
%0 Journal Article
%A Collins, DJ 
%A Sjovall, J 
%T The structure and function of oestrogens. IV. Synthesis of 17&#945;-ethynyloestradiol specifically polydeuterated in ring C
%J Australian Journal of Chemistry
%D 1983/02/01
%V 36
%N 2
%P 339-360
%K 
%R https://doi.org/10.1071/CH9830339
%U https://www.publish.csiro.au/paper/CH9830339 
%X Epoxidation of 17,17-ethylenedioxy-3-methoxyoestra-1,3,5(10),9(11)-tetraene( 5) by a two-phase procedure gave the labile 9&#945;,11&#945;-epoxide (11), treatment of which with lithium perchlorate in benzene gave 17,17-ethylenedioxy-3-methoxy-97#946;-oestra-1,3,5(10)-trien-11-one (7). Deuteration of this by prolonged treatment with the monosodium salt of (O,O'-2H2)hydroquinone in dry (O-2H)methanol gave mainly the 98,12,12-trideutero ketone (24) (92% 2H3). Reduction of this with lithium aluminium deuteride to a mixture of the 11-epimeric alcohols (27a) followed by dehydration gave 17,17-ethylenedioxy- 3-methoxy(l1,12,12-2H3)oestra-1,3,5(10),9(11)-tetraene (26) which upon reduction with lithium/ammonia gave 17,17-ethylenedioxy-3-methoxy(11&#950;,12,12-2H3)oestra-1,3,5(10)-triene (25). Hydrolysis and demethylation of (25) followed by treatment with potassium acetylide in liquid ammonia yielded 3,17-dihydroxy-19-nor-17a-(11&#950;, 12, 12-2H3)pregna-1 ,3,5(10)-trien-20-yne (29) (2H4, 9.2; 2H3, 84.1; 2H3, 3.1; 2H1, 2.2; 2H0, 1.3%). Reduction of the trideutero 9(11)-ene (26) with hexadeuterodiborane followed by treatment with alkaline hydrogen peroxide afforded 17,17-ethylenedioxy-3-methoxy(9&#945;,11&#946;,12,12-2H4)oestra- 1,3,5(10)-trien-11&#945;-ol (30a). Reduction of the corresponding tosylate (30b) with lithium aluminium deuteride, then hydrolysis, demethylation and ethynylation gave 3,17-dihydroxy-19-nor-17&#945;- (9,l 1,11,12,12-2H5)pregna-1,3,5(10)-trien-20-yne (35) (2H5, 84.5; 2H4, 8.5; 2H3, 4.4; 2H2, 0.9; 2H1, 0.8; 2H0, 0.9%). 
