Carl Djerassi

Steroids from sponges

Abstract The sponges Stelleta clarella Tethya aurantia, Lissodendoryx noxiosa, Haliclona permollis and Haliclona sp. were examined for steroids. All sponges contained C27-C29, Δ5, mono and diunsaturated sterols. In addition, the sponge Tethya aurantia contained Z - 24 - propylidene - cholest - 5- en -3β-ol (19) and the 5α,8α-peroxides of cholesta - 5,7 - dien - 3β - ol, ergosterol, ergosta - 5,7,24(28) - trien - 3β - ol and 24ξ - ethyl - cholesta - 5,7 - dien - 3β - ol (29, 30, 31 and 32). The sponge Stelleta clarella also contained 24 - nor - cholesta - 4,22 - dien - 3 - one (21), cholesta - 4,22 - dien - 3 - one (22), 24ξ - methyl - cholesta - 4,22 - dien - 3 - one (24), ergosta - 4,24(28) - dien - 3 - one (25), (E) - stigmasta - 4,24(28) - dien - 3 - one (28), 5α - cholestanol (5), 5α - ergostanol (7) and 5α - poriferastanol (9) The possible biosynthetic significance of these hitherto undescribed peroxides and enones from marine sources is discussed. A synthesis of 19 is also described.

Rotatory dispersion curves of cyclopropyl-ketones and epoxy-ketones☆

Abstract The optical rotatory dispersion curves of a wide variety of epoxy ketones and cyclopropyl ketones are reported and discussed; the results are analysed in terms of the Octant Rule. It is shown that cyclopropane and ethylene oxide (oxiran) rings make contributions to the Cotton Effect at ca. 290 mμ which are opposite in sign to those made by alkyl groups.

Birth control after 1984.

1) Eric Blair (alias George Orwell) can rest easy in his grave, because birth control by governmentally imposed methods, such as incorporation of a contraceptive agent into drinking water, is totally unfeasible by 1984. 2) Fundamentally new birth control procedures in the female (for example, a once-a-month luteolytic or abortifacient agent) and a male contraceptive pill probably will not be developed until the 1980s at the earliest, and then only if major steps of the type outlined in this article are instituted in the early 1970s. Development during the next decade of practical new methods of birth control without important incentives for continued active participation by the pharmaceutical industry is highly unlikely. If none are developed, birth control in 1984 will not differ significantly from that of today.

Minor and trace sterols in marine invertebrates 1. General methods of analysis

3beta-Hydroxy sterols occurring at a concentration of at least 0.001% of the sterol mixtures of Pseudoplexaura porosa and Plexaura homomalla have been fractionated using a series of refined techniques and subsequently analyzed using combined gas chromatography-mass spectrometry (GC-MS) in the development of a procedure for examining the minor and trace components of marine sterol mixtures. A total of 49 sterols were found which spanned a molecular weight range of 274 to 440. In addition delta4-3-keto analogs of cholesterol, 24-methylcholesterol and gorgosterol were found in the extracts of P. homomalla. Initial separation of various natural sterol-containing conjugates and free sterols was found to have a number of advantages. Fractional digitonin precipitation and alumina column chromatography were found to possess greater sterol separation abilities than previously recognized. Many of the minor sterols were found to possess novel structures including a series of short side chain sterols, 19-nor sterols, 5beta-stanols and 4-monomethyl sterols for which structure elucidation work is continuing.

Biosynthetic studies of marine lipids—3 : Experimental demonstration of the course of side chain extension in marine sterols

Abstract The Pacific sponge Aplysina fistularis was fed cholesterol-[4- 14 C],(24 R )-methyl-25-dehydrocholesterol-[26- 14 C] (epicodisterol[26- 14 C]), (24 S )-methyl-25-dehydrocholesterol-[26- 14 C] (codisterol-[26- 14 C]), and 24-methylenecholesterol-[28- 14 C]. Only epicodisterol, which has the same stereochemistry at C-24 as (24 R ,25 S )-24,26-dimethylcholesterol (aplysterol), was converted with high efficiency into (24 R )-24,27-dimethyl-25-dehydrocholesterol (25-dehydroaplysterol). Further side chain extension [to E -(24 R )-24,26,27-trimethyl-25-dehydrocholesterol (verongulasterol)] could also be demonstrated.

Steroid research at Syntex: "the pill" and cortisone.

The period from late 1949 through 1951 was an extraordinarily productive one in steroid chemistry and especially so at Syntex S.A. in Mexico City. Two of the most important Syntex contributions--the synthesis of 19-nor-17 alpha-ethynyltestosterone (norethindrone) and of cortisone from diosgenin--are described from a historical perspective.

Optical rotatory dispersion studies—XII: Absolute configurations of eperuic and labdanolic acids

Abstract A comparison of the rotatory dispersion curves of appropriate nor-ketones of the eperuic acid and labdanolic acid series with those of derivatives of onocerin and manool establishes the absolute configuration of these diterpene acids.

Isolation of sterols with cyclopropyl-containing side chains from the cultured marine alga peridinium foliaceum

Abstract The sterol fraction of the cultured dinoflagellate Peridinium foliaceum contains in addition to cholesterol, 24-methylcholesterol, 4,24-dimethylcholesterol and dinosterol ( 3c ) small amounts of the cyclopropyl-containing sterols gorgosterol ( 1a ) and 5α-gorgostanol ( 1b ) as well as 4α-methylgorgostanol ( 1c ) and E-4α,22ξ,23ξ (or 24ξ)-trimethylcholest-17(20)-en-3β-ol ( 6c or 7c ). The biosynthetic implications of the first isolation of such sterols from a free-living alga are emphasized.

Minor and trace sterols in marine invertebrates 40. Structure and synthesis of axinyssasterol, 25-methylfucosterol and 24-ethyl-24-methylcholesterol -- novel sponge sterols with highly branched side chains☆

Abstract The isolation, structure determination and synthesis of three novel sterols with unusual side chains is reported. A consistent scheme is proposed which accounts for the biosynthesis of all major and minor sterols in this sponge.

Mass spectral behavior and HPLC of some unusual molecular phospholipid species

The molecular species of the major phospholipids from the marine sponges Parasperella psila and Microciona prolifera were studied using chemical hydrolysis, enzymatic degradation and capillary gas chromatography (GC), high performance liquid chromatography (HPLC), desorption chemical ionization (DCI), fast atom bombardment (FAB) combined with collisionally activated decomposition (CAD) mass spectrometry. Two new solvent systems were developed for the isolation of these species from the sponges. Our investigations indicated the existence of unusual symmetrical phospholipids as major components. 1,2-Di-(5Z,9Z)-5,9-hexacosadienoyl-sn-glycero-3-phosph oethanolamine was found in both organisms, while 1,2-di(5Z,9Z,19Z)-5,9,19-hexacosatrienoyl-sn-gly cero-3-phosphoethanolamine was present in M. prolifera, 1,2-Di-(4Z,7Z,10Z,13Z,16Z,19Z)-4,7,1 0,13,16,19-docosahexaenoyl-sn-glycero-3- phosphocholine was the major molecular species in the PC fraction of M. prolifera.