Syntheses and medicinal chemistry of spiro heterocyclic steroids

• Laura L. Romero-Hernández,
• Ana Isabel Ahuja-Casarín,
• Penélope Merino-Montiel,
• Sara Montiel-Smith,
• José Luis Vega-Báez and
• Jesús Sandoval-Ramírez

Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152

• reported a novel and straightforward method for synthesizing spiro 2,5-dihydrofuran derivatives starting from 17-ethynyl-17-hydroxysteroids such as lynestrenol (38) (Scheme 12) [25]. The 17-hydroxy group of steroids underwent allylation using allyl bromide and sodium hydride. After formation of the alkenyl

• microwaved, a Diels–Alder reaction occurred, yielding the spiro product 41. The reaction conditions were also applied to 17-ethynyl-17-hydroxysteroids derived from mestranol and desogestrel obtaining similar results. The one-pot RCEYM/Diels–Alder reaction was only applied to mestranol and lynestrenol

Diversity-oriented synthesis of 17-spirosteroids

• Benjamin Laroche,
• Thomas Bouvarel,
• Martin Louis-Sylvestre and
• Bastien Nay

Beilstein J. Org. Chem. 2020, 16, 880–887, doi:10.3762/bjoc.16.79

• Paris, Palaiseau Cedex, France 10.3762/bjoc.16.79 Abstract A diversity-oriented synthesis (DOS) approach has been used to functionalize 17-ethynyl-17-hydroxysteroids through a one-pot procedure involving a ring-closing enyne metathesis (RCEYM) and a Diels–Alder reaction on the resulting diene, under

• microwave irradiations. Taking advantage of the propargyl alcohol moiety present on commercially available steroids, this classical strategy was applied to mestranol and lynestrenol, giving a collection of new complex 17-spirosteroids. Keywords: diversity-oriented strategy; 17-ethynyl-17-hydroxysteroids

• targeted strategy, lies on the 17-ethynyl-17-hydroxysteroids (Figure 1). They are commonly used as contraceptive while their skeleton is structurally diversified, especially at ring A. They are thus synthetically relevant as starting materials in a DOS approach. Indeed, after installing an alkenyl ether on