Reagents for photoaffinity labeling of estrogen binding proteins. Synthesis of some azide and diazo derivatives of estradiol, estrone, and hexestrol

Abstract

Fourteen estrogen derivatives bearing a photosensitive functional group have been synthesized for use as photoaffinity labels for estrogen binding proteins: diazoacetate derivatives of 173-estradiol and estrone, 16-diazoestrone, and 3-diazo-2-ketopropyl ether and ortho azide derivatives of estradiol, estrone, and hexestrol. All of these compounds are reasonably stable and easily purifiable. Attempts to introduce a diazo function at B-ring positions 6 and 7 of the estrogens have been unsuccessful: the 6-diazo derivative is thermally labile and the 6keto-7-diazo derivative fails to form. This is presumably due to the hindrance at position 7, as the corresponding position (2) in 7-hydroxy-l-tetralone is easily functionalized.

Oxidation of organic molecules in homogeneous aqueous solution catalyzed by hybrid biocatalysts (based on the Trojan Horse strategy)

“…8 3-O-Carboxymethylestrone was first prepared following the method described by Katzenellenbogen, 15 and the ketone function of estrone was then selectively reduced by 5 equiv of NaBH 4 (Scheme 1). The carboxy function of 3-O-carboxymethylestradiol was activated by 1.2 equiv of N-hydroxysuccinimide (NHS) in the presence of 1.2 equiv of carbodiimide in anhydrous THF at 0°C.…”

“…The solid was dissolved in a minimum amount of water and applied to a Na + -acti- 3-O-Carboxymethyloestrone was synthesized from estrone following the method described by Katzenellenbogen. 15 The ketone function (634 mg, 1.93 mmol, 1 equiv) was then selectively reduced by 8 equiv of NaBH 4 (600 mg, 15.8 mmol) in methanol at 0°C to obtain 3-O-carboxymethylestradiol (574 mg, yield = 90%). The carboxylic acid function was activated by N-hydroxysuccinimide (9.7 equiv) and dicyclohexylcarbodiimide (DCC) (9.7 equiv) in freshly distilled THF at 0°C.…”

Trace analysis of contraceptive drug levonorgestrel in wastewater samples by a newly developed indirect competitive enzyme-linked immunosorbent assay (ELISA) coupled with solid phase extraction

“…Second step: 1.5 g of LNG-OH (II) produced was dissolved in 10 mL tetrahydrofuran (THF). 600 mg NaH and 1.67 mL ethyl bromoacetate were added, and the reaction mixture was refluxed at 70 • C for 24 h under nitrogen gas [20]. The solvent was removed under reduced pressure and the resulting residue was also confirmed by TLC.…”

Chemical Cross-Linking in Biology

“…A biologically active fluorescent photoaffinity analog of acetylcholine, bis-(3-azidopyridinium)-1,1O-decane perchlorate, has been synthesized recently by Witzemann & Raftery (92). Photoaffinity analogs of steroid hormones were introduced by Katzenel lenbogen and his colleagues (40,41). A number of photosensitive deriva tives, 3-diazo-2-ketopropyl ether, and ortho azide derivatives of estradiol, estrone and hexestrol, were reasonably stable and could be purified easily.…”