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. 2023 Oct 13;28(20):7068.
doi: 10.3390/molecules28207068.

Montmorillonite Catalyzed Synthesis of Novel Steroid Dimers

Aneta M Tomkiel  1 , Adam D Majewski  1   2 , Leszek Siergiejczyk  1 , Jacek W Morzycki  1
Affiliations

Montmorillonite Catalyzed Synthesis of Novel Steroid Dimers

Aneta M Tomkiel et al. Molecules. .

Abstract

The reactions of sterols (androst-5-en-3β-ol-17-one, diosgenin, and cholesterol) and their tosylates with hydroquinone aimed at the synthesis of O,O-1,4-phenylene-linked steroid dimers were studied. The reaction course strongly depended on the conditions used. The study has shown that the major reaction products are the elimination products and unusual steroid dimers resulting from the nucleophilic attack of the hydroquinone C2 carbon atom on the steroid C3 position, followed by an intramolecular addition to the C5-C6 double bond. A different reaction course was observed when montmorillonite K10 was used as a catalyst. The reaction of androst-5-en-3β-ol-17-one under the promotion of this catalyst afforded the O,O-1,4-phenylene-linked steroid dimer in addition to the disteroidal ether. The formation of the latter compound was suppressed by using 3-tosylate as a substrate instead of the free sterol. The reactions of androst-5-en-3β-ol-17-one tosylate and cholesteryl tosylate with hydroquinone catalyzed by montmorillonite K10 carried out under optimized conditions afforded the desired dimers in 31% and 67% yield, respectively.

Keywords: 1,4-phenylene-linked dimers; DHEA; cholesterol; montmorillonite; steroid dimers; steroids.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Naturally occurring steroid dimers.
Figure 2
Figure 2
Target steroid dimers (1–3) and starting materials (4–6).
Scheme 1
Scheme 1
The reactions of androst-5-en-3β-ol-17-one tosylate with hydroquinone.
Scheme 2
Scheme 2
A presumable mechanism of 11b formation.
Scheme 3
Scheme 3
A presumable mechanism of 11a formation.
Figure 3
Figure 3
Ball and stick presentation of optimized structures of dimers 11a and 11b.
Figure 4
Figure 4
The diagnostic fragment of 1H NMR spectra of 11a, 11b, and 11c dimers.
See this image and copyright information in PMC

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