7alpha-Hydroxy-DHEA → HCID 56620856, compound

HRID 2393210Notes

Reaction equation

HRID 2393210 reaction equation
O([C@:3]12[CH2:20][C@@H:19]([OH:21])[CH2:18][CH2:17][C@:16]1([CH3:22])[C@@H:15]1[C@H:6]([C@H:7]3[C@@:11]([CH2:13][CH2:14]1)([CH3:12])[C:10](=[O:23])[CH2:9][CH2:8]3)[CH:5]=[CH:4]2)O.O[C@H:25]1CC[C@@]2(C)C(=C[C@@H](O)[C@@H]3[C@@H]2CC[C@@]2(C)[C@H]3CCC2=O)[CH2:26]1>>[C:25]([C@@H:18]1[CH2:17][C@@:16]2([CH3:22])[C:3](=[CH:4][CH2:5][C@@H:6]3[C@@H:15]2[CH2:14][CH2:13][C@@:11]2([CH3:12])[C@H:7]3[CH2:8][CH2:9][C:10]2=[O:23])[CH2:20][C@H:19]1[OH:21])#[CH:26]

Participants

3

Reactant 2

HCID 655177alpha-Hydroxy-DHEAHCID 566283895alpha-Hydroperoxy-3beta-hydroxyandrost-6-en-17one

Product 1

HCID 56620856HCID 56620856, compound

Procedure

Reaction of the less hindered 3β-hydroxy-5α-androstan-17-one 1 with t-butyldimethylsilyl chloride yields the 3β-t-butyldimethylsilyl ether 2. Treatment of this first with catechol phosphochloridate followed by displacement with iodine yields 3β-hydroxy-11β-iodo-5α-androstan-17-one 3-dimethyl-t-butylsilyl ether 3. Protection of the C-17 ketone as the 1,3-dioxolane 4 followed by alkenylation using dialkenyl dilithio cyano cuprate, (RCH=CH)2Cu(CN)Li2 yields 11α-alkenyl-3β-hydroxy-5α-androstan-17-one-3-t-butyldimethylsilyl ether 5. Deprotection of the C-17 ketone and 3β alcohol affords 11α-alkenyl 3β-hydroxy-5α-androstan-17-one 6. If 6 has R=2'-tri-n-butylstannyl ethenyl, then lead tetraacetate oxidation affords 11α-alkynyl-3β-hydroxy-5α-androstan-17-one. 6, (R=C≡CH). ##STR58##

Sources & evidence

ORD record
ord-a4deed6062ac494eb4612923b7b1a146
Source dataset
uspto-grants-1998_09
Patent number
US05804576

Reaction notes

Loading…