The Conversion of Hyodesoxycholic Acid to Progesterone

Abstract

A novel transformation of 3α,6α-dihydroxy steroids to their 3β-hydroxy-Δ5 analogues was developed and applied to the preparation of progesterone from hyodesoxycholic acid.

Spontaneous conversion of O -tosylates of 2-(piperazin-1-yl)ethanols into chlorides during classical tosylation procedure

“…79.6-79.88C (lit. 918C[52], 82.5 -838C[53], 848C[54]); 1 H NMR 2.610 (t, 2H, J 5.4, CH 2 -N), 2.680 (t, 4H, J 5.0, CH 2 -2 þ CH 2 -6 piperazine), 3.211 (t, 4H, J 5.0, CH 2 -3 þ CH 2 -5 piperazine), 3.664 (t, 2H, J 5.4, CH 2 -OH), 6.867 (tt, 1H, J 7.3, 0.9, p-Ph), 6.935 (dd, 2H, J 8.8, 0.9, o-Ph), 7.271 (dd, 2H, J 8.7, 7.3, m-Ph);13 C NMR 49.22 (CH 2 -3 þ CH 2 -5 piperazine), 52.88 (CH 2 -2 þ CH 2 -6 piperazine), 57.74 (CH 2 -OH), 59.29 (CH 2 -N), 116.09 (o-Ph), 119.82 ( p-Ph), 129.12 (m-Ph), 151.19 (i-Ph). 2d: 88% yield; R f 0.36 (10% methanol/DCM); colourless oil (lit.…”

“…The solvent was removed in vacuo. The product was purified by flash chromatography on silica gel by using a mobile phase with a gradient of polarity from DCM to 10% acetone in DCM: 61% ethyl 3-(4-phenylpiperazin-1-yl)propanoate[57]; colourless oil; R f 0.38 (10% acetone/DCM); 1 H NMR 1.258 (t, 3H, J 7.1, CH 3 ester), 2.532 (t, 2H, J 7.4, CH 2 -COOEt), 2.621 (t, 4H, J 5.1, CH 2 -3 þ CH 2 -5 piperazine), 2.752 (t, 2H, J 7.4, CH 2 -N), 3.181 (t, 4H, J 5.1, CH 2 -2 þ CH 2 -6 piperazine), 4.146 (t, 2H, J 5.4, CH 2 ester), 6.846 (tt, 1H, J 7.73, 0.9, p-Ph), 6.917 (dd, 2H, J 8.7, 0.9, o-Ph), 7.253 (dd, 2H, J 8.7, 7.3, m-Ph);13 C NMR 14.23 (CH 3 ester), 32.32 (CH 2 -COOEt), 49.06 (CH 2 -2 þ CH 2 -6 piperazine), 52.91 (CH 2 -3 þ CH 2 -5 piperazine), 53.54 (CH 2 -N), 60.41 (CH 2 ester), 116.01 (o-Ph), 119.68 ( p-Ph), 129.06 (m-Ph), 151.22 (i-Ph), 172.41 (C¼O).…”

“…open sci. 6: 181840 ), 4.069 (ddd, 1H, J 11.0, 3.9, 0.9, 1 2 CH 2 -1), 6.979 (dd, 1H, J 8.2, 0.9, CH-9), 7.114 (d, 1H, J 8.2, CH-10), 7.250 (d, 1H, J 0.9, CH-7);13 C NMR 20.45 (CH 2 -6), 21.52 (CH 3 ), 22.15 (CH 2 -5), 28.37 (CH 2 -4), 42.68 (CH 2 -1), 50.20 (CH 2 -2), 53.52 (CH 2 -2 0 ), 58.58 (CH 2 -3 0 ), 59.11 (CH-3a), 107.87 (C q -6a), 108.79 (CH-10), 118.34 (CH-7), 122.52 (CH-9), 128.20 (C q -6b), 128.72 (C q -8), 134.81 (C q -3a 1 ), 135.76 (C q -10a).…”

Bifunctional Bisamphiphilic Transmembrane Building Blocks for Artificial ­Signal Transduction

“…Replacement of this commercially available steroid by a cholenic acid template requires three additional steps but, nevertheless, was realized, because of its perfectly flat overall topology with an equatorial placement of its secondary hydroxy group (Figure 1). 4 The overall strategy is as follows: each steroid is first elongated at its carboxy terminus (C1) to a propargyl ester or less reactive amide derivative, then adorned at its O-terminus (C3¢) with an appropriate functional head group, either for primary messenger recognition, or for second messenger generation. In the key step, two of these lipids are connected by alkyne coupling, before in the final steps, all protecting groups are cleaved off.…”

“…J H,H = 2.5 Hz, 1 H), 3.42-3.58 (m, 1 H), 4.64 (d,4 J H,H = 2.5 Hz, 2 H), 5.32 (d,3 J H,H = 5 3. Hz, 1 H).13 C NMR (CDCl 3 ): d = 11.9, 18.3, 19.4, 21.1, 24.2, 28.1, 30.8, 31.0, 31.6, 31.9, 31.9, 35.3, 36.5, 37.3, 39.8, 42.3, 42.4, 50.1, 51.7, 55.8, 56.7, 71.7, 74.7, 77.8, 121.6, 140.8, 173.4.…”