatives

Steroid compounds

A process for producing an oxime derivative, which comprises protecting the hydroxyimino group of an oxime compound with a protecting agent, subjecting the protected oxime compound to a given reaction, and thereafter deprotecting the reaction product, wherein a 2-alkenylating agent is used as the protecting agent.

Process for production of oxime derivatives

Disclosed are a compound of Formula I: ##STR1## wherein R.sub.1 represents a hydrogen atom or a protective group for a hydroxyl group; and Z represents a direct bond (2,3-cis-5R*, 8S*) or an oxygen atom which forms an oxirane ring having a configuration of (2R*, 3R*, 5R*, 8S*), and a process for preparing the same. By use of the above compound as an intermediate, there can be synthesized periplanone-B which is a sex pheromone of periplaneta.

Novel 10-membered ring compound and process for preparing the same

A process for producing alpha,beta-unsaturated ketones represented by the following general formula ##STR1## wherein R.sub.1 represents a hydrocarbon radical, R.sub.2 represents an organic radical bonded through a carbon-carbon bond, R.sub.3 and R.sub.4 represent a hydrogen atom or a hydrocarbon radical, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be straight-chained or form a ring in arbitrary combinations, which comprises contacting an alpha-disubstituted-beta-keto acid ester represented by the general formula ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined, and R.sub.5, R.sub.6, R.sub.7 and R.sub.8 represent a hydrogen atom or a hydrocarbon radical, with a catalyst consisting essentially of (a) a compound of a platinum-group metal and optionally (b) a monodentate ligand (b).

Process for producing alpha, beta-unsaturated ketones

A process for producing an .alpha.,.beta.-unsaturated ketone of the general formula ##STR1## wherein R.sub.1 represents a hydrocarbon group, R.sub.2 represents an organic group bonded through a carbon-carbon bond, R.sub.3 and R.sub.4 represent a hydrogen atom or a hydrocarbon group, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be linear or may form a ring when taken together in arbitrary combinations, which comprises contacting an .alpha.-disubstituted-.beta.-keto acid ester of the general formula ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined, and R.sub.5, R.sub.6 and R.sub.7 represent a hydrogen atom or a hydrocarbon group, with a catalyst consisting essentially of (a) a compound of a platinum-group metal and (b) and .alpha.,.omega.-alkylenedi(disubstituted)phosphine.

Process for production of .alpha.,.beta.-unsaturated ketones

A compound of the general formula: ##STR1## wherein R.sup.1 is a lower alkyl group; R.sup.2 is H or a lower alkyl group; Y is an oxo group, H or an unprotected or protected hydroxyl group; X is a methylene or ethylene group, for example, 7,7a-dihydro-7aS-methyl-4-(3-butenyl)-1-tert. butoxy-5(6H)-indanone, which is an intermediate for steroids, is prepared by dehydrative cyclization of a compound of the general formula of ##STR2## wherein R.sup.1, R.sup.2, X and Y are the same as above.

Intermediates for steroid synthesis

A compound having the general formula ##STR1## wherein R.sup.1 is a lower alkyl group, R.sup.2 is hydrogen or a lower alkyl group and Y is a protected hydroxyl group, for example, (.+-.)-3.beta.-tert.butoxy-2,3,3a,4,5,7,8,9,9a.beta.,9b.alpha.-decahydro-3 a.beta.-methyl-6-(3-butenyl)-1H-benz(e)inden-7-one, which is an intermediate for steroids, is prepared by dehydrative cyclization of a compound of the general formula ##STR2## wherein the symbols of R.sup.1, Y and R.sup.2 are same as defined above.

Steroid synthesis

1,7-Octadien-3-one of the formula: ##STR1## and a process for preparing the same by oxidizing 1,7-octadien-3-ol.

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Kamakura, Japan

Jiro Tsuji