327048-79-3Relevant academic research and scientific papers
Hemisynthesis of 2,3,4-13C3-1,4-androstadien-3,17-dione: A key precursor for the synthesis of 13C3-androstanes and 13C3-estranes
Berthonneau, Clément,Nun, Pierrick,Rivière, Matthieu,Pauvert, Mickael,Dénès, Fabrice,Lebreton, Jacques
, p. 3727 - 3737 (2018)
In this contribution, we describe two simple and efficient routes for the preparation of keto-aldehyde 1, a key intermediate for the synthesis of 13C3-androstanes and 13C3-estranes. In the first route, the targeted aldehyde 1 was obtained in 40% overall yield from 1,4-androstadien-3,17-dione (3 mmol scale) via a two-step sequence involving a one-pot, abnormal ozonolysis/sulfur oxidation/retro-Michael/ozonolysis process. Alternatively, a second route from 4-androsten-3,17-dione, using a six-step sequence, was optimized to produce 40 mmol batches of the key intermediate 1 in 42% overall yield. At the final stage, the A-ring was reconstructed through a Wittig reaction with the 1-triphenylphosphoranylidene-13C3-2-propanone 2, followed by an intramolecular condensation assisted by thioacetic acid via a Michael addition/retro-Michael reaction sequence to provide 2,3,4-13C3-1,4-androstadien-3,17-dione.
Novel partial synthetic approaches to replace carbons 2,3,4 of steroids. A methodology to label testosterone and progesterone with 13C in the steroid A ring. Part 2
Kockert, Karlheinz,Vierhapper, Friedrich W
, p. 9967 - 9974 (2007/10/03)
Fragmentation of the A ring of the steroid hormone testosterone to yield the 10-formyl-5-oxo-des A intermediate was achieved by lactolization, lactonization, ozonolysis, and oxidation of the resulting methylol group. The reconstruction of the A ring was carried out via a Wittig synthesis with triphenylphosphoranylidene-2-propanone-13C3. Syntheses of the ylide, of the 13C3-testosterone, and of 13C3-progesterone took place in acceptable yields. (C) 2000 Elsevier Science Ltd.
