5953-69-5Relevant academic research and scientific papers
Convenient stereoselective synthesis of some 3-aminosteroid scaffolds
Solum, Eirik Johansson,Mohamed, Yasser Mahmoud A.
supporting information, p. 1159 - 1164 (2019/04/01)
An efficient stereoselective synthesis 3α- and 3β-aminoandrostan-17-one and 3α-amino dehydroepiandrosten-17-one based on a Mitsunobu reaction has been developed, using azide as the ammonia equivalent. All the products were isolated in high yield.
Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp3)-H Bonds
Wang, Yaxin,Hu, Xiafei,Morales-Rivera, Cristian A.,Li, Guo-Xing,Huang, Xin,He, Gang,Liu, Peng,Chen, Gong
supporting information, p. 9678 - 9684 (2018/07/21)
Reversible cleavage of C(sp3)-H bonds can enable racemization or epimerization, offering a valuable tool to edit the stereochemistry of organic compounds. While epimerization reactions operating via cleavage of acidic C(sp3)-H bonds, such as the Cα-H of carbonyl compounds, have been widely used in organic synthesis and enzyme-catalyzed biosynthesis, epimerization of tertiary carbons bearing a nonacidic C(sp3)-H bond is much more challenging with few practical methods available. Herein, we report the first synthetically useful protocol for the epimerization of tertiary carbons via reversible radical cleavage of unactivated C(sp3)-H bonds with hypervalent iodine reagent benziodoxole azide and H2O under mild conditions. These reactions exhibit excellent reactivity and selectivity for unactivated 3° C-H bonds of various cycloalkanes and offer a powerful strategy for editing the stereochemical configurations of carbon scaffolds intractable to conventional methods. Mechanistic study suggests that the unique ability of N3? to serve as a catalytic H atom shuttle is critical to reversibly break and reform 3° C-H bonds with high efficiency and selectivity.
Abnormal Beckmann fragmentation/ring closing metathesis route for preparation of 18-nor-Δ13(17)-androgens and their 18-nor-13,17-epoxide derivatives
Wang, Cunde,Rath, Nigam P.,Covey, Douglas F.
, p. 7837 - 7839 (2007/10/03)
The synthesis of 18-nor-Δ13(17)-androgens and the structurally related 13,17-epoxides is described. The synthetic route involves the cleavage of 17-ketosteroids by an abnormal Beckmann rearrangement, modification of the D-ring cleavage product
SYNTHESIS OF 5α-ANDROSTANE-3α,16α,17β-TRIOL FROM 3β-HYDROXY-5-ANDROSTEN-17-ONE
Newaz, S. N.,Tcholakian, Robert K.
, p. 445 - 456 (2007/10/02)
5α-Androstane-3α,16α,17β-triol was synthesized from 3β-hydroxy-5-androsten-17-one.The procedure involved catalytic hydrogenation of 3β-hydroxy-5-androsten-17-one to 3β-hydroxy-5α-androstan-17-one.This was followed by conversion of the 3β-hydroxy group to 3α-benzoyloxy group by the Mitsunobu reaction.Further treatment with isopropenyl acetate yielded 5α-androsten-16-ene-3α,17-diol 3-benzoate 17-acetate.This was then converted to 3α,17-dihydroxy-5α-androstan-16-one 3-benzoate 17-acetate via the unstable epoxide intermediate after treatment with m-chloroperoxybenzoic acid.LiAlH4 reduction of this compound formed 5α-androstane-3α,16α,17β-triol. 1H and 13C NMR of various steroids are presented to confirm the structure of this compound.
