Process for producing bicyclo[3.3.0]octanes

Details Process for producing bicyclo[3.3.0]octanes Process for producing bicyclo[3.3.0]octanes

1986-07-16

1990-12-18

Gerstl, Robert

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

562501, C07C17700

Patent

active

049787756

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

This invention relates to a process for producing bicyclo[3.3.0] octanes. More particularly, this invention relates to an industrially advantageous process for producing isocarbacyclins or their synthetical intermediates, bicyclo[3.3.0] octanes.


BACKGROUND OF THE ART

Carbocyclines are stable compounds of prostaglandin I.sub.2 and are very useful compounds as an antithrombotic agent. It has recently been found that 9(0)-methano-.DELTA..sup.6 -(9.alpha.)-prostaglandin I.sub.1 (isocarbacyclin) is a compound which displays the strongest anticoagulant action against thrombocyte coagulation among the analogues of carbocycline and is expected to be used as medicine (Ikegami et al., Tetrahedron Lett., 33, 3493 (1983); ibid., 33, 3497, (1983); European Laid-Open Patent Publication No. 0134246).
With regard to the process for producing isocarbocycline, a method in which an epoxide compound expressed by a formula ##STR3## is used as an intermediate (Ikegami et al., Tetrahedron Lett., 33, 3493 (1983)) or a method in which an enolic compound expressed by a formula ##STR4## is used (Ikegami et al., Tetrahedron Lett., 33, 3497 (1983)) has hitherto been known. In these methods, however, the synthetic preparation of the intermediate epoxide compound or enolic compound from the starting material inevitably requires many processes and accordingly these methods of synthesizing isocarbacyclin can hardly be regarded as advantageous ones from the industrial viewpoint.
Apart from these methods, methods have recently been proposed to synthesize isocarbacyclin by use of a bicyclo[3.3.0] octane compound which is expressed by a formula shown below. ##STR5## There are, for instance, such methods as (i) A method comprising introducing an .alpha.-chain to Corey lactone, a starting material, in the Wittig's reaction, establishing the aforementioned bicyclo[3.3.0] octane through an epoxide compound, and further subjecting to the oxidation reaction, Horner-Emmons reaction, and reduction reaction to give isocarbacyclin (Chemistry Letters, 1069 (1984)); a starting material, in the Wittig's reaction, establishing a diene compound via diol compound and aldehyde compound, which is then selectively reduced to give the aforementioned bicyclo[3.3.0] octane compound, and following the same procedures as taken in the preceding (i) to obtain isocarbacyclin (Chemistry Letters, 579 (1984)); and starting material, in the Wittig's reaction, establishing an aldehyde compound, which is then subjected to the intramolecular thermal reaction to establish the aforementioned bicyclo[3.3.0] octane compound, and subjecting this compound to the same procedure as taken in the abovementioned (i) to obtain isocarbacyclin (Tetrahedron Lett., 25, 1067 (1984)).
However, all of these methods have a demerit of being not industrially advantageous since they require multistage processes in obtaining the intermediate bicyclo[3.3.0] octane compound and the overall yield is not so large.


DISCLOSURE OF THE INVENTION

A primary object of this invention is to provide an industrially advantageous process for producing isocarbacyclins.
Another object of this invention is to provide an industrially excellent process for producing synthetic intermediates of isocarbacyclins.
A further object of this invention is to provide novel synthetic intermediates of isocarbacyclins.
Other objects of this invention will be clearly understood by referring to the following detailed description.
The objects and advantages of this invention will be achieved by the preparing process described below.
This is a process for preparing bicyclo[3.3.0] octanes expressed by the following formula (II) ##STR6## wherein R.sub.11 indicates a hydrogen atom, C.sub.1 .about.C.sub.10 alkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted alicyclic group, substituted or unsubstituted phenyl (C.sub.1 .about.C.sub.2) alkyl group, tri (C.sub.1 .about.C.sub.7) hydrocarbon silyl group or one equivalent of cation; R.omega.' indicates a substituted or unsubstituted C.sub.1

REFERENCES:
Al-Kozimi, J. Am. Chem. Soc. 77, 2479 (1955).
Garmaise, J. Org. Chem. 27, 4509 (1962).
Robins, J.A.C.S. 103, 932 (1981).
Gemal, J.A.C.S. 103, 5454 (1981).
Gram, Organic Chemistry, p. 15 (1964)

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