Totalsynthese von (+)‐D‐Homo‐19‐nortestosteron

Total Synthesis of (+)-D-Homo-19-nortestosterone A novel total synthesis of (+)-D-homo-19-nortestosterone (2) is described starting from (4a S, 5S)-5-(t-butoxy)-4a-methyl-4, 4a, 5, 6, 7, 7-hexahydro-3 H-naphthalen-2-one (3) as a chiral building block for the rings C and D. The key step involves combining of the derived reactive one-carbon atom adducts 5 and 6 with the β-keto ester 16, a synthon for the rings A and B, to give the Δ9-4, 5-secosteroid 21. 21 was readily transformed to the title compound 2 by hydrogenation and subsequent ring closure. Hydrogenation of the derived 3, 5-dione 22 followed by base-catalyzed cyclization gave the 17a-t-butoxy compound 27 and the 9β, 10α-D-homosteroid 29 as by-product.

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